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By W. J. Feuerstein

STRUCTURAL imperfections in crystals, in recent years, have received the attention of metallurgists concerned with single-crystal properties. Certain etching solutions cause local variations in the rate of etching at dislocations.' Dislocations are expected to be preferred segregation sites for impurities' and Dash" has shown that precipitation of copper occurs preferentially at edge-type dislocations in silicon. Diffusion rates along dislocations are probably higher than rates through more perfect crystalline regions.' These and other phenomena which may be influenced by dislocations may be studied by revealing dislocations as etch pits. This study was undertaken to develop an etch solution for silicon crystals to reveal low-angle grain boundaries associated with dislocation arrays and also etch pits with good contour definition. Additional etches have been reported by Dash," Vogel and Lovell.T rystals were sectioned on crystal lographic planes at various angles from the growth direction for microscopic examination of the etch pits. Experimental Crystals of 75-100 g mass and 3 cm diam were oriented and cut on crystallographic planes. Crystals were grown by Czochralski technique from a quartz crucible. Lapped wafers were chemically polished in a modified CP-4 etch for 1 min (bromine was deleted from the etch solution). The polished wafer was then etched* at room temperature for 5 min. The use of larger amounts of H2O and/or CH2COOH slows the reaction. The Cu(NO3),.3H2O was added to increase the reaction rate and give more definition to the etch pits developed. Some pertinent features concerning the attack of this etch on silicon can be summarized as follows:

Jan 1, 1959

By F. W. Gordon

THE Whitwell firebrick hot-blast stove, for furnace use, may be seen in its three, main stages of development in the accompanying drawings. Fig. 1 is the stove of 1869, the, year in which it was thoroughly tested at the Consett furnaces, England; Fig. 2, the stove of 1876 and 1877, in which it was intended to reduce the-cost by increasing the height; Fig. 3, the stove of 1880. Many modifications were made from time to time, generally in the direction of improvement, but the drawings illustrate the main features of progress. In the stove of 1869 the plan was to introduce the gas at A, and pass it up and down. between each alternate wall, the air in the reverse direction, passing in at B. The friction in this stove was so great, owing to the. restricted area of the passages and the many reversals of the gaseous current, that it was deemed imprudent to build the stoves higher than 28' 6'". Another reason was that the great importance of cleaning was carefully kept in view, and it was very difficult to operate any hand scraper even to this depth. For these reasons the 22' X 28 1/2' stove held the field for several years. A slight change made from this was to the 18' X 40' stove, where the height was increased, but the number of walls diminished. In this stove the friction was somewhat reduced, but so was the heating surface, and although it cost a little less it was not any better. The next important change, seen in Fig. 2, was by increasing the height to 60 feet and keeping the full number of walls in the stove. The heating surface and mass were much increased in proportion to the cost, and the friction decreased by alternating over and under two or more walls, instead of one, as formerly. This stove gave admirable satisfaction, but; although the proper doors were provided, it was very difficult to clean, owing to the long distance the scrapers had to traverse. Stove No. 3 is a modification of No. 2. The great question was how to decrease the cost without impairing in any yaw the

Jan 1, 1881

By F. W. Gordon

The Whitwell firebrick hot-blast stove, for furnace use, may be seen in its three main stages of development in the accompnying drawings. Fig. 1 is the stove of 1869, the year in which it was thoroughly tested at the Consett furnaces, England; Fig. 2, the stove of 1876 and 1877, in which it was intended to reduce the cost by increasing the height; Fig. 3, the stove of 1880. Many modifications were made from time to time, generally in the direction of improvement, but the drawings illustrake the main features of progress. In the stove of 1869 the plan was to introduce the gas at A, and pass it up and down between each alternate wall, the air in the reverse direction, passing in at B. The friction in this stove was so great, owing to the restricted area of the passages and the many revervals of the gaseous current, that it was deemed imprudent to build the stoves higher than 28' 6". Another reason mas that the great importance of cleaning was carefully kept in view, and it was very difficult to operate any hand scraper even to this depth. For these reasons the 22' X 28½' stove held the field for several yearn. A slight change made from this was to the 18' X 40' stove, where the height was increased, but the dumber of walls diminished. In this stove the friction was somewhat reduced, but so was the heating surface, and although it cost a little lea it was not any better. The next important change, seen in Fig. 2, was by increasing the height to GO feet and keeping the full number of walls in the stove. The heating surface and mass were much increased in proportion to the cost, and the friction decremed by alterllating over and under two or more walls, instead of one, as formerly. This stove gave admirable satisfactiou, but, although the proper doors were provided, it was very difticult to clean, owing to the long (distance the scrapers lid to traverse. Stove No. 3 is a modification of No. 2. The great question was how to decrease the cost mithotlt impairing in any yaw the

Jan 1, 1881

By Keith E. Robinson, Brian Stimpson

INTRODUCTION In inclined sedimentary strata slope failure may occur by sliding along bedding and along a discontinuity or weak zone, as illustrated in Fig. 1. This mode of failure may be called 'bi-linear', as the failure surface is comprised of two linear or approximately linear segments. This type of failure has been suggested for the famous Frank Slide, Alberta, Canada (Cruder and Krahn, 1973) in which an estimated 90 M 5 tons (8.97 x 10 MN) of rock separated from Turtle Mountain and buried the town of Frank. Also, with the increasing depth of open pits and the construction of highways through inclined sedimentary strata this mode of failure is of major concern to the rock slope stability engineer. A computer program for calculating factors of safety for this slope failure mode is provided and includes the ability to vary shear strengths of potential slide surfaces, ground water elevations and wedge geometry. LIMITING EQUILIBRIUM MODEL The simple limiting equilibrium model used in the analysis is shown in Fig. 2. It is assumed that jointing is orthogonal to bed- ding and that the interface between the upper and lower wedges there- fore corresponds to a joint plane or planes. No shear strength is attributed to the interface so that the resultant force, P, from the upper wedge acts normally across the interface. The normal loads

Jan 1, 1983

By Ralph Arnold

WITHIN the past three weeks the price of crude oil in the Mid-Continent field has been cut 50 .per cent. Similar action has been taken, or probably, shortly will be taken, in most of the other fields of this country. This cut is very drastic. Is it justified? Some of the causes advanced for the cut are: that it is in line with the industrial downward readjustment now taking place throughout the country, and that there is an over-production of oil, which can best be slowed down by lowering the price of crude. In part, these two reasons are logically advanced, but such underlying causes as the great production- in Mexico have not been prominently brought forward nor the fact that it would be advantageous at this time to fill up the empty storage of many of the consuming companies at a low 'price. In order to properly comprehend the situation let us compare for a moment the production- of oil in the United' States and that in Mexico. Oil in the United States occurs in numerous often widely separated pools, varying in individual area, but each usually relatively extensive, compared to the area or gathering ground from which it is ultimately derived: It occurs in mod-erately porous reservoir rocks under such conditions of pressure, mobility and availability as to preclude its withdrawal except over a period of years-varying from 1 to at least 40 (average, say 15 years, depending on-the pool). One well will usually drain a limited area-2 to 10 acres-so that rate of withdrawal of oil under each owner's property is determined by the owner. - The important point to remember is that no matter how intensive the development, the oil reserves of -the United States cannot be materially exhausted' for at least 20 years, and the total available supply, not including shale oil, will probably require 50 to 75 years, or longer, for its withdrawal, the yearly rate of production decreasing slowly from this time on.

Jan 1, 1921

By G. F. Comstock

The subject of transverse fissures in steel rails has been discussed very thoroughly in recent years from various points of view and the final opinions expressed may be roughly classified into two groups: That these fissures are the result merely of fatigue of the steel and are independent of the quality of the metal. That the quality of the metal and the mill practice must have something to do with them. The first point of view was most ably and logically presented by J. E. Howard,' and in the discussion of this paper, as well as in several other preceding publications, Dr. P. H. Dudley, Consulting Engineer of the New York Central Lines, has strongly defended the other opinion.2 The steel makers of the country have naturally rallied under Mr. Howard's banner, hoping to place the entire blame for these failures upon the railroads with their high wheel-loads, hard steel, heavy traffic, and sometimes inferior road-bed; while the railroad men, on the other hand, have been busy accumulating statistics and records in the effort to find an actual reason in the rails themselves that would account for the seemingly haphazard occurrence of transverse fissures under varying conditions and at widely separated points. The view that these fissures were due merely to normal fatigue under alternating stresses seemed most reasonable to the writer until quite recently, because from work done in this laboratory, as well as the work of other investigators, of the problem, no structural differences, in the vast majority of cases, were found between metal at the nuclei of transverse fissures and metal at similar positions in the same rails or in other rails that had not developed fissures. Within the last year or two, however, since the method of etching polished sections for the microscope with a oupric chloride solution has been tried systematically on lengthwise sections, passing through the nuclei of transverse fissures, evidence

Jan 1, 1920

By B. A. Joyce, R. W. Bicknell, R. J. Bennett, P. J. Etter

Epitaxial layers of silicon have been grown on single-crystal quartz and alumina by two types of chemical reaction the hydrogen reduction of trichlorosilane and b) the pyrolysis of silane. These reaction systems are described. The cqsfallography of the two systems, as determined by electron and X-ray diffraction, is discussed, and epitaxial mechanisms suggested. The electrical behavior is briefly considered, and the design and properties of field-evert devices fabricated in the epilaxial material are also discussed. RECENT work carried out in these laboratories" has shown that it is possible to obtain epitaxial deposits of silicon on single-crystal quartz and alumina. The purpose of this paper is to describe the method of preparation of these layers using both the hydrogen reduction of trichlorosilane and the pyroly-sis of silane, to compare the crystallographic behavior of films on the two substrates, and to present some initial results of the electrical behavior of silicon layers on alumina. The structural study has been carried out using electron and X-ray diffraction and electron microscopy. The electrical assessment has been made in terms of conductivity and mobility determinations by the van der pauw3 technique, and by measurements on metal-oxide-semiconductor assemblies. 1) FILM PREPARATION Both quartz and alumina substrates, approximately 1 sq cm in area and 0.4 mm thick. were prepared from slices cut parallel to within a few degrees of (11.0), (10.0), and (00.1), and polished mechanically down to about 0.3 p diamond grade. Chemical polishing of alumina slices, using phosphoric acid at elevated temperatures, has also been used; epitaxial silicon layers have been grown on these substrates, but the process is not entirely reliable, possibly because the large strain present in the Verneuil-grown alumina crystal affects the chemically prepared surface. The two reaction systems are fairly conventional and are described briefly below. a) Trichlorosilane-Hydrogen System. The apparatus is shown schematically in Fig. 1. The substrate was heated by induction, with a fused-quartz encapsulated graphite hemicylinder as susceptor. The procedure for carrying out a deposition was to heat the substrate to reaction temperature in a stream of

Jan 1, 1965

By Lawrence Wright

ON the steep slopes of the Kootenays, 15 to 20 miles south of Nelson, B. C., are a number of ore occurrences (Fig. 1). One that has many features of mining and geological interest is the Ymir Yankee Girl Gold Mines Limited. Discovery of this property was made in 1899 at an outcrop on the hillside, some 2500 ft. above the village of Ymir. This proved to be a branch vein 20 ft. long leading to two main veins, the Yankee Girl and the Spur (Fig. 5). The ore pattern as now delimited shows a remarkable increase in ore area with depth below the outcrop. This recent development is of interest particularly in view of the fact that the property was nearly con-demned, professionally. Another interesting feature, which has a bearing upon its history, is the persistent excess of tonnage produced from period to period over visible reserves. This is not ascribed to lagging mine development, but to detailed vein characteristics, which we will endeavor to make clear by giving a description of the veins and their surroundings.

Jan 1, 1938

By F. Paredes, W. R. Holman, R. W. Crawford

The diffusion coefficient for hydrogen in the ß titanium alloy containing 13 pct V, 11 pct CY, and 3 pct A1 was measured over the temperature range 20° to 500°C. Results fit the expression: D= 1.58 x lgs exp-------==-----) cm2,sec THE diffusion coefficient for hydrogen in the metastable ß-phase titanium alloy containing 13 pct V, 11 pct Cr, and 3 pct A1 was measured as part of an investigation of the effects of hydrogen on the mechanical properties of titanium alloys. Several theories on the mechanisms of hydrogen embrittle-ment include diffusion of hydrogen at ambient temperature as an important step in the embrittling process.'-5 In hydrogen-contaminated a-ß titanium alloys, it has been postulated that the rate-controlling step may be the rate at which hydrogen diffuses from the ß phase to stress- or strain-nucleated brittle hydride platelets at the a-ß interface.' However, embrittlement of the all-ß alloy investigated in this work may proceed by a different mechanism, since this alloy can be embrittled without the formation of detectable hydride platelets.6 Troiano has suggested that in this case the mechanism of delayed failure or embrittlement is similar to that proposed for high-strength steel, i.e., repeated crack initiation caused by a decrease in bonding energy as hydrogen diffuses to points of high tri-axial stress at the root of a notch. In both types of alloy the rate of embrittlement is believed to be controlled by diffusion of hydrogen in the ß phase. Accurate hydrogen-diffusion data in the vicinity of room temperature should therefore be of some assistance in understanding the mechanisms of embrittlement in these two classes of titanium alloys. Diffusion of hydrogen in pure titanium has been studied by Wasilewski and Kehl7 at temperatures above 500°C. Their measurements on diffusion in the ß phase were extended below the ß-a transformation temperature (882°C) to approximately 600°C. This was possible because of the 8 stabilizing effect of hydrogen. No results at lower temperatures have been published and there are no data in the literature on hydrogen diffusion in the ß -phase alloy used in this program. Hydrogen diffusion in metals is generally investigated by measuring the rate of transport of hydrogen past a solid-gas interface, i.e., by absorption, permeation, or degassing-rate measurements. These methods produce accurate diffusion data when bulk diffusion is the rate-determining step in the over-all process. However, at the lower temperatures of interest in hydrogen-embrittlement studies or under conditions where surface films are present, the measured rates may be surface-controlled and the calculated diffusion coefficients will be in error. Surface effects were eliminated in the present work by using a modification of the common welded-couple technique m which two bars with uniform but different compositions are joined before the diffusion anneal." The same type of step change in the initial concentration vs distance curve was produced by electrolytically hydrogenating thin-strip specimens which had been electrically insulated over half of their length. Concentration vs distance curves were determined, after appropriate diffusion-annealing treatments, by vacuum-extraction analyses of transverse samples sheared from the strips. Diffusion coefficients were calculated by the methods of Grube.M This technique was feasible because of the large concentrations of hydrogen which can be charged into p -phase alloys without the formation of hydrides15'16 and because of the extremely low degassing rates observed when hydrogenated titanium alloys are heated in air. EXPERIMENTAL WORK The diffusion couples were cut from a 0.022-in.-thick mi ll-annealed sheet.* Strips 8 in. long by 1/2

Jan 1, 1965

COMMITTEE OF ARRANGEMENTS. General Committee.-J. F. Lewis, Quinnimont, W. Va. Committee of Reception at Staunton.-Major Jed. Hotchkiss, Chairman ; W. A. Burke, M. E. Miller, R. N. Catlett, W. J. Nelson, J. T. Effinger, D. A. Kayser. Local Committee of Arrangements.-G. T. Wickes, Low Moor, Chairman; G. W. Bramwell, Stone Cliff, Secretary; J. E. Johnson, Longdale; H. Firm¬stone, Longdale; S. F. Morris, Quinnimont; O. A. Randall, Ferrol; William N. Page, Ansted; F. Lyman, Low Moor; S. M. Buck, Coalburgh; E. S. Hutchinson, Cannelton ; M. F. Maury, Saltpetre Cave. THE opening session of the Institute was held at Staunton, on Monday evening, May 30th, in the Opera House. Major Jed. Hotchkiss, Chairman of the Committee of Reception, called the meeting to order and introduced Mayor Balthis, who spoke a few words of welcome to the members present, and then introduced the Hon. A. H. H. Stuart. Mr. Stuart in addressing a formal welcome to the Institute to the " little city of the mountains," spoke of the value of the services of the mining engineer in developing the mineral wealth of Virginia and in solving the problems of her geological history. Mr. Metcalf, President of the Institute, replied on behalf of the Institute to the cordial welcome of the mayor and Mr. Stuart, and then read an inaugural address on Force. At the conclusion of the President's address the following papers were read The Electrolytic Determination of Copper and the Formation and Composition of so-called Allotropic Copper, by J. B. Mackintosh, Hoboken, N. J. Read by Professor Egleston. The New Unpublished Map of Chester County, Pa., by Professor Persifor Frazer, Philadelphia. The second session was held at the Opera House on Tuesday morning. The papers read at this session were: Investigations on the Ore Knob Copper Process, by Professor Thomas Egleston, School of Mines, New York city. A Volumetric Estimation of Manganese in Pig Iron and Steel, by F. H. Williams, Vulcan Steel Works, St. Louis, Mo. Read by the Secretary.

Jan 1, 1882

By H. H. Campbell

The following paper deals almost exclusively with the results of practice at the works of the Pennsylvania Steel Company at Steelton, Pa. From the records of the furnaces at this plant, both acid and basic, large and small, are drawn the data for the various demon strations, and on a long and intimate experience with their opera tions are founded many theories and generalizations. It may seem that universal laws should not be built upon a basis so restricted ; but in reality the condition is the strongest guarantee of validity. Each table investigates some- certain variable, and by virtue of the common origin of the factors, we have good ground for assuming the corresponding agents to be equal. The examples may or may not be instances of good practice, and may be open to criticism if regarded solely as exponents of • metallurgical success. But it must be remembered that the lists are not made up of selected specimens, nor are they chosen to show su perior results; they are gathered to investigate, by strict scientific methods, the formula? of the operation. In such work no untoward results should be eliminated, save those which bear upon their face the stamp of experimental error. If the worst members be omitted, then the best must also be omitted. Only by using every available case can an honest attempt be made to deduce a true average. It is recog nized, however, that with the most careful selection it is difficult, if not impossible, to collect data representing universal conditions. In each table the records tell of a special practice, and all conclusions drawn from them are true only within the limits between which the equations have been integrated. Not assuming the prerogative of speaking for American melters in all the opinions herein expressed, nor acting as a camera in por traying an ephemeral state of national metallurgical development,

Jan 1, 1894

By H. B. Pulsifer

THIS paper outlines a method for rapid production of flat, granular surfaces on many of the medium hard- alloys. Grinding wheels and fabrics on wheels are not used; the purpose is accomplished by rubbing on emery papers and on fine abrasives heaped on hand boards. The advantages of chromic acid in the solutions for etching nickel and copper alloys are explained. Steels may require an additional step in the mechanical smoothing owing to the lack of an ideal etchant. Chloric acid is a. rapid etchant for steel. Thirty-six photomicrographs illustrate the steps in smoothing and the clearness with which structures can be rapidly exposed. New structures in low-carbon steels are announced. After a little practice, many materials can be finished within two or three minutes. CUPRONICKELS In the previous papers on the metallography of copper and magnesium which the author has presented to this Institute there has been an attempt to demonstrate the advantages of minimizing the mechanical work of surfacing and depending more on chemical means; the present paper continues the research into a still wider field. It is obvious that the success of a chemical method for smoothing and etching depends almost entirely on the use of a suitable reagent. The etchant must remove the surface granulations and outline the structures. A very special type of reaction between reagent and metal must be displayed. Promiscuous corrosion or the intensification of the attack about local couples -formed by impurities or components must not be in evidence. There are several reagents that etch highly polished nickel and copper alloys very well. Acidified ferric chloride solutions, concentrated and dilute nitric acid solutions, and nitric and acetic acids in acetone have -been used to good advantage for the purpose. However, if they are expected to etch rather deeply-that is, smooth as well as characterize-the results may be far from satisfactory.

Jan 1, 1928

Jan 1, 1951

Jan 1, 1951

By R. F. Yap, N. Arbiter, C. C. Harris

A fully-instrumented driving mechanism has been constructed to study the power, aerating and solid suspension characteristics of several laboratory flotation machines. Machines operating over normal flotation speed ranges give substantially constant power numbers in liquid systems indicating that they operate close to fully baffled turbulent flow conditions. Owing to lack of geometrical scaling, power numbers for different sizes of cells of the same make are different. Even larger differences occur between cells of different manufacturers. For a given impeller, varying the tank size did not significantly affect the power consumption. Tank geometry and baffling has a slight effect on power consumption with shrouded impellers. For a given impeller speed, suspension height decreases while power increases with increasing mass of solids in suspension. While power consumption is hardly affected by particle size and clearance between the impeller and tank bottom, the suspension height significantly increases as clearance increases and as particle size decreases. Aeration was found to affect not only power but also the suspension characteristics of the machine. For closely sized particles, drastic sedimentation occurred when a critical value of the air flow number was exceeded. The critical air flow number decreased with increasing particle size. This effect was less marked with a wide particle size range. The self-aerating capacity of flotation machines increases with cell size at a given speed for the same impeller-shroud system, but decreases in the presence of frother and solids. Equations have been established for correlating all of the studied variables. Data taken from the literature were also correlated with these equations. The modern mechanical flotation machine has, over a period of 60 years, displaced other designs to become the dominant type. Once the correct chemical environmental conditions have been established, the major requirement, selective mineral-air adherence, is essentially a function of two operating variables — impeller speed and air rate. The special nature of this dependence is such that in the same apparatus, but under different operating conditions, adherence can be either prevented or destroyed. Another aspect of this observation is that flotation machines though differing in detail to a considerable extent can produce similar metallurgical results. It must be concluded that having determined the correct reagent levels, establishing the correct operating conditions are at least as important as machine design. Since about 1960, after 30 years of fairly stable circumstances, manufacturers have been developing new types of machines whose major feature is emphasis on pulp flow characteristics by virtue of new im-peller-stator designs. As far as can be ascertained, these new designs necessitate radical departures from accepted impeller speed-air rate values. Performance data are still awaited. Flotation machine development has been empirical, as is selection of operating conditions. The purpose of the work at Columbia University has been to elucidate the fundamentals of the subject so that the purely mechanical aspects of the flotation process can be understood in hydrodynamic terms.1-6 Hopefully, this might lead to intelligent selection of a particular machine and its operating conditions for a specific ore based on a minimum of testing, or even to new types of flotation machines. The present investigation is the most comprehensive to date.7,8 Earlier work, which was largely exploratory, has been repeated and extended and employes the most accurate measuring techniques available. Additionally, sufficient hydrodynamic data were obtained under flotation conditions to delineate the relevant operating ranges. Attention has been given to scaling in that several geometrically scaled tanks and impellers have been constructed and tested; it has been pointed out elsewhere that undistorted geometrical scaling rarely pertains in flotation machine design.5 This paper is divided into sections dealing with relevant combinations of the three phases: liquid, air and solid. Summaries of the literature have been given in previous publications2-4 and will not be repeated here. Recently, several reviews of mixing have appeared, which can be usefully referenced.9-11 It is of interest to note that flotation is not included

Jan 1, 1970

By Charles A. Chase

This paper, descriptive of a single mine, is presented in the belief that it may furnish useful suggestions to mine-managers encountering similar problems; and it includes the details which will enable them to estimate the value of the methods employed—especially where these depart from common practice. Tt should be added, however, that this mine is not typical of the San Juan district, but differs markedly from neighboring mines in physical conditions and metallurgical requirements. The Liberty Bell mine is situated in San Miguel county, Colo., on the west front of the San Juan mountains, 2 miles north of Telluride. The vein was discovered in 1876 by Wm. L. Cornett, who, with subsequeilt locators, took up claims along the apex. A few hundred feet of development-work was accomplished, and a few? tons of ore were smelted or milled; but profitable working proved impossible under existing

Jan 1, 1912

By M. S. Rashid, C. J. Altstetter

Allotropic transformations in cerium have been studied by dilatometric, resistometric, X-ray diffraction, and metallographic techniques. The dilatometric study indicated that, on cooling below O°C, the high-temperature fcc phase, y, transforms partly to the hexagonal phase, ß, and, on further cooling, to the collapsed fcc phase, a. The amount of $ phase present at room temperature is increased by repeated cycling through the a-y transformation. It has been shown metallograPhically that the y-ß transformation has many characteristics of a martensitic transformation. In contrast to the y-ß transformation the ?-a transformation does not give the manifestation of a shear transformation. Small cellular ? domains of random shape and size collapse to a in a short time with no apparent coordination with neighboring domains. The considerable confusion in the literature over the existence of more than one high-temperature fcc phase is discussed. Two such phases have been reported in the literature and an attempt is made in this study to clarify the situation. Twelve fcc and two hcp structures have been shown to be easily reproduced or eliminated. It is proposed that the two "additional" allotropes reported in the literature and fourteen of the phases detected here are not allotropes of cerium but are due to contamination. CERIUM exists in several allotropic forms, but there is some disagreement over what the forms are. Furthermore, the conditions favoring the presence of a particular allotrope and the nature of the transformations from one form to another are uncertain. The objectives of this research were 1) to ascertain the allotropic forms of cerium, 2) to establish the conditions under which the allotropes exist, 3) to study the effects of annealing and thermal cycling on the allotropic transformations, and 4) to study the transformation mechanisms. Dilatometric, resistometric, metallographic, and X-ray diffraction techniques were employed. The form of cerium commonly found at room temperature is fcc and is designated ?. A complex hexagonal phase, 8, forms when y is cooled to slightly below room temperature. At still lower temperatures the y fcc structure transforms to an fcc form with a much smaller lattice parameter, termed a cerium. A bcc form, 6, which exists just below the melting point (800°C), will not be considered further in this work. There is a substantial body of experimental evidence (reviewed by Gschneidnerl) which favors the acceptance of these four allotropes, though some investigators have tried unsuccessfully to observe the ß hexagonal form.'-' There is disagreement, however, over the phase-transformation temperatures, due, in part, to broad hysteresis and overlapping of the transformations between the a, ß, and ? forms. The transformations are also sensitive to prior thermal and mechanical treatment. The differing purity of cerium used by different investigators is undoubtedly a factor. Cerium is difficult to separate from other elements and is quite reactive, igniting spontaneously when it is filed in air. The highest purity of cerium to date is reported to contain several hundred parts per million by weight of impurities, and early investigations were carried out on cerium containing several percent of impurities. There have been reports of more than one fcc allotrope at room temperature. Gschneidner, Elliott, and McDonald5 obtained diffraction patterns of an fcc phase with a lattice parameter about 1 pct less than that of the ? phase, instead of the y phase, on slowly cooling cerium filings from 23° to -198°C and warming them back to room temperature. However, when the sample was heated to 447°C and cooled to room temperature it consisted of only the ? phase. They have designated this new fcc phase "a-? intermediate", and say it is quite sensitive to impurities. After prolonged high-temperature treatment of a powder specimen, Weiner and Raynor2 obtained a diffraction pattern of an fcc phase of lattice parameter about 1 pct less than the ? phase. This they called the y' phase. It could not be reconverted to the y phase and is claimed to be different from the a-? intermediate phase.5,6 Dialer and Rothe3 reported two fcc phases* after cycling their powder specimens between room temperature and -192°C. Gschneidner, Elliott, and McDonald5 suggested that one of the fcc structures obtained by Dialer and Rothe was equivalent to their "a-? intermediate" phase. Table I presents some pertinent data on the proposed allotropes. For the ?(fcc)-ß(hexagonal) transformation

Jan 1, 1967

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation 'YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari' reports a value of 100 * 5 kcal per mole, Hayden and Brophy' obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-' fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.'-' In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By Stanley L. Lopata, Eric B. Kula

The problem of preferred orientation has been considered in quantitative phase analysis by X-ray diffraction techniques. The average intensity of a diffraction peak can be obtained by integration over the whole pole figure, or by random rotation of the specimen in the X-ray beam, or by a combination of both. For rod or wire, where the pole figure shows rotational symmetry, the intensity is measured along a radius of the pole figure. Where no symmetry is present, rotational symmetry is imparted by rapid rotation of the sheet around its surface normal during measurement. These methods are applied to the determination of aus-tenite in an Fe-31 pct Ni rod and Fe-28 pct Ni sheet. X-RAY diffraction techniques are frequently used for quantitatively determining the relative amounts of two or more phases present in a structure.1,2 Briefly, the method requires a measurement of the intensity of a Bragg reflection for each phase. The method is based on the principle that the intensity of a Bragg reflection, IA, is directly proportional to the volume fraction of the given phase present, CA: T KRACA/2µ [1] where K is a constant independent of the diffracting phase, RA can be calculated and depends on the Bragg angle ? and the particular reflection measured, and µ is the linear absorption coefficient of the mixture.' For a mixture of two phases A and B, IA = RAcA [2] IA/IB=RAcA/Rbcb and CA+ CB = 1 [3] This allows the volume fraction of a phase to be calculated directly from the measured integrated intensities of the two phases present. This method is frequently used for quantitatively determining retained austenite in steels, but can be used for the quantitative determination of in titanium alloys, as well as phases in other alloy systems. The intensities are generally measured by diffracting only from planes whose normals are perpendicular to the specimen surface, with the implicit assumption being made that this intensity is typical of reflections from planes whose normals lie at other angles to the surface. If the specimen contains a texture or preferred orientation of the crys- tallographic planes by virtue of previous mechanical working, however, this measured intensity is correct only if the intensity level fortuitously is one times random. Examination of pole figures for actual rolled sheet shows that the intensity level at the center of the figure is seldom at the random level, and can very easily differ by a factor of five or more, leading to a commensurate error in the calculated amount of the phases. Textures have been commonly found in materials which are cold-rolled or recrystallized after cold rolling. This problem is becoming of greater importance since structural materials in use today, such as the high-strength stainless steels, frequently are further strengthened by cold rolling, and hence contain textures. Although high-strength carbon-containing alloy steels generally do not contain textures, some of the newer thermomechani-cal treatments will impart a texture even in these cases. In the case of hexagonal metals, such as titanium, probably every wrought sample will show some anisotropy. Since the standard X-ray techniques are inapplicable in all these cases, there is a clear need for some method of taking this anisotropy into account. The specific problem is to obtain the integrated intensity of a Bragg reflection for each phase, averaged over all orientations of the sample with respect to the X-ray beam. This can be done either by purely mechanical means or by a mathematical averaging. Mechanically, a small spherical speci-

Jan 1, 1965

By M. E. Fine

IN the apparatus for measuring internal friction shown in fig. 1, a modification of that described by Kê,1,2 the parasitic energy loss or background is equivalent to a Q-1 of approximately 4x10-5. This low value of background was obtained by using a jeweler's collet of appropriate size for the upper support, eliminating lateral motion without immersing the bob in oil, and designing the bob to reduce air resistance. The pendulum is supported on the frame through a snug fitting, sliding rotary joint (fig. I-B). A slight twist of the top imparts essentially pure torsional motion to the pendulum. No evidence of energy loss in the sliding joint has been observed. In the bob (E) steel balls are used in the torsion arm, and the bottom is filled with lead giving a total weight of 94 g. A lighter bob may be used for small diameter specimens. Another bob was a solid disc with provision for adding discs to change the frequency. The oscillating image of the filament is recorded on a revolving drum camera (fig. 1-3) driven by a synchronous motor. This allows use of frequencies higher than can be measured visually on a glass scale. Samples varying in diameter from 0.020 to 0.075 in. have been measured, the frequencies have ranged from 1 to 12 cps, and the maximum strain varied from 0.5 to 10x10-5. With appropriate modification the sample may be placed in a thermostat. The apparatus may also be used to measure the shear modulus. In the examples of measurement given in table I the internal friction of Permendur and the 46.8 Ni-Fe alloy are due, for the most part, to magneto-mechanical hysteresis8 (elastic hysteresis accompanying stress-induced magnetostriction) which depends on strain amplitude and increases with annealing. The internal friction of most materials decreases with annealing. References IT. S. K6: Physics Review (1947) 71, 533. 2 T. S. Kê: Transactions AIME (1948) 176, 448; Metals Technology (June 1948) TP 23703. 3 R. Becker and W. Döring: Ferromagnetismus. 365 (1939). J. Springer.

Jan 1, 1951