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By Ashok K. Sinha

During the course of an in~*estigation into the occurrence of ordered AB3 structures, the following new phases have been found —CrRh3 (AuCu3 type), CrCo3 (MgCd3 type), HfCo4 (Ths Mn23 type), and WPt, MoPh type). The composition of the TiPt3-x phase (TiNi, type) is close to Ti23Pl77. The alloy chenzistry of transition rnetal AB3 structures is rezliewed in the light of electron concentration correlations of hex-agonality recently obtained for quasi-binary alloys. The relatizte colurne contraction in the AB3 structures increases with increasing difference in volume of the conzponents. A family of ordered close-packed layered structures is formed by stacking identical layers of composition AB, in various sequences, such that the coordination is twelvefold throughout and there are no A-A contacts. Previous work' on quasi-binary AB3 alloys has led to the conclusion that the stacking sequence of the AB, structures changes with increasing radius ratio RA/RB from a purely cubic, through different mixtures of hexagonal and cubic stacking to a purely hexagonal stacking. However. for binary AB3 alloys, a correlation between the type of the crystal structure and the position of the components in the various volumns of the periodic table has been noted.2-5 It has been noted6 that this correlation appears to hold even though the radius ratio RA/RB may vary over a considerable range with the location of the components in the three long periods. Another study7" of several quasi-binary systems led to the conclusion that an increase in hexagonality of the stacking is associated with increase in the electron concentration e/a. as defined by the average per atom of the total number of electrons outside the inert gas shells. In apparent conflict with this conclusion, it is known that seven binary alloy structures isotypic with TiNi3 which is 50 pct hexagonal occur at a higher electron concentration (e/n = 8.5) than that (e/a = 8.25) for the 100 pct hexagonal MgCd3 type structure present in seven binary AB3 alloys. Table 111. In the present work, an investigation into the occurrence of binary AB3 structures in transition metal alloys was made, and a survey of binary AB3 structures is presented. EXPERIMENTAL The starting materials were pure metals of 99.9 wt pct purity. The alloys were arc-melted under partial pressure of argon and annealed in sealed silica capsules lined with molybdenum foil under argon at- mosphere. The total weight loss upon melting and subsequent annealing was always less than 1 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. Wherever the constitution permitted. the alloys were given a homogenizing treatment at 1200°C (3 days) prior to annealing. Unless otherwise stated all alloys were annealed at 900°C for 1 week and water-quenched. Sometimes the final annealing treatment was carried out on powders to accelerate the attainment of equilibrium. X-ray powder patterns were taken using a Guinier-de Wolff focusing camera (CuK, radiation) or an asymmetrical focusing camera (Co or CrK, radiation). For lattice parameter determination. internal silicon standards were employed. The intensity calculations were made using a Fortran IV program written by Jeitschko and parthe.9 RESULTS Twenty AB3 and three AB4 alloys were investigated. Table I lists the crystallographic data on some of the intermediate phases encountered in the present work. Table II contains the X-ray data for HfCo, (Th,,Mn,, type). The positional parameter, x. was assumed to be 0.378. the value for Th6Mnn2310 The X-ray pattern of ZrCo, was very similar to that of HfCo, and the previous structure determination of ZrCo, by Kuzma el al." was confirmed. Ordering in the alloy CrCo could be ascertained by the presence of only one weak super lattice line (101). the others being too weak presumably owing to the small difference in the scattering powers of chromium and cobalt. This line was observed in the X-ray pattern of powder from the massive sample annealed at 830°C (7 days) after the powder had been reannealed at 600°C (24 hr). The diffraction pattern of the powder similarly reannealed at 830°C (24 hr) contained only the lines due to a mixture of hcp and fcc Co(Crj solid solutions. Therefore, it appears reasonable to assume that O2 and/or N2 contamination which would be less likely to occur during the 600°C anneal was not responsible for the observed weak reflection. Also. this reflection cannot be identified with any of the strong lines of the neighboring s phase which is present in the Co-Cr system at higher chromium contents. The composition corresponding to the TiNi3 structure observed by Raman et al.12 in the two-phase alloy Ti,zt,, has been established in the present work as being between There was satisfactory agreement for the low-angle lines (up to d = 1.997A) between the observed diffraction pattern of TiCua and that calculated assuming the ZrAu, structure. as recently proposed by Pfeifer-et a1.I3 However. some of the superlattice lines. e.g., at d = 1.937 and 1.919A. predicted by the ZrAu, structure were not actually observed eve? though neighboring lines. at d = 1.947 and 1.986A. of comparable calculated intensity were present. The ZrAu

Jan 1, 1970

By C. E. Birchenall, J. R. Stubbles

ThE equilibrium between lead, lead sulfide (PbS), and atmospheres of H2 and H2S has been determined previously by Jellinek and Deubel,' and SudO.' Blbem and Kroger3,4 used Jellinek's data to calculate the sulfur dissociation pressures of PbS crystals (of

Jan 1, 1960

By N. A. Gokcen, S. Fujishiro

The dissociation pressure of Cr3C2 has been measured in the range of 1908" to 2237°K by means of graphite Knudsen effusion cells. It has been found that Cr3C2 vaporizes according to the following reaction: 1/3 Cr3C2 (s or 1) = 2/3 C (graph.) + Cr (g). The equilibrizcm pressure, P, of Cr (g) is found to be log Ps=- - (21,194/T) + 6.525 over solid Cr3C2 and estimated as log P, = - (19,535/T) + 5.76 over liquid Cr3C2. CARBIDES of chromium are of great importance in alloy steels and cemented carbides. The published data on their therm odynamic properties at high temperatures, however, are meager. The heat capacity and change in entropy of Cr3C2 were determined calorimetrically by Kelley and Moore1 in the range of approximately 50" to 300°K, and by Oriani and Murphy2 from 297" to 1188°K. The standard entropy of Cr3C2at 298.15°K, obtained by Kelley.7 was later confirmed by DeSorbo.4 Equilibrium in the reaction was investigated by Boericke.5 A recent tabular summary

Jan 1, 1962

By S. R. Goodman, Hsun Hu

The rolling texture of an 18-8 stainless steel (Type 304L or 304) has been found to change gradu -allv from the (110)[112] brass type to the (123)[412] copper type as the rolling temperature increases from 200° to 800°C. This texture transition is accompanied by a change in the stacking-fault frequencv or probability, similar to those found pre- In a series of previous publications, it was shown that the rolling texture of high-purity silver changes gradually from the brass type to the copper type with increasing temperature of deformati~n. A similar temperature dependence of rolling texture transition was found in electrolytic copper3—by lowering the temperature of deformation, the normally observed rolling texture of copper changed gradually viously in nonferrous fcc metals—the stacking-fault frequency decreases rapidly with the formation of the copper type texture. These results strongly indicate that the temperature dependence of copper type == brass type texture transition and its correlation with stacking-fault frequency is a general phenomenon in fcc lattices. to the brass type.* In both of these metals, the

Jan 1, 1964

By J. V. Emmons

IT has long been known that the outside skin of tool steel frequently exhibits properties widely different from the interior of the mass. Within the last few years it has been generally recognized that many of these properties were clue to surface decarbonization. The origin and effects of this altering of the composition have been but little studied. C. M. Johnson' arrives at the conclusion that, in annealing, "the most active agent in surface decarbonization is the rust or scale (present on the surface), which is actually reduced to metal at the expense of the carbon in the steel to which it adheres." W. H. Hatfield in his admirable paper, The Chemical Physics Involved in the Decarburization of Iron-Carbon Alloys,' has given us the most tenable theory of the removal of carbon from iron. While Mr. Hatfield's work has been principally clone in connection with the annealing of white cast iron to produce malleable castings, it is frequently applicable to the decarbonization of tool steel. The following equations which he proposed have been fully borne out by the author's experiments: 2Fe3C + 2CO2 = 3Fe2 + 4C0 2C0 + 02 = 2C02 Continuous 2C02 + 2Fe3C = 3Fe2 + 4C0 It is the purpose of the author to show, in a quantitative manner, the effect of various treatments in eliminating the carbon in tool steel. Some of the phenomena of the decarbonized surface will also be described, as well as the practical problems they present to. the manufacturer and user of tool-steel products.

Jan 9, 1914

By J. R. Stack, H. H. Alexander

Prior to 1915, numerous attempts were made to treat tin concentrates in the United States, but for various reasons they were unsuccessful. Tin ore is said to have been found in nearly every state, but none of the deposits has proved to be of commercial importance. An annual output of a few hundred tons in Alaska is the only domestic production; hence any considerable production of tin in the United States must be from foreign ores. The most promising occurrence of tin was found in the Black Hills, S. Dak.; in the early development stage, it was called the Cornwall of America. Associated with the tin is tungsten The story is told that an exceedingly fine specimen of the Black Hills ore was sent to England to encourage stock promotion; the desired effect was produced until a skeptic chipped off a small piece, which the analysis showed to be wolframite. First Attempts at Smelting One of the first promising attempts at tin smelting in the United States was made by R. T. White at Bayonne, N. J., in 1903. Mr. White, after spending some time in England studying the methods of tin smelting, organized a company called the International Tin Co., and erected a plant to treat tin concentrates from the Straits of Malacca. About the time the plant was completed, the English Government placed an export duty of 40 per cent. ad valorem on tin concentrates exported to other than British smelters, which duty made it impossible to operate this plant so the enterprise was abandoned, As this export duty is still effective, the only source of tin-ore supply for the United States is the Bolivian concentrates. Bolivian Tin Concentrates Unlike the alluvial placer deposits, nearly all Bolivian tin occurs in lode deposits and some of the highest grade ores contain only a small

Jan 1, 1924

By W. O. Philbrook, C. W. McCoy

The reduction of chromous oxide from lime silica alumina slags by carbon-saturated iron behaves as a first-order process having a rate of 0.001 grams Cr min 1 cm 2 (pct Cr ) , substantially independent of slag composition and temperature over an important range for iron smelting. The equilibrium ratio (pct Cr)/[pct Crl is below 0.04 for slags having lime-silica ratios above 0.6. MANY studies have been conducted on chromium in slag-metal systems under oxidized conditions. The Purpose of these investigations has been twofold; namely, (1) to determine those conditions which lead to greater chromium recovery in electric-furnace and open-hearth practice, and (2) to determine the nature of oxide inclusions and de-

Jan 1, 1959

Alabama.1 Arizona 1 Arkansas 2 California 2 Colorado 7 Connecticut 8 Delaware 9 District of Columbia 9 Florida 10 Georgia 11 Idaho 11 Illinois 11 Indiana 13 Iowa 14 Kansas 14 Kentucky 14 Louisiana 15 Maine 16 Maryland 16

Jan 1, 1952

HUDSON MAXIM, Brooklyn, N. Y.-Immediately after the creation of the Naval Consulting Board, Admiral Strauss, Chief of the Bureau of Ordnance of the Navy, told members of the Board that the most important problem for the scientists to solve was erosion in large guns. The Navy, for years, had been working on the problem with marked suceess, but there was much yet remaining to be accomplished. As Chairman of the Committee on Ordnance and Explosives of the Naval Consulting Board, I communicated with several experts in the manufacture of steel, principal among whom was Prof. Howe. He generously agreed to help in every way possible, and the work that he has done and the time that he has spent upon it can he appreciated only by reading his paper. Prof. Howe asked for some rings. from a, certain 14-in. gun which Admiral Strauss had mentioned in particular, and in which, he had informed us, at each shot the bore of the gun, was enlarged about 0.001 in.,' and that after a relatively small number of rounds it was considerably eroded. It has puzzled scientists for a long time to account for the peculiar erosive effect produced by the powder gases in a gun, arid: what Prof. Howe has done in his paper is worthy of Sherlock Holmes. He is a veritable Sherlock Holmes of science.

Jan 4, 1918

By Philip McKenna

WHEN a new material becomes available to industry, it is useful to describe its properties as a guide to its most effective application; and when the new material may be produced in compositions having a series of graded properties, tests to select the combination of properties best adapted for various uses are helpful. The class of materials to be con-sidered in this paper are hard tool materials produced by processes of powder metallurgy from hard carbide constituents and various matrices of iron, nickel or cobalt, or alloys of them with tungsten, or tungsten and carbon. The customary use of carbide hard alloys is for metal-cutting tools; although wire-drawing dies, lathe centers, follow rests, grinding rests, burnishers, rolls, extrusion dies, measuring gauges and micrometers, and a number of other tools are also made with these hard alloys as the essen-tial wear-resisting parts. The properties and tests to be considered are those affecting these uses. In the development of tool, materials since the industrial revolution we have had carbon tool steels, Mushet steel, high-speed steels, stellites, and now cemented carbide compositions. For an understanding of the latter category of materials their properties and uses relative to the older and more familiar tool materials will be considered.

Jan 1, 1938

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By D. F. Kelsall

The hydraulic cyclone, in simple or modified form, is finding increasing application in metallurgical processing. In this article, the author considers several aspects of conventional applications, less conventional applications and some potential uses of modified cyclones. Information concerning the mechanism of separation within a cyclone and the effect of the major variables is summarized. During the past twenty years, and especially in the last decade, hydraulic cyclones have found increasing application in metallurgical processing as classifiers and, under special circumstances, as thickeners. To a more limited extent cyclones have been used to extend heavy, or dense, medium separation into the finer size ranges, and several attempts have been made to separate dispersions of immiscible liquids with a view to use in the field of liquid-liquid extraction. A large proportion of published work reports incomplete data, applicable only to particular systems. The more useful papers, covering data of relatively wide significance, have been reviewed recently in considerable detail1,2 and no attempt will be made to cover the same material in the present paper. However, before considering several aspects of conventional application, less conventional applications and some potential uses of modified cyclones, it is considered pertinent to summarize information relating to the mechanism of separation within a cyclone and the effect of the major variables. LIQUID FLOW PATTERNS At any point within a simple cyclone the liquid velocity may be resolved into three components, i.e., the tangential or swirling velocity (v), the vertical velocity (w), and the radial velocity (u). The relative values of these components at selected positions within a typical cyclone have been established for water. 3 The extent to which similar flow patterns exist in systems of considerably higher viscosity, or apparent viscosity, operating under conditions of reasonable pressure drop, is not known with precision, but indirect evidence indicates that up to approximately five centipoise there is no marked change. Beneath the bottom of the vortex finder, envelopes of constant tangential velocity are cylinders coaxial with the cyclone, and, at any horizontal level, starting from near the conical wall, this component of velocity increases with decrease in radius (r) according to the relationship vrn = constant (where 0 < n < 1) This holds to regions near the center of the cyclone where v reaches a maximum value at a radius somewhat smaller than that of the inside wall of the vortex finder. At this point, the centrifugal acceleration, v2/r reaches a maximum value. As the radius is further decreased the tangential velocity decreases so that v = r. Above the bottom of the vortex finder there is a tendency for the first relationship to persist to near the outside wall of the vortex finder, until v reaches a maximum and then decreases rapidly as the wall is approached. The two most significant features of the vertical velocity distribution are an approximately conical Table I. List of Symbols v = liquid tangential velocity at any point in the cyclone w = liquid vertical velocity at any point in the cyclone u = liquid radial velocity at any point in the cyclone r = radius from cyclone axis to any point ? = half angle of conical portion of the cyclone ?= fluid viscosity d = particle diameter s = liquid specific gravity p = particle specific gravity d50 = the particle diameter which distributes 5090 to overflow, 50% to underflow e = overflow diameter, in. b = feed diameter, in. G = gpm of feed slurry

Jan 1, 1963

By R. W. Waterfill

MANY existing ore deposits of valuable metals have been worked out in their upper surface levels and the continued productivity of these mines is dependent on their extension to greater depths in the earth. The maximum depths at present reached are about 6000 to 8000 ft. below the surface, with no evidence of an impoverished ore vein. These mines are widely distributed; some of the best known are in South Africa, Brazil, India and in the western sections of the United States. Among the factors which increase the difficulty of working these mines at increasing depths are hoisting, rock pressure and temperature. The manner and effectiveness with which these problems are met will, no doubt, determine in a large measure the ultimate depths to which any mine can be profitably worked. The most critical of these three factors at present is the increase in temperature with depth. The high temperature and humidity in many of these mines at present is severely detrimental to the health of the workers and greatly hampers their efficiency. Some have almost reached a condition in which the human system cannot survive. The problems involved in the cooling and ventilation of mines have all been ably analyzed and presented in previous articles. For this reason, only a resume of conditions affecting the cooling and conditioning of deep and hot mines will be given in this paper before attention is directed to possible methods of improving atmospheric conditions in the working levels.

Jan 1, 1929

By Volker Weiss, George Sachs, AE. P. Klier

PHYSICAL chemistry contributes to the understanding and efficient operation of hydrometal-lurgical processes in many ways, among them by providing quantitative answers to the following questions. 1) Can a given chemical reaction or process be made to operate and. if so, under what conditions? 2) what are the&apos; factors which determine the rate of the reaction and how can this rate be regulated in practice? Thermodynamics attempts to answer the first of these questions and kinetics the second. The answer

Jan 1, 1958

By B. M. Larsen

ATTEMPTING to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic " and " macroscopic," depending on whether the variations in concentration of solutes? or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also underly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all segregation effects. UNDERCOOLING AND NUCLEI FORMATION It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus tempera¬ture. In practical terms this means that the nuclei number increases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. TEMPERATURE GRADIENTS AND HEAT DISSIPATION DURING FREEZING Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period: Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1944

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Experimental results are given for the rate of reduction of silica from silicate melts by paphite-saturated iron in the presence of carbon monoxide. It is shown that, when gas bubbles are present at the slag-metal interface, the interfacial chemical reaction is the rate-controlling process in the transfer of silicon from slag to metal. From the silicon-concentration profiles in the metal sample, the diffusivity of silicon in paphite-saturated iron is found to be (5.4 * 0.4) x 10 sq cm per sec at 1600°C. Some consideration is given to the transport of oxygen from the slug-metal interface to the walls of the gvaphite metal container as becoming the rate-controlling process in the absence of gas bubbles at the slag-metal interface. ATTEMPTS were made by Fulton and chipman1 to investigate the kinetics of reduction of silica from calcium alumino-silicate melts by graphite-saturated iron in an atmosphere of carbon monoxide. In these experiments with 400 to 500 g of metal and slag, both phases were stirred in such a manner that the interface was essentially undisturbed. Initially, the graphite-saturated iron contained about 15 pct Si and, after about 8 or 10 hr of reaction time at 1600°C, the silicon content of the metal in- creased by about 0.2 pct. In a written discussion on this paper of Fulton and Chipman, schuhmann2 pointed out the possibility that this observed slowness of the reduction of silica could be due to the transport of oxygen across the liquid metal boundary layer at the slag-metal interface. Although this explanation of Schuhmann is quite feasible for the experimental data of Fulton and Chipman on silica reduction, such a reasoning should not be extended to other rate data on slag-metal reactions unless sufficient evidence is available satisfying the boundary conditions for such a transport process. The hydrodynamics of stirred liquids are very complex and even for a simple method of stirring there is no exact mathematical solution which will predict the mass transfer coefficient accurately. The best available solution of this problem is that given by Lewis&apos; and later modified by mayers~ for a two-liquid system where liquids are stirred by counter-rotating stirrer blades without disturbing the interface. In such a system the mass transfer coefficient is estimated from an empirical relationship using the data on viscosity and density of the two liquids, rate of revolution, the length of stirrer blades, and the diffusivity of the element which is transferred from one phase to the other. It was found in these investigations&apos; that the estimated and observed mass transfer coefficients, in systems containing two immiscible aqueous solutions, agreed within *40 pct. Although this is not considered to be an unreasonable error for the study of industrial processes, uncertainties of this magnitude cannot be tolerated in any theoretical study of reaction kinetics. In view of the complexity of the

Jan 1, 1963

By H. I. Aaronson, S. Toney

When the component grains of .ferritic hicrystals of an Fe-1.55 pct Si alloy are disoriented through an angle "6 " about a conzmon [ll0] axis, the tendency for preferential growth of austenite crystals along the grain boundary during transformation at elevated temperatures is small when 11 deg, but increases rapidly at larger angles. This type of orientation-dependence indicates that grain boundary diffdsion promotes preferential growth along large-angle boundaries. Morphological differences between austenite crystals formed at small-angle [1101 and [loo] boundaries suggest that precipitate morphology can be dependent on the dislocation structure of the boundary. ThE morphology of precipitate crystals nucleated at a grain boundary can be significantly affected by the structure of the boundary.&apos; The limited amount of experimental evidence available in the literature indicates that the morphological effects of boundaries made up of arrays of dislocations, such as subbound-aries and small-angle grain boundaries, are different from those of boundaries having essentially disordered structures, i.e., large-angle grain boundaries. On the basis of indirect evidence, it has been concluded that large-angle grain boundaries give rise to the formation of grain boundary allotriomorphs (crystals which nucleate at grain boundaries, and grow preferentially and more or less smoothly along them)2 in the proeutectoid ferrite and the proeutec-toid cementite reactions in plain-carbon steels, and apparently also in many non-ferrous alloys.&apos; At small-angle grain boundaries in a plain carbon steel, on the other hand, ferrite crystals were found to take the form of primary side plates. Similarly, Guinie, loys. Primary sideplates formed at a subboundary with a constant orientation tend to be parallel to only one, or occasionally two matrix habit planes, and a marked change in the orientation of the boundary is accompanied by a change in the habit plane. Previous studies on the morphological effects of grain boundary structure were performed on poly-crystalline aggregates. Information on the disorien-tation of the pairs of grains forming the boundaries at which the various morphologies appeared in these specimens was largely either qualitative or semi-quantitative. Precipitate morphologies accordingly could not be accurately and systematically correlated with grain boundary structure, and thus theories which have been proposed for the various morphological effects could not be satisfactorily tested. This investigation was undertaken in an attempt to remedy these deficiencies by studying the morphological effects of grain boundary structure with a method in which the boundaries are formed by matrix grains whose disorientations are known and controlled with reasonable accuracy. EXPERIMENTAL PROCEDURE The crystallographic requirements of this study were fulfilled by means of oriented bicrystals of silicon-iron. Disorientation of the component ferrite crystals was carried out about common, major crystallographic axes through angles ranging from 1/2 to 44 deg. The silicon content was low enough SO that the bicrystals could be partially transformed to austenite by heating to elevated temperatures. The silicon-iron used had the following initial composition: 1.55 pct Si, 0.04 pct C, 0.0031 pct N, 0.17 pct Mn, 0.020 pct S, and 0.002 pct P. The alloy was obtained in the form of 0.036-in. sheet. The procedures employed to prepare seed crystals in strips of this sheet, to reorient the seeds, and to grow them into bicrystals are essentially those described by Dunn and Nonken and aynes." The characteristics of the bicrystals are given in Table I. The "bicrystal type" indicates the crystallographic plane parallel to the broad faces of the strip in both grains and the crystallographic direction which was parallel to the long edges of the strip in both grains prior to disorientation. The angular disorientation of the grains, 8, which was performed about the direction normal to the plane of the broad faces of the strip, was measured between the [ 00l] directions. Orientation of the grain boundary, , was taken as the angle between the plane of the grain boundary and a plane containing the axis of disorienta-

Jan 1, 1962

By R. Buehl

ALTHOUGH the main features of the transformations occurring in 18-8 have been published already,1-4 certain conclusions merit questioning and discussion. The questions may be summarized as follows: PERCENT REDUCTION BY COLD ROLLING FIG. 1.-VARIATION OF FERRITIC INDUCTION AND PERCENTAGE OF FERRITE WITH COLD REDUCTION. Composition of Alloy: C, 0.08; Mn, 0.40; Si, 0.24; P, 0.014; Cr, 18.13; Ni, 8.94. 1. If ferrite is formed by cold-working austenite, what happens to the carbon with which the ferrite and austenite are both pre-sumably supersaturated? 2. What is the nature of the alpha-ferrite formed at grain boundaries by chromium-carbide precipitation at these boundaries?

Jan 1, 1939

By D. F. Kaufman, H. R. Spedden, A. M. Gaudin

MANY studies of comminution have been made to ascertain the size distribution of the product and to evaluate the work of comminution in the light of the size distributions of the feed and product. Up to now, these studies have been essentially statistical in character, that is, a certain lot of feed was subjected to comminution in some specified way, and the aggregate product was fractionated into sizes, thereby losing all knowledge of individual relationship of feed to product pieces. Radioactive tracers offer a means to do something in this respect which could not be done before, namely, to follow the rupturing of some particular piece in its normal environment of other pieces. That is, it permits going beyond the usual statistical limitations of size distribution studies to what may be termed a personalized or individualized study. The purpose of this paper is to present some preliminary experiments conducted with this tool. The method employed was to mark radioactively some constituent of a feed. It is possible, of course, to consider the preparation of two lots of material of which one is radioactive and the other is not, and to blend the two ahead of the comminuting step; but to do so is open to the objection that the two preparations may not be identical. Therefore a technique has been chosen that removes this objection by merely taking out a size fraction of a comminution feed, rendering that fraction radioactive by exposure to a neutron flux, and then by returning it to Table I. Size Distribution of Offspring Albite Particles Originally 28/35 Mesh and in Admixture with Other Sizes After Grinding 2 min in a Steel Ball Mill Specific Activity &apos; Cumu- Corrected Distrl- latlve Size for Back- butlon In Distri- Fractlon ground, Weight, Product, button, of Product, cpm/gm g Pctb Pct Mesh (A). (W) (P) (ZP) + 28 0 56.0 0 100.1 28/35 62.6 54.0 24.8 75.3 35/48 62.8 59.4 27.7 47.6 48/65 41.1 53.0 16.2 31.4 65/100 29.6 45.7 10.2 21.2 100/150 23.7 37.0 6.6 14.6 150/200 23.3 25.1 4.4 10.2 200/270 20.1 19.0 2.9 7.3 270/400 17.8 21.2 2.9 4.4 -400 22.9 25.2 4.4 — 100.1 a These activity determinations were made in rapid succession in the order given. The specific activity (Ao) of the active 28/35 mesh fraction of the feed was measured at the beginning, after the measurement on the 65/100 mesh size fraction of the product, and; The end. The decay-corrected activities at those times were 246.7, 241.0. and 236.9 cpm per gm. The weight (W0) of the active 28/35 mesh fraction in the feed was 55.0. b Example of calculation for P in the 65/100 mesh oroduct frac- A W tion; A = 29.6, W = 45.7, Ao = 242.7, Wo = 55.0: P = — x — Ao Wo = 0.102 = 10.2 pet. the remainder of the charge for the comminution experiment. A relatively simple procedure was developed by which albite, containing sodium, was activated in the M.I.T. cyclotron. The cyclotron makes highspeed deuterons which impinge on a beryllium target, thereby producing a concentrated neutron flux. The mineral was exposed to this flux for 2 hr. This treatment changed enough of the sodium to sodium 24 (14.8 hr half-life, 1.4 mev ß) as to make detection and measurement easy. The nuclear reactions taking place were: 11Na23 (n,?) 11Na24 (irradiation) 11Na24 ß,?,? 12Mg24 (decay) The detailed technique of the experimentation was as follows: 40 kg of hand-sorted, lump albite were crushed to pass 10 mesh. After careful mixing of the lot, a screen analysis was made. The whole lot of material was fractionated on standard Tyler screens from 14 down to 200 mesh. Samples for experiments were compounded from these fractions in accordance with the screen analysis. When it was desired to make an experiment in which, for example, the 28/35 mesh size fraction was to be studied, the blend of size fractions was made as indicated above, except that the 28/35 mesh size fraction was added only after irradiation in the cyclotron. The blended charge containing the activated albite was ground for 2 min in a laboratory ball mill with a steel ball charge of controlled size distribution. The ground product was carefully sized on a set of Tyler screens in a Ro-tap. Each size was analyzed for radioactivity by the use of an end-window Geiger-Mueller counter and standard scaling circuit. This analysis was carried out in detail as follows: a 20-g sample was placed in a Petri dish, packed carefully to obtain reproducible geometric distribution with reference to the Geiger-Mueller tube, and the activity was counted for a 2-min period. Several determinations of the activity of the active size fraction in the feed were made at various times to establish the decay in activity with time. Linear interpolation was used to evaluate the activity that the active size fraction in the feed would have had at any given instant. The ratio of the observed activity in a size fraction of the product to the activity that the active size fraction in the feed would have had at the same time gives the fraction in the product size that came from the irradiated size in the feed. The general formula for finding the distribution, P, of a specific individual size fraction in the feed

Jan 1, 1952

By C. A. Heiland

THE investigations described were made on a portion of Clear Creek basin near Golden, Colo. (A portion of the area under survey is shown in Fig. 1. The photograph was taken in the vicinity of station No. 2 of Line II.) Three principal purposes were in the minds of the investigators: 1. To repeat with modern, more sensitive and more reliable instruments magnetometric placer investigations previously made. 2. To disprove the recently advanced theory that deposits of the glacial period have no pronounced magnetic effects. 3. To develop in detail the theory of the magnetic effects produced by placer deposits. Six years ago, the first magnetic observations were published, which proved that it is possible to locate gold-bearing channels with relatively crude instruments.1 Two years ago, K. C. Laylander published results obtained with similar instruments.2 The measurements of the latter were discussed by the senior author of this paper.3 At that time, however, the material available for such a discussion was somewhat scarce and not made with the most modern magnetic instruments, although very brilliant results were obtained. Therefore, the senior author felt that magnetic investigations should be made on very clear geologic conditions with the most modern instruments.

Jan 1, 1928