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By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By S. Weinig, E. S. Machlin

IN a previous study of the grain boundary stress relaxation phenomenon,' the authors had arrived at the conclusion that two successive steps were involved in the complete relaxation of stress at a grain boundary. These two steps were grain boundary migration and grain boundary slip. It was further suggested that the slower of these two processes is rate controlling. In an attempt to ascertain the validity of the above, a study of grain growth kinetics on the same alloys used for the previous study was undertaken. Separate wire specimens, 0.030 in. diam, in the same as-deformed state (99 pct reduction in area) as in the previous investigation were heated to the various temperatures for a sequence of times. The compositions used and the temperatures of testing are summarized in Table I. A statistical determination of grain size was then made on each specimen, using the average length of traverse between boundaries as a measure of the grain size. Examples of typical results obtained are shown in Figs. '1 and 2. The grain growth law D = ktn was found to fit most of the data. Using this relation, values of the grain growth exponent n were calculated and the inter -esting dependence of n on solute content shown in Figs. 3 and 4 was then obtained. Also, it was found that the constant K which was obtained from extrapolation is roughly independent of solute content. (K is uncertain to within ±25 pct.) An estimate of the activation energy for grain growth was made using the technique of Burke? This method utilizes the plot of the reciprocal of time necessary for the grain size to increase from a definite starting size Do, to a final size D, for each isothermal heat treatment. The slope of this curve corresponds to the heat of activation for the process. In Fig. 5 the rate of grain growth is plotted against the reciprocal of absolute temperature. The activation energies were obtained from these curves and are summarized in Fig. 6. Discussion It is interesting to note that the same saturation in the variability with concentration has been found for the grain growth exponent n in this research as was found in the previous researches on both grain boundary stress relaxationa and internal friction of dislocation origin." The significant feature is that saturation in the variation of these properties has been found to occur at about the same level of solute concentration, namely, between 0.1 and 0.5 atomic pct. The only characteristic common to these different quantities is that solute adsorption at grain boundaries and dislocation can take place and affect these values in a similar fashion. Thus, it is concluded that the grain growth exponent n depends upon solute adsorption at the grain boundaries. It appears, therefore, that theoretical considerations leading to the contrary conclusions5,6 have not treated the real process by which solute atoms exert their effect on grain growth. Prior to the analysis of the observed activation energies, certain of the aspects of the aforementioned grain boundary stress relaxation investigation will be briefly reviewed. It was found that with the addition of solute atoms the grain boundary stress relaxation peak (internal friction vs temperature) decreased in intensity. Simultaneously a second peak was observed which increased with increasing solute atoms. Both of these peaks were shown to be the result of grain boundary stress relaxation. They have been termed, respectively, poire peak and solute peak. It was suggested that the solute peak was dependent upon grain boundary migration, whereas the pure peak was a manifestation of grain boundry slip. Activation energies for both peaks were obtained as a function of Solute content. The value of the activation energy in the temperature range corresponding to the solute peak was

Jan 1, 1958

By T. M. Morris

THE rate of flotation of solid particles determines the percentage recovery of these particles which can be obtained during a given time interval. It is an established fact that the recovery is greatest in the fine sand size range and falls off on either side of this size range. It is also a fact that the history of the development of concentrating devices has been marked by a desire to recover the small particles: tables were developed to treat material too fine to recover in jigs; flotation recovers material too fine to be recovered on tables. As our ores become more complex and require finer grinding, a greater proportion is in the slow-floating size range. It is therefore of economic importance that the effect of size of particle upon rate of flotation be studied. Many studies have been made along this line. The present investigation attempts to quantify the rate of flotation by means of a rate equation, and then compares the effect of size upon the rate of flotation. It was found that the flotation rate constant increases with increase in diameter of particle in the size range smaller than the optimum size particle. The flotation rate constant decreases with an increase in diameter of particle in the size range coarser than the optimum size particle. This suggested two different actions taking place, and these are discussed. Suggestions for further work in order to improve the flotation rate of both fine and coarse particles are made. The usual method of expressing rate is to plot cumulative percent recovery vs time. If we knew the equation of this kind of curve we could replot it as a straight line, and the slope of the line would be an index of the magnitude of the flotation rate. It is easier to compare straight lines than curves. The basis used for obtaining the equation of the recovery vs time curve is the law of mass action. This law states that the "rate of a chemical reaction is proportional to the `active masses' of the reacting substances present at any given time." This, of course, implies a constant temperature. We can modify this for our use by using the term flotation reaction instead of chemical reaction and the term floatable particle instead of active masses. [ ] where C denotes concentration of particles, t denotes time, k denotes a proportionality constant. If the exponent of C is 1, then we have a first order rate reaction. If the exponent of C is 2, then we have a second order rate reaction. For a first order rate reaction, we obtain, after integration, [ ] where k is again a proportionality constant and has the dimension of the reciprocal of time. C, is the original concentration or weight or percentage of floatable particles. C, is the concentration or weight or percentage of floatable particles remaining in the flotation cell after time t. If all particles of the mineral to be floated were capable of floating we could take C, as 100 and C, would be 100 - R, where R is the cumulative percentage recovery of mineral at time t. But it is not usual for all of the particles to be capable of floating, because of surface oxidation, etc. Therefore, we must introduce a factor x which is the percentage of unfloatable mineral. Hence the first order equation is [ ] It has been proposed by various workers1-3 that this equation describes the flotation rate. More recently N. Arbiter4 states that a second order rate equation fits the recovery vs time curve more closely than does a first order rate equation. Morris' has discussed the evidence presented for this statement. It has been concluded that the first

Jan 1, 1952

Objective To accurately measure very low air velocities (0-100 ft/min) in U.S. large-opening underground metal/nonmetal mines. Background Hundreds of metal/nonmetal underground mines operate throughout the United States. They extract commercial products from deposits such as limestone, salt, and gypsum. Mining generates a wide variety of gases and dusts, such as silica, diesel exhaust, radon, blasting byproducts, and perhaps even methane. If these substances become airborne, they can adversely affect the health and safety of underground workers. Many metal/nonmetal mines have large cross-sectional airways that could be 60 times larger than an average underground coal mine entry. These large airways require adequate volumes of fresh air to dilute, make harmless, and exhaust the toxic and, at times, explosive byproducts. However, in some underground mine sections, air movement is barely perceptible. The technology of measuring very low air velocities will become increasingly more important for operators of large-opening stone mines in order to monitor miner exposure to diesel particulate matter. Conventional anemometers (e.g., vane) are capable of accurately measuring air velocities only above 100 ft/min. Thus, it was necessary to investigate other anemometry technology to detect low air velocities in the range of 0-100 ft/min. Two different portable ultrasonic anemometers were tested. Actual testing was done in an underground limestone mine with openings about 51 ft wide by 29 ft high. Ultrasonic Anemometers Vane-type anemometers are commonly used by engineering personnel throughout the underground coal mine industry. They work well in measuring air velocities >100 ft/min. However, a separate technology, e.g., portable ultrasonics, is needed to measure air velocities much below 100 ft/min at various places within the large mine opening. Laser-doppler technology was also considered for this application, but was ruled out because of its high cost and other technical limitations. With no moving parts, the portable ultrasonic anemometers are claimed to be accurate down to about 1or 2 ft/min. The first type of ultrasonic anemometer that was examined underground is manufactured by Gill Instruments Ltd., Hampshire, U.K. The U.S. distributor is IN USA, Needham, MA. The Gill Instruments Solent Volometer (figure 1) is a battery-powered, single-axis anemometer meant for measuring low to medium air flows up to1,999 ft/min. It uses the ultrasonic "time of flight" principle where pulses of high-frequency sound are transmitted along the air flow path and the time taken to reach the receiver is measured. The faster the air speed, the quicker the pulses reach the receiver. The second ultrasonic anemometer that was examined under-ground is manufactured by Airflow Developments Ltd., Buckinghamshire, U.K. The U.S. distributor is Airflow Technical Products, Inc., Andover, NJ. The Anemosonic UA-6 (figure 2) is a battery-powered, handheld instrument with digital display. It measures air velocity (0 to 9,999 ft/min) or volume flow, flow turbulence intensity, and air temperature. Neither device is considered to be intrinsically safe for use in underground gassy coal mines. A comparison of salient specifications of both instruments is shown in table 1. The total suspended weight includes the instrument (Gill) or instrument probe (Airflow) plus about 35 ft of connecting cable attached to the pole. This combination of instrument plus cable length allows two operators to measure air velocities up to about 30 ft above the mine floor. Figures 1 and 2 show how each unit would be attached to an extensible, graduated fiberglass rod in order to position the sensor probe at a certain spatial point (centroid of the quadrate) within the underground large opening.

Jan 1, 2003

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By W. R. Hibbard

It has been proposed1 on the basis of slip and flow that the ideal deformation texture of drawn wire for face-centered cubic metals is a (111) direction parallel to the wire axis. Under these considerations, an intermediate [loo] texture is permissible but should eventually change to the stable [Ill] orientation. This theory does not explain why copper and its alloys containing up to about 30 pct nickel, 5 pct zinc and 1 pct aluminum were found to have a double [Ill], [100] texture, while alloys with at least 8 pct zinc and 2 pct aluminum developed essentially a single [Ill] texture.1,2 It does suggest, however, that the [loo] component of the former alloys should disappear with additional deformation.3 Some evidence exists to support this suggestion. Howald4 reported that annealed copper wire previously drawn 93.8 pct and 98.5 pct developed a single [Ill] texture. Since, in wire, the drawn and annealed textures are similar, these wires probably had a single [Ill] deformation texture before annealing. In addition, although cold rolled polycrystalline copper and 80-20 brass were found to form different types of pole figures,5,6 single crystals of these metals when rolled from the stable (110) [112] orientation were found to produce essentially the same polo figure.7.8 It may be, therefore, that while the addition of solute elements changes the path by which the final texture is obtained, the final texture is not changed. Experimental Results The wires remaining from the previous investigation1 already drawn about 50 pct reduction in diameter were further drawn to 86 pct and then to 96.4 pct total reduction in diameter. The textures were determined after these stages by transmission X ray photograms taken with a copper K-alpha beam rotated 0 degrees toward the wire axis. It was found that the ratio of the [111].] and [100] intensities of the double texture in copper and its alloys containing 0.94 pct aluminum, 30.70 pct nickel, 2.61 pct zinc and 4.99 pct zinc increased from about 3:l for the 50 pct reduction to about 9:l for the 86 pct reduction. After 96.4 pct reduction, these wires exhibited essentially a single [lll] texture. Summary Thus, the drawn wire deformation texture of copper and its alpha solid solution alloys containing aluminum, nickel or zinc is essentially a single [Ill] texture as predicted by theoretical considerations of slip and flow.' For copper and its alloys containing up to about 1 pct aluminum, 5 pct zinc and at least 30 pct nickel, an intermediate [loo] component is found after about 50 pct reduction in diameter, but disappears after about 95 pct reduction in diameter. For alpha solid solution alloys containing at least about 2 pct aluminum and 8 pct zinc the single [Ill] texture is developed considerably more easily and is found after about 50 pct reduction in diameter. No explanation of this compositional effect is apparent. Similar work is contemplated for cold rolled and cold compressed alloys. References 1. w. R. Hibbard, Jr. and M. K. Yen: Trans. AIME 175, 126. Metals Tech., Feb. 1948, TP 2334. 2. W. R. Hibbard, Jr. and D. E. Trout, 11: Trans. AIME 185, 620. Jnl. of Melals, Sept. 1949, TN 18. 3. W. R. Hibbard. Jr.: Disc. of R. M. Brick's paper on Deformation Textures, ASM Symp. on Cold Working of Metals, Oct. 1948. 4. T. S. Howald: Disc. of Ref. 1. Trans. AIME, 175, 126. Melals Tech. Aug. 1948, TP 2449. 5. R. M. Brick, D. L. Martin and R. P. Angier: Trans. ASM (1943) 31, 675. 6. 0. Dahl and F. Pawlek: Zlsch. Melall. (1936) 28, 266. 7. C. S. Barrett and F. W. Steadman: Trans. AIME (1942) 147, 57. 8. J. E. Burke and C. S. Barrett: Trans. AIME 175, 106. Melals Tech., Feb. 1948. TP 2327.

Jan 1, 1950

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By L. Burris, C. H. Stockman, I. G. Dillion

Zone melting is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Equations are presented which 1—predict the concentration profiles after successive passes of the zone and 2—give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing in the last zone length. These equations were solved numerically using an electronic computer, and the concentration profiles are presented as a function of the solute distribution coefficient and the ratio of molten zone to total bar length. ZONE MELTING is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Separation occurs if the solid freezing from a solution at any moment has a composition different from that of the liquid from which it is freezing. Solutes which lower the freezing point will tend to remain in solution and will be moved in the direction of zone travel. Solutes which raise the freezing point will preferentially freeze out, and they will be moved in a direction opposite to that of zone travel. After repeated unidirectional passage of a molten zone through a bar of material, impurities will be concentrated in the ends of the bar. A limiting concentration gradient will be reached in the bar after a large number of passes of the molten zone. Both the magnitude of this limiting concentration gradient and the rate of movement of solute in any pass depend on the zone length and on the equilibrium concentrations of solute in the liquid and solid phases. The basic theory of zone melting was thoroughly covered by Pfann.1 The purpose of this paper is to extend the theory of zone melting by presenting 1—equations which relate the concentration profiles in successive passes of the zone and 2—equations which give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing* in the last zone length concentration of a given solute in the solid to the concentration of the same solute in the liquid. Analytical methods for determining the concentration profiles after any pass have been developed by Lord2 and Reiss. The method developed by Lord does not take into account normal freezing in the last zone and also becomes very complicated when the number of passes becomes large. The method developed by Reiss enables the direct calculation of the complete concentration profiles (including that in the last zone) after any pass for values of k close to unity (0.9 < k < 1.1). Both methods are useful and provide valuable insight into the zone melting process. The equations given in this article are based on the same assumptions used by Pfann. These are: 1—uniform composition in the liquid, 2—negligible diffusion in the solid, 3—constant distribution coefficient, 4—constant length of the liquid zone (except at the ends), and 5—solubility of the solute in the melt is not exceeded at any point. Equations for Concentrations in Successive Passes For a melted zone of length 1 at the left-hand end of a bar of uniform unit cross-section, the amount of solute in the liquid is J0Cn-1(x) dx [1] where the subscript is the number of the pass. Cn-1(x) represents the concentration (expressed as weight per unit volume) obtained in the previous

Jan 1, 1956

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".&apos; The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley&apos;s publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1&apos; for ?H°, and the entropy function.

Jan 1, 1952

By Richard E. Thill

The Bureau of Mines&apos; Oil Shale Data Bank (OSDB) was created in 1976 to serve as a centralized source for the storage, retrieval, and dissemination of technical literature, patents, and information on research projects in oil shale. Thousands of bibliographic references, patents, and research projects relating to the mining of oil shale have been identified, abstracted, and indexed according to selected keyword topics. The resulting data bank listings are contained in three sections, each with a separate keyword breakdown for use in rapidly identifying references pertaining to a specific subject. All references cited in the OSDB were published prior to an established cut-off date of May 1, 1981, when a redirection of Bureau of Mines programs resulted in the loss of project funds and the subsequent phasing-out of data bank operations. ACKNOWLEDGMENTS The oil shale data bank listings are the result of a team effort of the project staff. The contributions of Jimaleen Jansma for keypunching, information acquisition, and data entry, and John Brandenburg and Sandra rake for keywording and information acquisition are gratefully acknowledged. Appreciation is expressed to the staff members of the Smithsonian Science Information Exchange, Washington D.C. for their cooperation in supplying data on recent research projects in oil shale for inclusion in the OSDR listings. Appreciation is extended also to the staff of the Gallegos Research Group for assisting with computer services to obtain the final printouts and transfer of files onto magnetic tape.

Jan 1, 1982

By J Kinal, P Steinier

A considerable volume of work exists in the literature examining the electrochemical interactions between grinding media and sulfide minerals. Broadly, most sulfide minerals are more noble than forged steel grinding media used during comminution, therefore a galvanic couple between the media and the sulfide mineral(s) exists, which increases the corrosion rate of the grinding media. The corrosion products of the grinding media, iron oxy-hydroxide species, invariably precipitate on to the surfaces of the sulfide minerals thereby affecting their floatability. This paper explores the science behind these corrosion reactions, and provides an explanation of their impact on the pulp chemistry of sulfide mineral slurries and subsequent flotation behaviour. A number of laboratory and plant case studies are used to illustrate the benefits of changing to a more inert grinding media.

Jan 1, 2005

By Hamid-Reza Manouchehri

"Sustainability calls for maintenance, rational use and enhancement of natural resources as well as balance consideration of ecology, economy, and social justice. The challenges in mining industry call for a sustained global effort using the leverage of available technologies and emerging new technologies. The industry uses significant amount of energy with the highest portion in comminution. To conserve energy, attempts have been made to improve the efficiency of the conventional crushing and grinding equipment. Nevertheless, the new and energy efficient comminution technologies are favorable through a longer term strategy. Since crushers are more energy efficient than mills, it is logic to conduct part of milling, in the crushing stage. After years of research and development, Sandvik introduces a new crushing technology, VibroconeTM, to change traditional crushing concepts. The new crushing device is able to crush and grind particles with a higher reduction ratio, more than two fold, than that of conventional crushers. By implementation of the new technology, a suitable feed size for milling can be provided to conserve energy as well as media and liner consumption, to reduce milling circulating load or increase mill capacity. There are other benefits associated with this machine, one of them being providing a higher surface area. This paper discusses the performance of the machine and its applications for comminuting different ores."

Jan 1, 2014

By P. Schmidt, M. Hopf

Water-cooled parts of submerged arc furnaces are potentially dangerous, especially if molten matte or slag contacts the water. Explosion hazards and metal run-outs generate high costs for production loss and repairs - not mentioning the possible loss of human life. This paper reports about practical results of wear measurement on intensive water-cooled tap-holes and spray-cooled side walls. On the one hand an embedding technology has been developed, that is used e.g. in water-cooled copper tap blocks or copper side wall coolers. Second the application of the sensor installation on the inner side of a water-cooled steel shell will be discussed. The fibre-optic sensor is fed through a specially arranged piping system and measures numerous temperatures over its entire length. By using the thermal conductivity of the installed refractory materials the lining thickness is calculated. The practical installation of the sensors will be discussed and the results of the wear measurement will be compared to the theoretical FEM calculations. The highly sensitive and accurate temperature measurement, as well as the recalculation of the impact of differences in the cooling water temperature, allows the exact determination of the remaining lining thickness. The discussed technologies offer efficient and safe monitoring of tap-holes, side walls and other endangered parts of pyro-metallurgical smelters.

Jan 1, 2015

By T. Wang, R. G. Reddy, D. Mantha

"A new eutectic LiN03-NaN03-KN03-KN02 quaternary molten salt system was calculated using thermodynamic modeling. The eutectic temperature was predicted to be 100°C. The melting point and heat capacity of the salt eutectic composition were determined using DSC. The experimentally determined melting point is in excellent agreement with the predicted value. The melting point is more than 124°C lower than that of the KN03-NaN03 solar salt. The density of the molten salt was experimentally determined as function of temperature. Using the density, heat capacity and the melting point, thermal energy storage density and gravimetric storage density of the quaternary molten salt were calculated and compared with that of solar salt. The larger storage density value of this molten salt indicates that this salt has a better energy storage capacity for solar power generation systems.IntroductionMolten salts have been used as thermal energy storage media for solar energy applications. Nitrates are being used in the solar energy applications for their low melting point, low unit cost, high heat capacity, high thermal stability, negligible vapor pressure and high energy storage density [l]. Solar salt (NaN03/KN03: 60/40) is the most popular thermal energy storage medium which is currently being used with the freezing point of 221 ·c [2]; another ternary system HITEC® which contains NaN03, KN03 and NaN02 has freezing point of 141°C [3]. Newer nitrate salt mixtures are being studied and projected as potential candidates for thermal energy storage (TES) and heat transfer (HT) applications. Based on these favorable features, molten salt can work directly as the energy storage medium below 500°C [l]. Development and synthesis of newer molten salt mixtures with freezing point lower than those currently used for thermal energy storage applications is necessary for sustained utilization of solar energy. The approach to develop lower freezing point molten salt mixtures is by the prediction of new eutectic mixtures and also by the development of new nitrate compounds."

Jan 1, 2012

By Alton B. Cook

In the Scurry Reef field, Scurry County, Tex., a study was made to determine the physical properties of the oil in all parts of the reservoir by a new method developed for this study. The method involved correlation of data from a survey 1 of the gravity of the produced oil, from measurements of gas-oil ratios on key wells selected to give representative data for the entire reservoir, and from laboratory analyses of reservoir oil samples. A field survey was made of the API gravities of the produced oil by testing oil samples from 107 key wells. Precise gas-oil-ratio tests were made on 45 key wells that were producing under comparable separator-operating conditions. Subsurface-oil samples were obtained from seven wells, selected to provide reservoir oils ranging approximately from a minimum to a maximum in saturation pressure. The physical properties of the subsurface-oil samples were determined, and correlations were made of these laboratory data with the field gas-oil-ratio test data. These correlations were then used to estimate physical properties of the oil throughout the reservoir. A logical procedure of determining the variations in physical properties of reservoir oils in most fields is to obtain and analyze subsurface-oil samples from enough key wells to provide an ample coverage of the field. Under this procedure, data from a large number of samples would be needed to provide the desired information on the Scurry Reef field, as it is one of the largest known in the United States.

Jan 1, 1955

By H. Masuda

The lijima Zinc Refinery started operation in 1972, and has today an annual capacity of 200,000t-Zn. The hematite process was employed for the first time and the ideal of waste-free refinery has been pursued for 30 years. In recent years, however, only half of the hematite produced would be sold to the cement industry and hence a reduction of arsenic level has been necessary in order to sell the entire amount produced. The arsenic cementation process with zinc powder, developed through a long time laboratory research was found among some options as the best for the hematite process. The construction work started in 2000 and the facility was put into operation in 2001, As a result in the same year all hematite were sold to the cement industry. The outline of this project, present operations and technical issue are reported in this paper.

Jan 1, 2003

By Muhlis Nezihi Saridede, Burak Birol

"The scraps of high quality steels generally contain expensive alloying elements such as chromium, vanadium, nickel, etc. These scraps are melted in an induction or an electric arc furnace and refined in ESR (Electroslag Remelting) purification process. A significant amount of alloying elements are lost during these processes. In order to avoid these losses, scraps can be utilized directly in ESR by skipping the melting step. In this study, 316L stainless steel scraps were refined in ESR with selected synthetic slags. The products were analyzed by optic emission spectrometry and the effects of slag compositions on the alloying element losses were examined. According to the analysis of the scrap and the products, generally chromium, nickel and manganese losses were encountered. It was determined that the alloying element losses has no connection with electrical conductivity. The slag containing CaF2, Al2O3, and FeO gives the optimum Cr and Ni losses.IntroductionElectroslag remelting (ESR), which is the consumable electrode refining process, finds a wide range of utilization for the production of high quality, low inclusion alloys. This process is based on melting a consumable electrode under a molten synthetic slag containing CaF2, Al2O3, CaO etc. The synthetic slag provides the chemical refining and insulation of molten metal from air which leads to a higher purity and an inclusion-free product. [ 1,2] A schematic diagram of ESR system is shown in Figure 1."

Jan 1, 2011

By Erwin Stötzer, Renato Fiorotto, Wolfgang G. Brunner, Manfred Schöpf

"Deep mixing methods can be used economically for the construction of cut-off or excavation support walls where other systems such as traditional soldier beams and lagging walls would yie ld unsatisfactory performance, where the installation of vibrated or driven sheet piles could cause vibration induced settlements and where concrete diaphragm walls would be time consuming and expensive. The new CSM method can largely replace the more conventional single or multiple auger methods of soil mixing or jet grouting. The cutter tool is similar to a cutter used in diaphragm walls or cut-off walls and is operated with a Kelly mounted on a drill rig. With this system much deeper walls can be installed and even hard soil layers can be penetrated. CONVENTIONAL SOIL MIXINGIn 1962 Norman Liver patented an auger-based soil mixing technique that has become the basis for the world's current technology.The deep mixing method (DMM), as it is known today, is an in situ soil treatment and improvement technology where the soil is blended with binders and/or other materials that are introduced in a slurry or dry form.Typically one or more hollow, rotating mixing shafts tipped with some type of cutting tool are mounted vertically to the mast of a base carrier and are driven into the ground by hydraulic or electrically powered rotary heads. The shafts above the cutting tool may be further equipped with discontinuous auger flights and/or mixing paddles. The binder is injected through the hollow shafts to nozzles located near the cutting tool where it is mixed with the ground to form columns of treated soil.Individual column diameters range from 0,6m to 1,5m and may extend to 40 m in depth. They can be arranged individually or in contiguous or secant patterns to produce a wide range of treated soil structures on both land and marine projects. Typical configurations are: Single elements, rows of overlapping (secant) elements, grids, lattices and blocks (Fig. 1 )."

Jan 1, 2005

By P Craig, A Crosky, H Ramandi, S Saydam, H Chen

Frequency of reports on premature failure of rock bolts and cable bolts have increased in past two decades. Such a failure threatens both the safety of underground mine workers and the economic viability of the operations. Herein, we report on analysis of rock bolts and cable bolts failed recently in three underground mines in Australia. Magnetic particle inspection (MPI) and scanning electron microscope (SEM) techniques were used to study the failed bolts. MPI showed a number of subcritical cracks on the surface of the bolts. The majority of the cracks in both cable bolts and rock bolts were initiated from the base of ribs (indentation) where the stress concentration was high. SEM examinations showed tearing topography surface (TTS) in all failed rock bolts and cable bolts. These indicated that the failure occurred through hydrogen assisted stress corrosion cracking (HISCC). The results of this study enhanced the understanding about the failure of rock bolts and cable bolts in underground mines. CITATION:Chen, H, Ramandi, H, Craig, P, Crosky, A and Saydam, S, 2018. Analysis of premature failure of rock bolts and cable bolts failed in underground coal mines, in Proceedings The Fourth Australasian Ground Control in Mining Conference (AusRock), pp 407–413 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Nov 30, 2018

By R. G. Diale, H. R. Chauke, T. M. Ledwaba, P. E. Ngoepe

FeCo alloys play an important role in soft magnetic materials with a wide range of technological applications due to their high saturation magnetization and Curie temperature. However, these alloys have low ductility at room temperature. The ductility can be improved by the ternary addition of elements such as V. A density functional theory supercell approach was used to generate B2 Fe50Co50-xVx (0 ≤ x ≤ 50) structures and the properties were evaluated at different atomic percentage compositions to determine the ductility at room temperature. The structures were fully optimized to obtain better equilibrium ground-state properties such as lattice parameters and thermodynamic properties for both binary and ternary systems. The stability of Fe50Co50- xVx was evaluated from the heats of formation, elastic properties, and phonon dispersion curves. Furthermore, magnetic strength was evaluated from magnetic moments. It was found that all structures are thermodynamically stable due to the negative heats of formation. The calculated Pugh’s ratio and Poisson’s ratio confirm that alloying with V effectively improved the ductility. It was also found that Fe50Co50-xVx showed a positive shear modulus for the entire concentration range investigated, in agreement with phonon dispersion curves. The ternary addition of V to the FeCo system resulted in reduced magnetic strength due to a decrease in magnetic moments. These findings reveal that B2 FeCo-V alloys can be used as components and actuators for the automotive industry.

Jun 10, 2024