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By Fred D. DeVaney and

The coercimeter, as its name implies, is an instrument for measuring the coercive forcet of magnetic substances. It was developed by Davis and Hartenheim in the Special Studies Section, Metallurgical Division. A detailed description of this apparatus may be found elsewhere.2 The coercive force determinations of magnetic materials are interesting because of the relationship established by Gottschalk,4 who showed a linear relationship between the magnetization coercive force and the specific surface of comminuted particles. The value of this relationship in determining grinding efficiency has been shown by Dean.3 The determination of the surface contained in the subsieve sizes has always been a difficult problem for investigators. They made approximate measurements of the surface of coarse materials by sizing on screens, but for the determination of the surface of the sub-sieve sizes it was necessary to make detailed grain counts or elutriation tests, or to study dissolution rates. The technical literature contains many references to other methods for determining these surfaces, either by some special apparatus or by mathematical calculations based on distribution lines. Many of the methods are long and tedious, and the results of some, at least, are questionable. he turbidimeter gives quick results on ground cement. By using magnetite as the material to be ground, a simple determination of its coercive force by the coercimeter, requiring 10 minutes or less, can be transposed directly and accurately into units of relative surface. This subject has been pursued further by the U. S. Bureau of Mines in cooperation with the Missouri School of Mines and Metallurgy, Rolla, Mo., and the following is a description of the results.

Jan 1, 1939

By Fred D. DeVaney and

The coercimeter, as its name implies, is an instrument for measuring the coercive forcet of magnetic substances. It was developed by Davis and Hartenheim in the Special Studies Section, Metallurgical Division. A detailed description of this apparatus may be found elsewhere.2 The coercive force determinations of magnetic materials are interesting because of the relationship established by Gottschalk,4 who showed a linear relationship between the magnetization coercive force and the specific surface of comminuted particles. The value of this relationship in determining grinding efficiency has been shown by Dean.3 The determination of the surface contained in the subsieve sizes has always been a difficult problem for investigators. They made approximate measurements of the surface of coarse materials by sizing on screens, but for the determination of the surface of the sub-sieve sizes it was necessary to make detailed grain counts or elutriation tests, or to study dissolution rates. The technical literature contains many references to other methods for determining these surfaces, either by some special apparatus or by mathematical calculations based on distribution lines. Many of the methods are long and tedious, and the results of some, at least, are questionable. he turbidimeter gives quick results on ground cement. By using magnetite as the material to be ground, a simple determination of its coercive force by the coercimeter, requiring 10 minutes or less, can be transposed directly and accurately into units of relative surface. This subject has been pursued further by the U. S. Bureau of Mines in cooperation with the Missouri School of Mines and Metallurgy, Rolla, Mo., and the following is a description of the results.

Jan 1, 1939

By Herbert Banks Johnson

DURING the past 10 or 12 years very little information has been made generally available concerning the commercial possibilities of separating materials by means of static electricity; and yet during that same period important improvements have been made in various branches of the science of electricity, which, when taken together, and applied to electrostatic separation, have resulted in important improvements in that art as well. For example, much improvement has been made in high-voltage electrical equipment such as full-wave vacuum-tube rectification and improved mechanical rectification. Great strides have likewise been made in the development of insulators for high-voltage work, not only in the materials used but also in the design of the insulators themselves. Again, in another field, the development of air-conditioning equipment has improved the technique of controlling the surface condition, through drying or humidifying, of the various materials that are passed through the electrostatic separator. In many authoritative publications and textbooks, the electrostatic separation process is declared to require a balance far too sensitive for general commercial application. For example, one publication1 in the past has referred to an unfavorable effect on the process caused by varying atmospheric conditions such as humidity. Some2 have even gone so far as to state that sunlight and shadows may seriously affect the separating efficiency of the process. Such statements may have been true in the early development of the art, when the source of static electricity was derived from a friction disk machine, such as the Wimshurst. The Blake Mosher equipment and the work of Huff in applying motor- generator sets, transformers and mechanical rectification overcame much of this kind of objection to the commercial application of the electrostatic separating process. Another objection made periodically is that it is generally considered necessary to feed the particles into the electrostatic field in a stream that

Jan 1, 1938

By J. W. Furness

Before attempting any discussion of the importance of tariff enactments as applied to exhaustible resources, certain basic factors should be emphasized. First, it must be remembered that minerals differ from organic substances in that they are irreplaceable, and when once taken from the earth's crust enter into uses which ultimately dissipate them, so . that they cannot be recovered for future use. A second factor entering into the problem is the unequal distribution of the mineral deposits of the world. No industrial nation has within its political confines a sufficient quantity of all the minerals necessary for the maintenance and advancement of present civilization; hence international exchange of these commodities is inevitable. As minerals are essential to modern industry, the supply available to any given nation constitutes a factor which limits its ambition to advance industrially. A nation which has this ambition endeavors to secure not only a supply of minerals sufficient for its current needs, but also sources which will assure it expansion. Should mineral raw materials be withheld from such a nation by enactment, it seems inevitable that every effort will be made to obtain them, and that, should the nation deem itself sufficiently powerful, its ultimate recourse will be force. Thus the importance of tariff enactments, not only from the standpoint of industrial prosperity but from the standpoint of international peace, can be appreciated.

Jan 1, 1932

THE metal iron has physical and chemical properties which are somewhat different from those of steels, but a knowledge of the pure metal is a useful starting point in studying the behavior of steels. Solid iron exists in two different crystalline forms, called alpha (a) and gamma (?) iron, the former being the ordinary form at room temperature. When heated above the "A2 point," 1400°F. (760°C.), the metal becomes non-magnetic, and at the "As point," 1670°F. (910°C.), it undergoes a change in crystalline form to become gamma iron. In the range 1400 to 1670°F., it is sometimes called beta (0) iron to distinguish it from the magnetic alpha, but the two are identical in crystal structure. When gamma iron is further heated to 2550°F. (1400°C.), it changes into delta (d) iron, which is identical with beta or non-magnetic alpha iron. Pure iron melts (in a hydrogen atmosphere) at 2795°F. (1535°C.); the melting point is generally lowered by alloys or impurities. PROPERTIES OF IRON AT HIGH TEMPERATURES Many of the properties of iron undergo abrupt changes at the transition temperatures. (1) For example, in heating through the As point a sudden shrinkage in volume occurs. Similarly, melting is attended by sharp physical changes such as an increase in volume. Table 27 contains a summary of the measured physical properties of pure iron at several temperatures. Usually the properties change smoothly within the range of stability of a given form, but this is not always the case. For example, the specific heat reaches a sharp maximum at the A2 point although no transformation occurs. Solvent Powers of Liquid Iron. Liquid iron is capable of dissolving most of the other metals and many nonmetallic elements as well. Of the metals which are liquid at the melting point of iron only lead, silver, and bismuth refuse to dissolve to an appreciable extent. The non-metals presumably dissolve by virtue of the formation of an iron compound; for example, sulphur is thought to dissolve as the compound FeS. However, there is no satisfactory method of proving that this

Jan 1, 1944

By W. C. Ellis, M. E. Fine

WHEN certain binary Fe-Ni alloys are worked cold and then stabilized by a stress-relief anneal, their Young's moduli are nearly invariant over a substantial temperature range determined by composition and work-anneal history.' In the present investigation addition of molybdenum to such alloys (besides increasing the yield strength) was found to diminish the sensitivity of the thermal coefficient of Young's modulus to composition changes. Such alloys are of interest for applications requiring 1 a metal with controlled, low temperature coefficient of Young's modulus and substantial magnetic permeability.' Young's modulus ordinarily decreases with rising temperature. In ferromagnetic alloys a change in modulus on heating due to loss of ferromagnetism modifies the .temperature dependence. Far below the Curie temperature ferromagnetism alters the modulus in two ways: a—Addition of the energy of magnetization, a function of interatomic distance, changes the relation between interatomic energy and distance.' This lowers the modulus in the Fe-Ni and Fe-Ni-Mo alloys of this investigation. b—An applied stress changes the ferromagnetic domain arrangement so that linear magnetostriction contributes to the strain and further lowers the modulUs.~ Since in the alloys of this investigation both effects lower the modulus, loss of ferromagnetism on heating changes the slope of the modulus-temperature curve in a positive direction. With increasing temperature the slope of the modulus-temperature curve, due to progressive loss of ferromagnetism, becomes less negative, goes through zero (the modulus is minimum), becomes positive, and resumes its normal negative value above the Curie temperature.' The increase in modulus and decrease in curvature in the modulus-temperature curve occurring on work hardening have been attributed to a reduction in effect (b).'. Vn the absence of ferromagnetism work hardening through introduction of residual strains would be expected to decrease the modulus.' Alloy Preparation—Test Methods Four series of alloys having nominal molybdenum contents of 5, 7, 9, and 10 pct and containing 47 to 58 pct Fe (the analyzed compositions are given in Table I) were melted in air and cast as bars weighing from 2 to 6 lb. The charge consisted of electrolytic nickel, Armco iron, molybdenum (99+ pct) or ferromolybdenum (62 pct Mo), manganese, and aluminum as a deoxidizer. The bars were swaged cold to the desired diameters with intermediate anneals. Alloys in this composition range are reported" to be face-centered cubic and ferromagnetic at room temperature. The Curie temperatures" decrease with molybdenum. For example, keeping the Ni/Fe ratio at unity and increasing the molybdenum from 0 to 17 pct decreases the Curie tempera- ture from approximately 500°C to room temperature. (The 17 pct Mo alloy requires quenching to retain a single phase.~) Young's modulus at a series of temperatures from —50" to 100°C was determined by a dynamic method previously described.', " In this method Young's modulus is calculated from the resonant frequency (in this case approximately 50,000 cycles per second) of a rod sample (approximately 2 in. long) vibrating longitudinally in the first mode. The densities of the samples at room temperature, Table I, were determined by the standard method of weighing in air and reweighing in redistilled bromobenzene. The linear coefficients of expansion, Table I, needed to calculate the sample length and density at the temperature of measurement, were obtained by observing the change in length (22" to 100°C) of an 8 in. gage distance with a two microscope cathetometer. The values of density and coefficient of expansion in the few samples checked are independent of treatment to the accuracy reported. This was assumed to be general for all the samples. The modulus values are accurate to &0.05x101' dynes per sq cm. However, values of thermal change in modulus are accurate to 20.005~ 10" dynes per sq cm. Young's Modulus Values at 25°C: The modulus values of O', 5, and 10 pct Mo alloys at 25 °C are plotted in Fig. 1 as functions of nickel. After working cold, the samples were either recrystallized at 950" to 1000°C or given a low temperature stabilizing anneal at 400° C. The 400°C anneal does not reduce the hardness nor cause recrystallization. Annealing at 400 °C does

Jan 1, 1952

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of' heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker's Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.' At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By G. R. Gohn, S. M. Arnold

The results of stress-corrosion tests upon several non-ferrous sheet metals are presented in this paper. The metals include tough pitch copper, five binary brasses, two leaded brasses, one copper-silicon alloy, two tin bronzes, and two nickel-silver alloys. The tests indicate that for most of these sheet metals, externally applied bending stresses below the yield point (0.01 per cent offset) do not result in stress-corrosion cracking as determined by the A.S.T.M. Tentative Method of Mercurous Nitrate Test for Copper and Copper Alloys (B 154-41T).~ Only in the cases of low brass, high brass and medium leaded brass, all cold-worked 4 B & S numbers hard, was any corrosion cracking observed below the yield strength, and in all cases such failures occurred at stresses above the proportional limit for these materials. However, when some of the same materials which showed no evidence of stress-corrosion cracking at stresses below the yield strength, are stressed beyond the yield point, stress- corrosion cracking is quite apt to occur. Since experience has shown that some of these materials, particularly the brasses, are susceptible to stress-corrosion cracking under service conditions, these tests would indicate that, besides externally applied stress and corrosion, plastic deformation in addition to that resulting from the original cold working of the material is also required to produce conditions conducive to stress- corrosion cracking.

Jan 1, 1945

By M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of' slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By Paul R. La Pointe

GEOTECHNICAL OBJECTIVES OF UCG PROGRAM Underground coal gasification (UCG) is one of several in situ extraction technologies for utilizing deep, otherwise unmineable coal. This technology involves the injection of air or oxygen into the target coal seam, ignition of the coal and recovery of product gases. Geotechnical characteristics of the coal and enclosing rock strata strongly influence the success of this Process. The flame front follows the coal cleats (Hill, 1979), and cleating and bedding control the manner in which coal collapses into the cavity, thereby affecting recovery efficiency (Ramirez and others, 1982). Moreover, coal seams typically behave as fracture dominated aquifers in which cleat orientations govern subsequent contaminant dispersal. For these reasons, the Anaconda Minerals Co. undertook a detailed study of fracturing within the Wyodak-Anderson Coal in the eastern Powder River Basin (PRB) near its Rocky Hill UCG test site (Fig. 1). STRESS HISTORY AND FRACTURING IN THE POWDER RIVER BASIN Vertical jointing, or cleating, in coals may arise from shrinkage shortly after deposition under low confining pressures, or later in time, soon after burial but after the coalification process is well advanced (Ting, 1977). There is much evidence to support the formation of cleating after coalification (e.g. Hawkes and Mellor, 1970; McCulloch and others, 1974), which suggests that the stress state existing at that time strongly influences cleat formation. McCulloch and others (1974) argue that the typically better developed face cleat forms parallel to the plane containing [ol] and [o2]. Where the relation between cleats and stess has been studied (McCulloch and others, 1974; Stone and Snoeberger, 1977; Ward, 1977; Kulander and Dean, 1978), the highly systematic face cleat strongly parallels the [o1] direction. Stone and Snoeberger (1977) report face and butt cleat measurements of N70E and N29W for the Felix Coals 220 m stratigraphically above the Wyodak at the Hoe Creek UCG site (Fig. 1). Structural trends also indicate the past state of stress in the PRB. Glaze and Keller (1963) suggest that the NE-SW regional compression during the late Permian formed major N-S fold lines and basement magnetic anomalies. Mapel (1959) describes folds having N60W and N30W rends in the northern PRB, as well as a large normal fault trending northeast. Glass (1976) also describes normal faults trending northeast. Similarly, Olive (1957) mapped normal faults

Jan 1, 1984

By Henry E. Wood

In my opinion, the concentration of minerals by flotation is the most interesting problem in ore-dressing, and will command eventually far more consideration than it has at present. For many ores it furnishes a complete method of concentration absolutely independent of specific gravity, and thus simplifies the milling of many difficult combinations. Not having to recognize the influence of specific gravity, we are also able to dispense with some of the complications resulting from classifying-conditions. Where flotation cannot be used for a complete separation of the minerals from the gangue, it will be found, in nearly all cases, to save those portions which are generally lost by reason of their fine state of division. For this reason, it should be looked upon mainly as an aid to general concentration, although there are many ores so well adapted to flotation that more than 90 per cent. of the valuable metals can be recovered from them in one operation by this process. In presenting the results of my investigations in flotation, I have endeavored to theorize as little as possible. That side of the subject has been extensively discussed by others. My earliest work with flotation was done in 1895, when I used various oils, grease, soap, etc., with results that were remarkable. I did not realize then that with water alone equally good separations could be made. Up to 1906, my endeavors were confined to attempts to keep the concentrates on the tables well wetted and away from exposure to the air. In common with others, I observed that when there mas any obstruction in the wash-water on the table of sufficient size to divert the water to either side, the concentrates collected, and, on exposure to the air, would promptly float away. This convinced me that the sulphides were all good "swimmers," and that if,

Jan 1, 1913

THE Copperton mill in reality was a sort of proving ground. It was. designed to serve three purposes: (1) to verify the accuracy of the mine sampling by actually treating substantial tonnages of ore, (2) to demonstrate on a reasonably large scale the percentage of the copper in the ore that could be recovered, and (3) to permit the testing of various kinds of machines and devices for crushing and concentrating the ore, so as to guide the engineers in designing the proposed 6000-ton milling plant at Garfield. As a matter of fact, it contained a lot of second-hand equipment sent by MacNeill and Penrose from the works of the United States Reduction &Refining Co. in Colorado; and it was by no means a model installation. Probably it would have been even less efficient, except for the skillful work of George O. Bradley and-Frank-G, Janney, both of whom had worked with Jackling at Mercur. Bradley was a mechanical engineer employed to design the plant. Later he directed the design of the concentrator at Garfield and remained as consulting mechanical engineer to the company until 1915. Janney, who afterwards became manager of mills, a position that he retained until his death in 1916, was a skilled mechanic at the Golden Gate mill at Mercur when Jackling built the plant in 1897. His flair was making machinery do what it was intended to do. He was not an ore-dressing engineer in a technical sense; but Jackling him- self was a specialist in this respect as well as in designing and construction and Janney's mechanical aptitude made him a particularly valuable man in the Utah organization. John McDonald, another of Jackling's Mercur associates, was the first mine superintendent. With practically all of the available funds earmarked for construction of the Copperton

Jan 1, 1933

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By J. R. Mihalisin

Phase changes in as-cast alloys in the Ni2 CoCr-Ni, Ti-NSAl system containing 0.1 wt pct C were studied after heat treatment at 1650°F. It was found that a vegion of CrCo-type s was developed in this system after I1000 hr. The tendency for s formation was dePendent upon the aluminum and litanium content, the s -forming tendency generally becoming more pro-nounced as the latter two elements are increased. s lended to form in interdendritic regioues and was associated with solutioning- of- carbide phases. Electron- vacancy computations for prediction of s formation on these alloys mere in sufficient agreement with what was observed experimentally to indicate that the method should be of value in assessing a-forming potential in cast alloys. However, the correlation of electrotz- vacancy numbers may not be as favorable in cast as cormpared to wrought alloys. THE increasing use of high-temperature alloys for longer times at higher temperatures has resulted in a real need for obtaining information on the phase changes taking place in these alloys since these changes often have a direct effect on properties. This paper reports on a study of the phase changes in Ni-Cr-Co-Al-Ti alloys after prolonged heating at 1650°F. The alloys were selected from the pseudo-ternary system Ni2CoCr-Ni3Ti-Ni3Al and this system was chosen because it is the basis of many of the newer cast commercial superalloys. The attempt here was not to define accurately the boundaries of s formation in the NizCoCr-Ni3Ti-Ni3Al system but to delineate the phase transformations taking place upon heating alloys covering a wide range of chemistries in this system. An addition of carbon was made to all alloys to further simulate commercial alloys. It was hoped that the information generated in this manner would be of more direct use to superalloy designers than an equilibrium diagram approach since commercial alloys generally have outlived their usefulness when equilibrium is attained. EXPERIMENTAL PROCEDURE The alloys were vacuum-melted from carbonyl-nickel pellet, vacuum-grade chromium, electrolytic cobalt, high-purity aluminum and titanium, and spec-trographic-grade carbon.

Jan 1, 1968

By G. S. Cole, G. F. Bolling

ThIS note accompanies a study of grain structure changes in metal ingots produced by the alteration of fluid motion.1 Although the Prandtl Number of aqueous solutions is much higher than that for metals, it is quite instructive to see the simulation of freezing, as pointed out by Jackson and coworkers.2-4 Accordingly we have observed the effects of natural thermal convection, the changes induced by a steady-state rotation in one direction, and the changes under oscillation.' Temperature measurements were made under duplicate conditions whenever the visual observations appeared interesting. A solution of 15 pct NH4C1 in water was chosen. In each case the solution was preheated to 90°C in a 4-in.-diam Pyrex beaker filled to a level of about 5-in. depth and covered to prevent convective air cooling. The beaker was then placed in a container of iced brine, suitably arranged on a rotating table for movement about its cylindrical axis. Upon immersion in the brine under static conditions, fluid flow was observed near the wall of the beaker before the onset of crystallization, which generally commenced only after the temperature fell to 51.5"C. The region of flow extended about 1 mm from the wall and could not be observed elsewhere. The measured radial temperature increased sharply within 1 cm from the wall and thus over a distance considerably greater than that observed for the flow. However, we note that this difference of approximately one order of magnitude between hydrodynamic and thermal boundary layers should be expected for aqueous solutions, in contrast to metallic liquids. Beyond this layer the temperature was isothermal at a given height and in general nearly 10°C warmer than at the wall. The overall visual observation was therefore supported quite well by temperature measurement. There was also a vertical temperature gradient of nearly 2°C per cm throughout the liquid increasing from the colder bottom; this of course could not be observed visually. Eventually crystals precipitated from solution. (It

Jan 1, 1968

By E. L. Tucker

IN THE metallurgy of precious metals, it has been standard practice for years to use cyanogen compounds, so it was but natural that early investigators in the field of flotation should consider these compounds as possible flotation reagents. In Australian Patent 9508, of 1913, alkali cyanides were described as suitable reagents for the separation of heavy sulfide minerals, the reagents being employed either in an alka-line or neutral circuit. In U. S. Patent 1236501, of 1917, to John M. Tibbet, the use of cyanide in conjunction with soda ash or lime is described. One of the claims of this patent reads, "An improvement in the cyanide process for the treatment of ores comprising, mixing the ore with cyanide solution and oil and alkali: emulsifying the oil in the presence of the ore, the alkali and the cyanide solution, floating a portion of the values in the pulp by producing gas bubbles in the mixture-and removing the values floated." More recently, Sheridan and Griswold, in U. S. Patents 1421585 and 1427235, describe a somewhat similar process and have, successfully introduced it in. the mill of the Timber Butte Milling Co. U. S. Patent 1429544, of 1922, to Stevens, describes the use of double cyanides of copper, zinc, and lead. The success of cyanide as a reagent in the differential flotation of lead and zinc sulfides in highly complex ores is proof that these patents have a solid foundation.. Although the technique of their application to particular ores has been worked out in many cases, no one, so far as is known, has attempted to describe the nature of the action of the cyanide or to determine the ideal conditions for its, application. It was the purpose of the present investigation to gather information on these points. Naturally this would have been an exceedingly ambitious.

Jan 8, 1925

By John C. Osmond

One of the least known geologic regions in the U.S. is the area now called the Basin and Range Province. It is paradoxical that so little geologic information has been compiled for a province that has yielded billions of dollars worth of metals and is currently producing a small amount of oil. Regional stratigraphic studies of parts of this large territory have been published only recently, and regional structural interpretations of even parts of the province are rare in the literature. This, of course, does great injustice to the earliest workers: Gilbert, Russell, Le Conte, Spur, Louderback, and others, who recognized the area as distinctively different from the rest of North America. Their simplified picture of the structure of the ranges and the province as a whole is the groundwork for present understanding and has never been superseded. Since their early works, however, geologic data from the province has consisted largely of detailed reports of widely scattered mining districts. Each district has been described as though it were an island in an unknown sea.

Jan 3, 1960

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By F. L. Wolf

The catenary system of line construction possesses so many desirable characteristics from the operating standpoint that it has wide application for all types of electric traction. Many steam roads are electrifying sections of their lines, and in most cases are operating both steam and electric locomotives over the same track. This means that the overhead catenary system is subjected to the severe corrosive action of locomotive smoke, and data concerning the resistance of various alloys to this form of corrosion are very desirable from every point of view. Reliable and specific information and data on the subject of corrosion due to steam and smoke from locomotives are extremely meager and, on this account, extensive service tests, together with accelerated tests, have been made on a number of commercial metals and alloys. The observations and data recorded in this paper are the result of a preliminary test which was started in 1923 and which has been carried on to the present time. The recognition of the need for even more detailed and accurate data has resulted in the undertaking of another test which has been in progress for about a year. The result of this test will be published in due course. Some years ago The Ohio Brass Co. was asked by one of the large steam railroad companies to furnish data on construction details for a catenary system which it was considering for one of its divisions. The selection of materials which would give the necessary physical characteristics as well as withstand the severe corrosive action of locomotive gases caused electrical railroad engineers considerable concern. At that time, there were available no specific or authentic data on these important questions: no systematic investigation of the problem appeared to have been made, even though it's importance was generally recognized. Such observations as had been made were crude in that they had been limited largely to visual inspection which too frequently is most misleading. However, the scattered information which was collected gave important clues as to how best to start an investigation. Technical literature was studied, metallurgical experts were consulted, and the problem was discussed with engineers who were in close contact

Jan 1, 1930

By R. M. Brick, Arthur Phillips

The Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic problems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segregation. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute concentration, with a resultant normal segregation or coring effect during freezing. Theoretically, musion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions aluminum-copper alloys segregate inversely and aluminum-magnesium alloys segregate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937