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By S. C. Sun, T. Chao

The reaction of gaseous sulfur trioxide with different aluminum-bearing minerals for the conversion of their alumina content into water soluble sulfates has been investigated. Theoretical considerations indicate that this reaction is thermodynamically feasible and that preferential sulfatization can be accomplished. The five minerals tested were gibbsite, boehmite, diaspore, kaolinite, and halloysite. In general, over 90% sulfatization could be achieved in 1 hr when using sodium sulfate as an additive at a temperature between 500° and 600°C. It was found that sulfates of the light alkali and alkaline earth metals exhibited some effectiveness in promoting the sulfa-tizing reaction. Selective sulfatization of alumina in a mixture of calcined halloysite and ferric oxide was accomplished. The gas-solid type of sulfatizing reactions have become increasingly important in recent years for the treatment of the oxides of such nonferrous metals as cobalt,' nickel,' manganese,3 zinc, and copper.4-6 Similar reactions were attempted in the present investigation for the recovery of aluminum from the low grade aluminous ores. Unlike the Bayer process in which silica is a serious contaminant, or the acid processes whereby iron usually causes difficulties, the reactions between gaseous sulfur trioxide and various aluminous minerals could hopefully be selective for aluminum. THEORETICAL CONSIDERATIONS Reactions between aluminum-bearing minerals and gaseous sulfur trioxide have been shown respectively in Table I and Fig. 1 to be thermodynamically favorable for temperatures below 1000°K approximately. Calculations of the thermodynamic functions were where ?G, ?H, ?Cp and ?S are changes in free energy, enthalpy, constant-pressure specific heat, and entropy of the system under consideration, respectively; T is the absolute temperature, R the universal gas constant, and K the equilibrium constant. Thermochemical data so far available for these calculations were based on sources given by T. Chao.7 In Table I, the free energy values indicate that reactions between the gaseous sulfur trioxide and

Jan 1, 1968

By T. R. Lippard

PURE gypsum may be broken down into its constituents as follows: [ ] Standard specifications (ASTM Designation C22-25) state that a material shall not be considered gypsum if it contains less than 64.5 pct by weight of CaS042H2O. Anhydrite, the second calcium sulphate mineral found in nature, may be broken into its constituents as follows: [ ] PROPERTIES OF GYPSUM AND ANHYDRITE Pure gypsum is colorless to white but various impurities change its color to shades of gray, brown, red, or pink. It has a hardness of 2 in the Mohs scale and can be scratched with the fingernail. The specific gravity of pure gypsum is 2.3 to 2.4, so that rock gypsum, free from moisture, weighs about 145 lb per cu ft. Gypsum crystallizes in the monoclinic system in tabular crystals that exhibit good cleavage

Jan 1, 1949

By Robert G. Van Nostrand, John H. Henkel

TRANSIENT potentials obtained in resistivity prospecting can be separated into two classes. The first is electromagnetic, has a comparatively short time constant, and increases in relative amplitude as the electrode separation is increased. These electromagnetic transient potentials, of which an excellent theoretical treatment is given by Yost: are the result of changes in the current and can be classed as differentiated signals. The second class is electrochemical, has a comparatively long time constant, and decreases in relative amplitude as the electrode separation is increased. The electrochemical signals are generated by the current flow itself and can be classed as integrated signals. The transient potentials due to electrochemical factors are the subject of this article. The phenomenon is referred to as induced polarization. Schlumberger" was the first worker to observe induced polarization, but he was unsuccessful in attempts to apply the principles of induced polarization in electrochemical prospecting. Other workers, notably Bleil; have studied polarization and in some cases pointed out its possibilities, but no theory has been presented that describes polarization and its time dependence adequately. It is the purpose of this discussion to present the essence of a theory to geo-physicists and to show that it leads to results consistent with experimental evidence. The theory on which this analysis is based has existed in electrochemical circles since 1910."

Jan 1, 1958

By Charles E. Weaver

During the past few years there has been considerable activity in prospecting for oil and gas in several parts of western washington. From time to time seepages of oil or emanations of gas have been reported from various places. Several companies have been organized for the purpose of drilling, but only a part of these have actually begun operations. In certain localities very small seepages of oil occur, but up to the present time no oil or gas in commercial quantities has been obtained. In order to determine the conditions which may be favorable or unfavorable to the occurrence of petroleum it becomes necessary to know the character and extent of the geological formations in which such deposits might occur. In other regions where producing wells have been developed it is possible to know what formations contain the oil and what structural conditions influence its concentration in reservoirs or zones. It is usually possible to determine those strata which contained the materials from which the petroleum may have been derived and also the position and distribution of the more porous sandstone belts into which it may have collected. Detailed stratigraphic surveys may even determine the depth at which a certain known oil-bearing zone may be tapped at any particular place. It is also possible to recognize those formations which are presumably barren of oil, as well as those which are absolutely so. In new regions far distant from any of those which are now producing or have produced in the past, it becomes absolutely impossible to foretell whether oil may exist in commercial quantities or not. Assuming that such deposits do exist, it is extremely difficult to predict at what depth the produciqg zone or zones occur. However, in prospecting in a new and unexplored region, use should be made of such laws as have been found to govern the occurrence of petroleum deposits in other well-developed fields. Such deposits in their world-wide distribution are found almost exclusively associated with sedimentary rocks. Areas composed predominatingly of igneous and metamorphosed rocks are to be rcgarded as extremely unfavorable localities for the occurrence of commercial deposits of oil or gas. Assuming that such oil deposits are

Jan 1, 1916

By H. I-Lieh Huang, O. D. Sherby, J. E. Dorn

RECENT investigations1-4 have suggested that the total plastic strain, C, for high temperature creep under a given stress can be correlated by means of a temperature-compensated time, te- where t is the duration of test, e is the base of natural logarithms, aH is the activation energy for creep, R is the gas constant, and T is the absolute temperature. A typical set of data on which this deduction was based is given in Fig. la. Inasmuch as the e-in t curves for the various temperatures are identical except for their displacement along the In t axis where f and are appropriate functions. If the increase in creep rate with an increase in temperature is exclusively ascribable to a single process involv- ing thermal activation, (T) should equal RT and therefore it = constant [2] where ?= te Assuming the validity of this relationship, ? = ?2 at the same strain, or where the subscripts refer to two alternate test conditions.

Jan 1, 1957

By G. F. Jenkins

The word asbestos is a broad term that has been accepted and applied to a number of fibrous mineral silicates found in nature. They are incombustible and can be separated by mechanical means into fibers of various lengths and thicknesses, but differ in chemical composition and other properties. It is generally recognized that there are six varieties of asbestos; the finely fibrous form of serpentine known as chrysotile, and five minerals of the amphibole group, i.e., amosite (not fully recognized as a mineral species name but accepted in asbestos terminology), anthophyllite, crocidolite, tremolite and actinolite. (Figs 1-4.) Physical and Other Properties The structures of asbestos fibers have been studied intensely in recent years. X-ray diffraction patterns 1 to 15 have been used as a means of identification and classification. The amphibole group structures have been fairly well established while the serpentine group has been the subject of many investigations during the past six years. Low-angle X-ray scattering techniques5 have shown that the chrysotile fibrils are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 180Å* units to 300Å units, while the amphibole fibers are many times larger in cross section. The electron micrographs of chrysotile asbestos (Figs 1-4) have also indicated that the fibrils might be in the form of a hollow tube. This point has been the subject of considerable controversy by a number of investigators.7 to 16 Density measurements17 made on a sample of high quality Arizona fiber did not indicate that the fiber had a hollow tube structure; however, the so-called "sheet structure" of the fibril could be distorted in such a way that it gives the appearance of a hollow tube in the electron microscope. It is of interest to quote one investigator, F. L. Pundsack,17 in this connection: Although the empirical composition of chrysotile is 3MgO.2SiO2.2H20, the true unit cell[#] composition is best represented as Mg12(OH)16Si8O20. This cell has dimensions of a= 5.3Å, b = 9.2 Å, and c = 14.6 Å where the "a" direction is the fiber axis. The calculated density of this unit is 2.56 g/cc, a value in close agreement with experimentally determined density values for chrysotile. The exact manner in which the unit cells of asbestos are stacked together to build up a single fiber of chrysotile is not known, but from various

Jan 1, 1960

By C. BARING HORIVOOD

(Chattanooga Meeting, October, 1908.) THIS paper is intended, in the light of recent investigations, to call attention to some of the essential features of good practice in sampling and mine-valuation. Mine-sampling may be divided broadly into two classes : (1) development-sampling and computation of ore-reserves; and, (2) stope-sampling and estimation of stope-values. DEVELOPMENT-SAMPLING. It is with development-sampling only that this paper deals-the term development being taken to mean the opening-up of a mine by cross-cuts, drives, connections, etc., preparatory to actual extraction of the ore for milling. In development-sampling the work of the sampler and the consequent estimation of the probable value of the mine or portions of the mine, as the case may be, cannot be verified until a later period, when the ground thus sampled has been exploited; hence, extreme care and accuracy are essential. Moreover, the development-sampler has to foresee and allow for contingencies which may arise when stoping is started. It follows that the sampling, in development-work, demands familiarity with the conditions likely to be encountered later in actual mining. In stopes, on the other hand, sampling is clone under actual working-conditions, and the sampler's valuations are immediately checked by the gold-output, or in some cases by a second sampling of the broken ore. A stope-sampler therefore need not be an experienced miner, though he should possess sound technical training and work accurately. Should he be somewhat inexperienced, be soon has his errors discovered for him, and learns to avoid them. Taking these facts into account, it is obvious that a mining company employing two or more samplers should

Jan 1, 1909

By G. A. Guess

THIS investigation was started with the idea of determining whether copper-nickel mattes might not have a lower flowing temperature than copper mattes, and thus perhaps aid in accounting for the difficulty so far experienced in attempts at pyritically smelting copper-nickel ores. We have used the term flowing temperature to avoid confusion with the usual melting temperature. The idea at first was that there might be a greater viscosity range in the one matte than in the other. In the early experiments it was in our minds to determine the relative fluidity of the mattes at a given temperature. Looking to this end we tried pouring equal quantities of matte at the same temperature down an inclined graphite slab, and comparing the distances traveled. Results from such experiments were not satisfactory. We next tried pouring equal quantities at the same temperature through a drilled hole in an Acheson graphite crucible, timing the flow with a stop watch, the whole operation being carried out in the muffle. The flowing temperatures of the mattes tried in this way appeared to be about the same, and there was no marked difference in their fluidity when well fused. Oxidation gave some trouble. These experiments finally led to the adoption of the following apparatus which we thought at the time was wholly original with us, but which we have since found was described by W. McA. Johnson.' The tray used was a slab of graphite 8 in. long, 2 in. wide and ¼ in. thick. It had six holes, into each of which sat a cup of Acheson graphite. Centrally in the bottom of each cup was a vertically drilled hole 3/16 in. in diameter and ½ in. long. The mattes to be tested were put into the cups, in a solid piece. The cups were covered with inverted Battersea "A" cups. The tray was put into the muffle of a gas-fired furnace. Supports on .each end held the tray about 2 in. from the floor of the muffle. Udder

Jan 6, 1916

By Arthur Tauber, Horst Kedesdy

FERRITES are sintered metallic oxides of the spinel structure type1 and belong to the class of soft ferromagnetic materials. Similar to a ceramic, they can be formed and fired to a dense body, exhibiting a high electrical volume resistivity ranging from 10 90 10' ohm-cm as compared with 10-6 hm-cm for some of the metallic magnetic materials. This high resistivity, with resulting low eddy current losses, finds special application at high frequencies. The dispersive susceptibility of ferrites at microwave frequencies has also led to many applications in this field. Where high resistivity with high permeability is desirable, ferrites are used in low frequency applications. During the last few years ferrites exhibiting rectangular hysteresis loops have been developed for computer and magnetic memory systems. The general formula for ferrites is MeFe2O4 where Me is a divalent metal ion such as Ni, Zn, Mg, Mn, Cu, Cd, and Fe. Only two of these ferrites are nonferromagnetic, namely, those with Zn and Cd. Solid solutions can be formed between different ferrites, and it is of interest to note that solid solutions of a ferromagnetic ferrite with a nonferromagnetic ferrite yield much better magnetic materials than the basic ferrite body. In general, it can be said that the solid solution formation between ferrites has widened the field of ferrite synthesis and has led to methods of preparing materials with a large variety of magnetic properties. During the last two decades the synthesis of ferromagnetic oxides has been the object of extensive research, but commercial production has been started only within the last ten years. Along with more fundamental studies, there remains the never- ending task of developing ways to realize the optimum characteristics of materials in large-scale production. Ordinarily, to produce a ferrite material it is necessary for the constituent oxides to be mixed intimately, pressed, and then fired at temperatures above 1000°C. Ferrite Synthesis: Formation of a basic ferrite by solid state reaction from Fe,O, and a monoxide such as NiO, under normal atmospheric conditions, is governed by a progressive diffusion of cations between adjacent particles of the constituents. Firing temperature, furnace atmosphere, and cooling can vary the magnetic properties, however. If, for example, a dioxide, a sesquioxide, or an oxide of the Me0 type is substituted for the monoxide, the reaction mechanism becomes more complex and extremely dependent on atmospheric conditions and firing cycles. For this reason reproduction often

Jan 1, 1958

By J. B. Cohen, S. L. Sass

The nucleation process for y', Ni3Ti, is shou'n to change from heterogeneous to uniform as the undercooling within the phase boundary increases. As unifornz nucleation beconres copious, (100) alignment is observed in the early stages of aging; howecer. whether or not the alignment is due to spinodal decomposition could not be determined. The presence oi a large-scale reversible segregation of titanium and not the intermediate precipitate y' may be the cause of the initial strengthening in this alloy system and the discrete regions detected magnetically by Ben-Israel and Fine. Evidence is presented for the role of dislocations in the formation at long aging tines oJ the equilibrium precipitate . ThE nickel-rich portion of the Ni-Ti phase diagram consists of a terminal fcc solid solution of titanium in nickel called y.' For temperatures below 1290°C if the solubility limit is exceeded and the temperature is high enough, the excess titanium will combine with nickel to form q, Ni3Ti, a four-layer hcp ordered structure with stacking sequence ABAC."~ Since a change in structure is involved, formation of q is slow and a metastable precipitate referred to as y' forms. This metastable precipitate is an ordered cubic phase in the unconstrained state having a structure similar to Cu3Au (LIZ) with the composition Ni,Ti."'5 From X-ray studies,8, 7 the following sequence is indicated for the precipitation reaction at low temperatures: 1) The appearance of satellites around low-index diffraction spots and splitting of high-index spots, indicating the formation of a slightly tetragonal phase in an imperfectly periodic arrangement. The tetragonal phase is y' or the depleted matrix, depending on the volume fractions of matrix and precipitate (and hence, the alloy composition); tetragonality apparently arises from coherency strains. 2) The appearance of diffraction spots from the equilibrium second phase, q. Ben-Israel and Fine'" used magnetic methods to measure the changes in matrix composition during aging, and to estimate the precipitate composition in a Ni-10.1 at. pct Ti alloy. They observed that the alloy, solution-treated at 1270°C and quenched, contained heterogeneities with discrete compositions which gradually vanished upon aging. It was suggested that y' may initially form as a defect structure with several possible compositions deficient in titanium as compared to Ni3Ti; the composition Ni3Ti develops with prolonged aging. The initial composition was Ni6Ti which would require a very large deviation in stoichiometry for y'. It was noted that at 700°C the precipitation reaction was 80 pct complete after 2 hr and that the volume fraction of second phase was 0.2 after 1 hr. Mihalisin and Decker' suggested that the equilibrium precipitate, besides being nucleated at grain boundaries, could also form at stacking faults. ~errick" examined the formation of in Ni-Cr-Ti, and suggested that a collapsed vacancy cluster within y' acted as a nucleus for intragranular q at high temperatures, 820" and 900°C. After long aging times at lower temperatures, 650" and 750°C, diffraction patterns taken from regions containing ribbons of stacking faults showed spots associated with q. Aging greatly enhances the mechanical properties of these alloys, even at high temperatures, and the metastable precipitate y' is thought to be responsible.' At 600°C the hardness of a Ni-10.1 at. pct Ti alloy increases rapidly during the first 20 hr of aging and continues to increase slowly thereafter.'" At 700°C the hardness reaches a maximum at 1 to 2 hr and then decreases.l1 In this paper the kinetics of formation of y' and the mechanism of transformation to in a Ni-Ti alloy are described. Evidence is presented that suggests that large-scale regions of titanium segregation are present initially and these may have an important influence on the initial strengthening of the alloy: these regions may be the heterogeneities detected by Ben-Israel and Fine. I) EXPERIMENTAL TECHNIQUES The Ni-10.3 at. pct Ti-0.6 at. pct A1 alloy was prepared by vacuum melting. Its chemical analysis is given in Table I. A 0.007-in.-thick strip was sandwiched between foils of the alloy and placed in an open Vycor tube with titanium chips (to get oxygen) and solution-treated for ; hr at 1150°C in a Globar Furnace under a flowing argon atmosphere. Following a quench into an ice-brine mixture at -5" to -2"C, a sample to be aged at temperatures up to and including 700°C was sealed in an evacuated Vycor capsule before being put into a fused salt bath. Aging above 700°C was carried out on bare samples in a salt bath. When removed from this bath and quenched into an ice-water mixture, the sample was normally coated with a thin layer of oxide easily removed with emery

Jan 1, 1970

By G. C. Rauch, T. H. Courtney, J. Wulff

The superconducting behavior of Nb-Ti alloys containing 40 and higher wt pct of Nb and variable oxygen content was studied as a function of thermomechanical processing. Critical current density (Jc) us applied transverse magnetic field (H) data were obtained for 0.010 in. diam wires at 4.2° Kin steady fields up to 120 kOe. The precipitate responsible for increase in Jc in each of the alloys studied was related to niobium and oxygen content. In alloys containing 40 to 60 wt pct Nb with less than about 1600 ppm of oxygen, w precipitation in the range 350° to 450°C appears to be responsible for the maximum value of Jc observed. In alloys of higher oxygen content (-2500 ppm), the oxygen-enriched a phase which precipitates in the temperature range 450° to 550°C is a more effective fluxoid pinner. Maximum Jc in low oxygen (350 ppm) 80 wt pct Nb alloys was achieved by 600°C aging heat treatments. Measurements of resistive critical field also reflect the changes in composition accompanying precipitation in these alloys. It is well known that the superconducting critical current density, Jc, of solid solution superconducting alloys can be increased by precipitation heat treatments.1-4 The precipitate, to serve as an effective superconzlucting fluxoid pinner and increase Jc, must be of proper size and spacing.' Its electronic properties must also be different from those of the matrix.6 As in age-hardenable systems, optimum temperature and time of aging are dictated by the composition and history of the particular solid-solution alloy under consideration. The alloy diagram of Ti-Nb7-9 shown in Fig. 1 is typical of ß-stabilized Ti alloys. Precipitation to achieve high Jc in Ti-Nb and Ti-Ta alloys is usually carried out in what is believed to be a two-phase a + ß region.1,2,4,10 Previous work on Ti-Nb4,11 and on other ß-stabilized systems such as Ti-V, Ti-Mo,12-14 has shown, however, that the first precipitate to appear is not necessarily (Y. Under specific conditions the meta-stable w phase is precipitated instead. A further complication arises in such alloys from the strong influence of contained oxygen on the phase stability and on the kinetics of precipitation.15,16 The superconducting critical current density of Nb-Ti alloy containing less than 36 wt pct Nb has been studied by Vetrano and Boom1 and Kramer and Rhodes.4 The most effective aging temperature was found to be about 425°C; fluxoid pinning was attributed to the precipita- tion of a by Vetrano and Boom and of w by Kramer and Rhodes. Although the latter workers used recrystal-lized material and the former cold-worked, studies carried out in our laboratory lead us to believe that the type of precipitate responsible for increased Jc is unaffected by prior cold-work.17 That other types of precipitates may also be effective, especially in higher oxygen-containing alloys, has been demonstrated by Reuter, et al.2 in this laboratory with the aid of electron microscopy. Reuter et al. found that at an aging temperature of 600°C, fee-TiO is precipitated, resulting in high values of Jc. Even higher values of Jc were observed after heat treatment at 500°C, but the precipitate could not be indexed as fee-TiO. Whether the precipitate was oxygen-rich w or a could not be clearly distinguished. The work nevertheless indicates that appreciable amounts of oxygen alter the nature of the phases precipitated at different temperatures, at least in alloys containing more than 36 wt pct Nb. Since such compositions are more readily worked into suitable wire than lesser niobium content alloys, it was decided to study the response to aging of the alloy compositions reported in the present paper with the hope of clarifying the effect of composition on the precipitation processes responsible for high values of Jc. I. EXPERIMENTAL Nb-Ti alloys containing 40, 50, 60, and 80 wt pct Nb were prepared by are-melting 35 g ingots of iodide crystal bar titanium and electron-beam melted niobium.

Jan 1, 1969

By B. D. Cullity

A distribution of residual stress after plastic elongation is proposed, in which the bulk of the material is strained in compression and a very small portion in tension, This distribution is shown to account both for the X-ray observations and for the effect of plastic straining on magnetic losses in silicon steel. The regions left in compression are tentatively identified with the interiors of the sub-grains revealed by the electron microscope. THIS paper is concerned with the general problem of the nature of the residual stress which is produced in metals by plastic elongation. A particular stress distribution will be suggested which accounts for the main X-ray diffraction observations which have been made. It will also be shown that certain magnetic measurements made on silicon steel can be understood in terms of this stress distribution. X-RAY OBSERVATIONS Uniform straining of a crystal lattice (macro-strain) causes a diffracted X-ray beam to shift its position, and nonuniform straining (microstrain) causes line broadening. If a bar of metal is plastically elongated in the longitudinal x direction and then unloaded, diffracted X-ray lines are observed to be both shifted and broadened.'-= Although the observed line shift indicates the presence of macro-strain, experiments have shown that no macrostrain, in the usual engineering sense of the term, exists.5"7 For example, removal of a layer from one surface of a stretched and unloaded bar does not produce curvature in the remainder of the bar 5'7 Fig. 1 shows the variation of lattice strain in the x direction, as determined from X-ray line shifts, with the applied stress in the same direction. The curve ABC is the normal stress-strain curve of the material, AB being the elastic portion and BC the plastic. In the elastic region AB, the strain measured by X-rays, called the lattice strain, and the strain measured mechanically are both proportional to the applied stress, and both return to zero when the applied stress is removed. Above the elastic limit the lattice strain would be expected to continue to increase along the line BD. Actually, it increases less rapidly with respect to stress, or even decreases, as shown by BE. If the applied stress is then decreased, the lattice strain decreases along EF, which is parallel to AB. As a result, there is a compressive residual lattice strain FA after unloading. STRESS DISTRIBUTION. Since a stretched and unloaded bar does not contain macrostress, it follows that the observed line shift must be due to a special distribution of mi-crostress. Such a distribution is shown in Fig. 2, which shows the variation of the stress u, across a stretched and unloaded bar. The material is assumed to consist of two kinds of regions: regions C, stressed more or less uniformly in compression, comprising the bulk of the volume of the material and responsible for the observed diffrac-

Jan 1, 1963

Do not write until you have something to say. Think first; then write. In order to be understood, you must know what you wish to say. Clear writing is the consequence of clear thinking. Therefore consider your subject well before you begin to write; ruminate on it; marshal the salient facts in your mind; saturate yourself with the ideas you wish to express and with cognate ideas; then express yourself deliberately. If you are bubbling over with your subject the words will come, but you might as well expect to sail without a breeze as hope to give life to words without the living thought. Here I may advert to the fact that among the uneducated it is a common expectation to acquire the knack of writing without taking the trouble to study the art of literature. I overheard a woman in a suburban train remark to her neighbor: "I'd like to be able to write well without stopping to think about it". She was one of many that would like to do a thing well without the trouble of thinking; but it cannot be done in respect of anything to which thought is essential. The possession of a good voice does not justify a person in expecting to sing successfully to a large audience; before singing in public one has to master the technique of singing; one has to learn first how to breathe properly, how to enunciate, and many other things. The successful singer is an artist, not a megaphone. Most of us would regard a man or a woman without any training in the art of singing as a fool or an impostor if he or she were to give a public concert, yet we do not recognize the equal foolishness and imposture of persons that write books before they have studied the technique of writing. That is why so many books are unreadable, and why many books by clever men are difficult to read. They start to write books before

Jan 1, 1931

By R. F. Domagala, D. J. McPherson

Iodide zirconium was combined with calculated amounts of ZrO2 or master alloys and arc-melted. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat treated specimens permitted construction of the binary phase diagram from zirconium to ZrO2. Oxygen additions to zirconium raise the transformation temperature as well as the melting point. Features of the diagram include the peritectic formation of beta, the formation of alpha directly from the melt, an intermediate phase ZrOB with a' range of homogeneity, and a eutectic between alpha and Zr02. PHASE relationships in the Zr-0 system were determined in the range 0 to 66. 7 atomic pct 0 (ZrO,). Arc-melted alloys were annealed at temperature levels between 600" and 2000°C. Determination of the phase boundaries was accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to determine solidus curves, and X-ray diffraction work was employed to study the lattice parameters of the a solid solution and the phase ZrO,. Experimental Procedures Westinghouse "Grade 1" iodide zirconium crystal bar (approximately 99.8 pct pure) was employed for the investigation. This material is substantially free of the impurity inclusions characteristic of most zirconium metal. Previous work has shown it to be the most satisfactory grade for phase diagram studies. The zirconium crystal bar, as-received, was coated with corrosion product from autoclave tests by which its grade designation is determined. The bars were sand blasted lightly, pickled for 1 min in a 20 pct HN0,-5 pct HF aqueous solution, rinsed in water and acetone, and dried. The bars were rolled to about 1/32 in. strip, cut into 10 in. lengths, and pickled again. The material was sheared to approximately Y4 in. squares, cleaned with acetone, and stored for use. Two pounds of specially prepared "chemically pure," and 100 grams of spectrographic grade ZrO, were obtained for the preparation of alloys. The "Specpure" ZrO, was obtained from Johnson, Mat-they Co.. Ltd.. and Titanium Alloy Manufacturing Div. of National Lead Co. supplied the other grade of oxide. The "chemically pure" material (henceforth referred to as C.P. ZrO,) was used for the preparation of all alloys employed in the determination of phase relationships. A limited number of alloys were prepared with the "Specpure" oxide to recheck certain phase boundaries. Analyses of the two grades of oxide are given in Table I. The C.P. ZrOI was received in powder form, not suitable for arc melting. Therefore, this material was compressed to wafers 1 in. in diameter and about Vn in. thick. These were segmented and stored for use. The "Specpure" material, in the form of small granules, was suitable for use in the as-received condition. A nonconsumable electrode arc-melting furnace was used to prepare alloys. A water-cooled copper crucible and tungsten-tipped electrode were employed. The material was placed in the crucible and rapidly melted under a protective atmosphere of helium gas by striking the arc on a tungsten stud and directing it upon the charge material. Details of operation, including drawings of this type furnace, have been published.'

Jan 1, 1955

By H. S. Kalish, F. J. Dunkerley

INTRODUCTION AND PREVIOUS WORK THE determination of the low temperature tensile properties of tin and tin-lead alloys was initiated as part of an extensive research program on the phasial equilibria of tin binary systems below 13.2°C and the property changes associated therewith. A survey of the literature revealed that, although some room temperature tensile data were available for tin and a few tin-lead alloys, there existed no survey report of the low temperature tensile properties of these alloys. Accordingly, the tensile data for tin and a series of pure tin alloys containing from 0.01 to 50 pct lead were measured at eleven temperatures from -196 to +20°C and are presented here in survey form. In addition to the importance of these tensile data as a preliminary to certain fundamental research, this information promises also to be of commercial importance because of the 'extensive use now being made of tin-lead solders in refrigeration and gas liquefaction equipment. Occasional failures of the solders in low temperature service have been attributed by some metallurgists to low temperature mbrittlement, while others hold that failure results from the transformation of the tin-rich phase of the solder from the solid white (beta) to the powdered gray (alpha) form. From the data previously available in the literature, neither of these explanations can be completely corroborated. Cohen and van Lieshout1 have established the beta to alpha tin transformation at 13.2°C and have shown that strain accelerates the transformation. Further, they showed that although I pct lead retarded the transformation, it was not eliminated. It will be pertinent, then, to note whether the beta to alpha transformation of the tin-rich phase will occur in a short-time tensile test. Polanyi and Schmid2 studied the tensile . properties of tin single crystals at -185°C and report that tin is brittle at-this temperature. In 1946, Kostenets3 reported that pure tin was brittle at -196 and -253°C, while lead remained ductile at both these temperatures. He also studied the tensile properties of tin-lead alloys containing from 10 to 75 pct lead at -253, -196 and +17°C. The ultimate tensile strength increased more than two times in going from room temperature to -196°C and about three times that value on further cooling to -253°C. All the alloys were brittle at -6°C except those containing more than 75 pct lead. Even at -253°C, the 75 pct lead alloy retained 36 pct elonga¬tion in a 30 mm-ga. length. Creep is also an important phenomenon

Jan 1, 1948

By Howard Martens, Pol Duwez

IN two papers published in 1949, alloys of chromium with the refractory metals tungsten, molybdenum, tantalum, and columbium were investigated in view of their possible use as high temperature resisting materials. For the Cr-Ta system, a partial phase diagram was presented and the only intermediate phase was identified at Ta2Cr3. A phase of the same composition was also observed in the Cb-Cr system. The X-ray diffraction data presented in these papers, however, were insufficient for crystal structure determination. It is shown in the present study that the only intermediate phase in both the Ta-Cr and the Cb-Cr systems corresponds to the ideal stoichiometric ratio TaCr2, or CbCr2. Both structures are cubic, MgCu, type. At high temperature, however, TaCr2 has a hexagonal MgZn, type structure, which can be retained at room temperature by fast cooling. The alloys were prepared by melting in a helium arc furnace on a water-cooled plate. The design of the furnace was essentially the same as that described in ref. 3. Some alloys were also obtained by sintering compacts made of the mixed powders pressed at 80,000 psi. The sintering was carried on for 4 hr at 1375°C. The tantalum and columbium powders were supplied by Fansteel Metallurgical Corp., North Chicago, 111. The tantalum powder was the reagent grade, with a particle size smaller than 400 mesh and a total impurity content less than 0.1 pct. The columbium powder was smaller than 325 mesh and contained approximately 0.1 pct C and traces of Fe, Ti, and Zr. The electrolytic chromium powder from Charles Hardy, Inc., New York, was smaller than 300 mesh and contained about 0.1 pct Na, 0.05 pct Ca, and traces of Cu, Al, Mg, Si, and Co. Powder diffraction patterns were obtained with a 14.32 cm camera, using copper Ka radiation filtered through nickel foil. The powder pattern of the TaCr2 alloy obtained by sintering at 1375'C was different from that obtained on the same alloy rapidly cooled from the melt. Contrary to this result, the powder pattern of CbCr2 was the same, whether the alloy was made by sintering at 1375°C or by melting, and was similar to that of the TaCr, sintered. It was also found that the structure of the TaCr2 specimen obtained by melting was retained after heating for 4 hr at 1590°C, but transformed into the structure found in the sintered specimen after heating for 4 hr at 1375°C. Hence, the structural change of TaCr2, appears to be a reversible polymorphic transformation. CbCr2 and ToCr2 Structure, Low Temperature Form By using large scale Hull-Davey charts, the powder pattern of CbCr, and of the low temperature form of TaCr2 were readily interpreted on the basis of a face-centered cubic lattice with a parameter of approximately 6.95 kX. The indices of the reflections together with the values of sin' 0 are given in Tables I and 11. From this list of observed reflections, it appears that the (200), (600), (024), (046), and (028) reflections are missing. The lack of (h00) reflections for h 4n indicates a four-fold screw axis. The missing (Okl) spectra for k + 1 An indicate the existence of a diamond glide d. The combination of these symmetry elements can be found in the O— Fd3m space group, which is therefore the most probable one. After having determined the approximate density of TaCr, by the immersion method, the number of molecules per unit cell was calculated and found to be nearly eight. This information, added to the fact that the most probable space group is O leads to the consideration of a structure of the MgCu2 type, in which the atoms have the following positions: 8 magnesium in a and 16 copper in d. On the basis of this structure, intensities were computed by means of the usual formula: 1 cos'20 I a sin2 cos where F is the structure factor; 8, the Bragg angle: and p, the multiplicity factor. As shown in Tables I

Jan 1, 1953

By KING HAMILTON GRAYSON

IRON and steel were the only basic industries in the Soviet Republic in 1928 that lagged behind the pre-war production on a comparative basis. This was due to the almost complete obliteration of all industrial units manufacturing iron and steel products during the Revolution, which resulted in the production of 1921 being only 4 per cent of that of 1913. By the end of 1927 the production of pig iron had reached a point equal to 70.5, per cent of 1913; steel was 84 per cent ; and rolled iron was 78 per cent. According to the. planned program of the Supreme Economic Council, the pre-war level of the iron and steel industry was to have been reached and exceeded during 1929-30. The production of the entire period from 1917 to 1928 in comparison with 1913, is shown in the following table

Jan 1, 1929

By T. D. Yensen, R. K. McGeary

While we have not been primarily interested in the determination of hydrogen in the alloys that we have been dealing with, we arc very glad to cooperate in this symposium on sampling and analysis for hydrogen, as we can never tell when we may find it desirable to perform such analyses. Vacuum-fusion Method Our primary interest has been oxygen and carbon, in the analysis of which we think we have become very proficient. Our oxygen-analyzing apparatus is of the vacuum-fusion type (Fig. I). This employs Dr. Derge's type of graphite cruciblc and slit sleeve, with graphite powder between, for heat insulation (Fig. 2) supported in a clear quartz bulb connected to the Pyrex glass system by means of a carefully made ground joint. The latter is kept cool by means of an air blast from a circular copper tube surrounding the joint. The crucible is heated by high-frequency induction and the 24 one-gram samples successively dropped in from the horizontal tube at the top by means of a magnet. The gases (H², CO, N2) are passed through the CuO catalyst held at 300°C. (converting CO to CO²I, H² to H²O) and the CO² and H2O frozen out in the main liquid air trap, while N2 is evacuated. At the end of the operation, shown by the termocouple vacuum gauge indicating a pressure of 10-4 mm. Hg, the analyzing system is isolated by means of the mercury cutoffs, and the CO² and H2oare determined by transferring first the CO2 and then the HzO to the small trap at the right. This is done by placing liquid air on the small trap, then removing the liquid air from the large trap for one minute, which is sufficient to evaporate the Co2 and transfer it to the small trap. The CO2 is then measured by closing the mercury cutoff at the extreme right, removing the liquid air from the small trap, warming it up to room temperature, adjusting the mercury level to one of the three marks on the glass tube (corresponding to three volumes calibrated so that I mm. Hg of CO² corresponds to 0.001, 0.002 and 0.010 mg., respectively, of oxygen) and finally reading the pressure. Liquid air is now replaced on the large trap, the mercury cutoff at the right opened, transferring the COz back to the large trap. The cutoff to the pumps is then opened, the liquid air removed for one minute, thus evacuating the CO², the pumps again cut off and the H2 O transferred to the small trap as before, except that it is now necessary to warm the large trap with a Bunsen burner in order to evaporate all the H2O. This requires about three minutes, as the inner tube must be heated to at least 100°C. In order to prevent H²O from being adsorbed on the glass walls, the glass tubing beyond the catalyst (i.e., to the right in Figs. I and 3) is kept heated to about 150°C. by means of Nichrome ribbon as shown in Fig. 3. For a I-gram sample the above amounts of oxygen (0.001, 0.002 and 0.010 mg.) 35

Jan 1, 1945

By Michael Hoch, Seong Kwan Rhee

The ternary system Zr-Cr-0 was investigated at 1200°, 1500°, and 1700°C. The isotherms at these temperatures were determined by metallographic and X-ray diffraction analysis of carefully selected alloys. AS a part of a series of investigations1-4 of the ternary and quaternary phase diagrams on refractory metals and their compounds, the ternary system Zr-Cr-O was investigated at 1200°, 1500°, and 1'700°C. The binary diagrams Zr-Cr, Zr-O, and Cr-0 as reported by Hansen5 and Levin et a1.' and the existence of a ternary coompound ZrsCrsO (q-carbide structure a. = 11.96A) provided a good base for this investigation of the Zr-Cr-O phase diagram. MATERIALS The materials used and their suppliers were: Zirconium powder, 99.4 pct pure, Charles Hardy, New York; Zirconium dioxide, Fairmount Chemical Co., Newark, N.J.; Chromium powder, 99.85 pct pure, Fairmount Chemical Co., Newark, N.J.; Chromium sesquioxide, 99.86 pct pure, J. T. Baker Chemical Co., Pillipsburg, N.J. Though the materials used were not "hyperpure", the impurities present do not affect the results (lattice parameters, phase boundaries) within the experimental accuracy. EQUIPMENT AND PROCEDURE The detailed procedures and equipment used for this investigation were similar to those described elsewherel' "ith the exception that in this study an induction-heated argon-atmosphere furnace was used. The latter furnace was used to prevent the vaporization of chromium metal in samples in the higher temperature range (above 1200°C). The tungsten crucible was induct ion-heated in a vertical quartz tube filled with argon gas. The quartz tube was 1-1/2 in. in diameter and 10 in. long; it was connected at the top and bottom to water-cooled copper plates. The argon gas of a purity 99.995 pct was further purified by being passed through zirconium metal chips which were maintained at 800°C in a silica tube 1 in. in diameter and 30 in. in length. The furnace was flushed with argon gas for an hour before starting heating; during heating, a slight (3 cm oil) overpressure of argon was maintained in the system. Power was supplied by a 20-kw Ther-Monic Induction Generator. The samples rested on a tungsten-wire basket; the wire basket was connected to a tungsten wire which passed through the tungsten crucible lid, and entered the system on top through a Wilson-type seal. By pulling on the wire, the sample was removed from the crucible and dropped to the water-cooled copper base of the furnace. Because of the presence of argon gas, the cooling of the sample was even more rapid than in the vacuum furnace.' EXPERIMENTAL RESULTS AND DISCUSSION 1) Isothermal Section at 1200°C. The compositions investigated have been numbered within the phase diagram, Fig. 1, and all the pertinent information about the samples can be found in Table I. This table lists the composition of the samples, the phases present in the room-temperature diffraction patterns, the phases detectable in the microstruc-ture, and calculated lattice parameters of the a-zirconium phase. The shapes of the various phase

Jan 1, 1964

By Eugene McAuliffe

The mining press, as well as certain federal and state bulletins, refer from time to time to the relative hazards that attach to loading bituminous coal by hand when compared with the so-called "mechanical loading" process. Much of the coal coming under the head of hand-loaded coal is won in part by the use of machinery; the coal-cutting machine is in general use, the electric power drill employed to a lesser extent. Therefore it may be said that the principal difference in the process employed, mechanical loading versus hand loading, lies in the fact that some type of loading machine is employed in the mechanical loading process to lift the coal from the face of the room, place or entry, after it is mined, placing it in the pit cars for transport to the tipple. It is a common practice to compute accident records on the basis of tons mined per fatal and per nonfatal accident, disregarding the fact that it is possible to produce by the aid of coal-loading machines the same daily, monthly and annual tonnage with a much smaller force than is required where the coal is all shoveled by hand. Inasmuch as the men who are released by the substitution of machinery for hand labor must find employment elsewhere, suffering some measure of hazard in their new occupation, we are of the opinion that the true relative hazard that attaches to the processes of mechanical loading and hand loading can be determined only by using as the basis of comparison "man shifts worked" or "hours of exposure" experienced per accident. The Union Pacific Coal-Co., beginning with the year 1929, undertook to maintain a true record of man shifts worked per compensable accident, giving equal weight to fatal and nonfatal accidents. Accidents lacking sufficient severity to come under the compensable terms of the Workmen's Compensation Act were not included in the compilation, the Act providing that "no compensation, except the expense of medical attention, shall be allowed for the first seven (7) days of disability, unless the incapacity runs beyond the period of twenty-one (21) days, in which case the compensation shall run from the time of the injury." With the further thought that all accidents suffered by employees engaged in any service, in or about the place where the loading process

Jan 1, 1931