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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.".' 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'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' for ?H°, and the entropy function.

Jan 1, 1952

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton' reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler' stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

By J. I. Budnick, W. B. Ittner III, D. P. Seraphim

A reliable technique has been developed for producing single crystals of tantalum in the form of small diameter wires. By suitably heat treating these and polycrystal samples, first in an oxygen atmosphere and finally in vacuum, it has been found possible to reduce residual resistivities to 10-3 microhm-cm. The purity of these samples is thus comparable to the purities obtained in zone-refined silver, copper, and aluminum. THE growth and purification of pure single crystals of the transition metals is, in general, difficult. The high melting and annealing temperatures of these metals make it necessary to employ rather special techniques in any crystallization process. In addition, the transition metals show a great affinity for and are easily contaminated by nitrogen, oxygen, and carbon. Recently, however. a number of investigators have been successful in growing,

Jan 1, 1961

By C. B. Alcock, R. G. Hudson

Sulfur pressure measurements above FeS in equilibrium with iron have been carried out by the Knudsen orifice method. A comparison is made of the weight loss of the cell per unit time obtained in the above experiments, that calculated from Richardson and Alcock's measurements of the S2 pressure above FeS in equilibrium with iron, and the dissociation constant for diatomic sulfur from spectroscopic and thermal data. EXTENSIVE equilibrium measurements have been made to determine the sulfur potentials of a great many systems of metallurgical interest.' In order to confirm their reliability, to supply data which may be of use in further thermodynamic calculations, and to establish the reliability of the Knudsen orifice in obtaining accurate thermodynamic values at high temperatures, the present investigation on the pressure of the gaseous species above FeS in equilibrium with iron has been carried out. The Knudsen orifice method has been used for these pressure measurements. Experimental The apparatus and general technique for this investigation are the same as that reported for the determination of the vapor pressure of silver.' To reduce the residual gas pressure in the evacuated chamber, a titanium getter, maintained at run temperature, was introducbed. Several types of Knudsen cells were used—platinum, zircon, and fused silica. The orifice in the zircon cell was fashioned with a small diamond wheel. The same precautions were used in this investigation as were employed in the work on Mo2S2.3 The FeS-Fe mixture was prepared by heating a sample of pure FeS,, supplied by K. K. Kelley of the Bureau of Mines, with excess iron powder, cp grade, obtained from the Fisher Scientific Co. These two substances were heated in a closed Armco iron crucible at 960°C, held in a vacuum of less than 10" mm Hg for 24 hr. The mass was then removed from the cell and ground in an agate mortar. In this form it was charged to the various Knudsen cells. Heating the Knudsen cell for an additional two days was sufficient to obtain constant rates of weight loss of the cell. The data obtained in this investigation are recorded in Table I. To establish whether or not a sulfide of iron is volatile at these temperatures, 0.7646 g of the FeS-Fe mixture, described above and containing 69.2 pet Fe, was placed in the zircon Knudsen cell. Run Nos. 103 to 109 were performed on it. After the completion of these runs, the total amount of iron left in the cell was obtained by chemical analysis. It contained 0.537 g Fe, compared to 0.529 g in the original charge. Thus, there was an apparent gain in iron of 1.5 pet. This is attributed to unknown experimental error, and the conclusion is that no sulfide of iron is volatile. The vapor pressure of pure iron4 is about one thousandth that of the sulfur pressure' at these temperatures. The vapor pressure of iron inside the Knudsen cell will be almost exactly that of pure iron, since in the iron-rich phase the percentage of sulfur is of the order of 0.025 pet.At this low percentage of sulfur Henry's law is probably obeyed by the sulfur. Thus, the iron will obey Raoult's law. In any event, the vapor pressure of iron will be lower than that of pure iron and, since the vapor pressure of pure iron is negligible compared to the pressure of sulfur, the weight loss of the cell due to the vaporization of iron should be negligible. Since neither iron nor FeS is volatile to an appreciable extent, the total weight loss of the cell must be due to the vaporization of sulfur. Discussion and Calculations On the assumption that S, is the only gaseous species present in appreciable quantity, its pressure

Jan 1, 1957

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe's formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade's exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By Leo Brewer, Gerd M. Rosenblatt

Thermodynamic calculations predict the species vaporizing from metal-oxide mixtures when reliable free energy functions, enthalpies of formation, and dissociation energies are available for the possible gaseous and condensed oxide components. Calculations of the oxygen to metal ratio in the vapor phase compared with the oxygen to metal ratio in a liquid metal saturated with oxide impurity are presented The possibility of purifying metals contaminated with oxide by vacuum melting or by distillation is discussed. Kinetic considerations affecting rates are neglected. IN recent years extensive information has been obtained on the thermodynamic stability of gaseous oxides of metals due to a variety of new types of measurement. Perhaps the greatest amount of information has come from the application of mass spec-trometry to the study of high-temperature vapors.' In many instances oxides of quite unusual oxidation states are found to be important in the high-temperature vapors. At low temperatures the standard free energy change for a reaction as given by the equation ?F° = ?H° - T?S° is determined primarily by the AH" value. However, at higher temperatures where the value of T in the T?S° term is large, the entropy term becomes equal to or greater than the AH term. At low temperatures only reactions for which AH is negative or only slightly endothermic are of importance. This restricts the main equilibrium species largely to those with completed octets or those with the principle oxidation number of the element. At

Jan 1, 1962

By R. A. Davidson, L. Silverman

RESIDENTS of many urban centers are becoming increasingly aware of the obscuring effect of fume and smoke discharge from power, metallurgical, chemical, and other industries; and they, as well as the legislatures of these affected cities, are agitating for cleaner air. Management's most pressing problem is to find an economical way to reduce process effluents in response to the growing pressure from population and legislative demands. The removal must be done, if possible, without handicap to the current operation, since the costs of relocating are often excessive or prohibitive. In fume recovery or disposal, an important item to consider is whether or not the material being discharged has any value. If it has commercial value, the cost of its recovery may offset or aid amortization. For this reason, in making a study of the specific problem in hand, a major factor was the nature of the material emanating from the stack: in particular, its particle size, size range, and its chemical and physical composition, as well as its potential value and utility when recovered (in either a wet or dry state). Should the product have no commercial value, it must be disposed of at minimum cost in a way to prevent recontamination. Initial studies were therefore made to determine stack concentrations and volumes of material evolved from the operations. The next phase of the study concerned the physical and chemical nature of the collected fume. The third portion of this paper describes the wet and dry collector studies undertaken to recover the fume. Cleaning Requirements for Ferroalloy Furnace Operation The basic need for any effluent collection equipment is the highest possible efficiency and the lowest tolerable resistance when the power consumption involved is considered. Since the electric furnace effluent is largely composed of fume of small size (less than 0.5u), it has high light obscuring properties, and even low concentrations will cause some loss of visibility and be evident to nearby residents. The permissible limit for fly ash emission in many cities is based on a weight value (viz, approximately 0.4 grains per cu ft), but the smoke density values are dependent upon a shade of color. In the case of the Los Angeles County code, emission is restricted to pounds per pound of material processed per hour basis (but not exceeding 40 lb per hr for any one given plant operation). If an average particle size of the fume from ferro-silicon alloy electric furnaces is assumed to be 0.4u (as shown later, this is the approximate mean size) and an average loading of 1 grain per cu ft (stp), each cubic foot of stack gas will contain approximately 75x10 10 particles (based on assumed, and confirmed, spherical shape and a standard deviation of unity). When it is realized that the air in metropolitan areas, which are also general industrial areas, contains approximately 5x108 particles, the tremendous light scattering effect of this concentration becomes apparent. Consequently, nearly 100 pct collection would be necessary to equal the average concentration. Fortunately, however, discharge from a high point above ground (50 to 100 ft) will result in at least a thousandfold dilution, or the stack concentration reaching the ground in the foregoing case might result in a ground concentration of ' particles. If the concentration at the source could be reduced by a factor of 100 (99 pct efficiency of collection), then a concentration of 75x10" particles would be diluted to 7.5x10' which would be very satisfactory. An efficiency of 90 pct (factor of 10 decontamination) at the source would result in a discharge of 75x109 articles which upon dilution yields 75x10 which is still 15 times the general air value. Another approach to this consideration is to use the value of concentration of 0.005 grains per cu ft for the value of a visible effluent as cited by Kayse.1 To attain this value with an average loading of 1 grain per cu ft would require an efficiency of 99.5 pct. Since the foregoing value is not based on any reported size of fume particles, it is felt that the numbers' approach given previously is more reliable. These calculations serve to indicate the desirability of thorough cleaning, preferably at the source, and with efficiencies well above 90 pct, preferably above 95 pct (dilution 1:20). One of the most important items in any control program is to reduce the concentrations as close to their sources as possible. The use of better furnace design, deeper coverage over the electrodes, and the prevention of blows or breaks in the surface all help to reduce dissemination; consequently, all of these improvements should be made, if possible, to cut down the effluent load. In addition, in order to minimize the volume of contaminated air that has to be cleaned, the furnace should be enclosed as much as possible. Test Arrangements Before fundamental studies with collectors were made, a furnace stack selected for the test program was sampled to determine the gas temperatures and

Jan 1, 1956

By Ramin Motamed, Joseph A. W. Toth

Evaluation of the capacity of large-diameter drilled shafts using current load test methods present challenges when considering the magnitude of loads required to fully mobilize their capacities. Often, these full scale tests do not fully mobilize the capacity through side resistance. Therefore, the need for innovative solutions to extrapolate side resistance and interpret nominal capacity are of key interest. In this study, we evaluate three methodologies for extrapolating unit side resistance based on bi-directional load test data. Fellenius (2001) presented these methods for interpretation of pile capacity using static load tests. Our interpretations are based on the evaluation of 116 load tests. Unit side resistance was calculated and reviewed for each load test and categorized using three criteria of mobilization; (A) full, (B) partial and (C) linear. This study specifically focuses on load tests that showed fully mobilized unit side resistance behavior (Criteria A). The three methodologies were applied assuming Criteria (A) load tests were mobilized to 50% of their measured values. Subsequent comparisons of each extrapolation were then compared against the full measured values for each test and generally showed good agreement. INTRODUCTION It is widely accepted that conducting load tests such as standard top-down tests or bi-directional (i.e. O- cell) tests can help designers understand load-settlement behavior and the nominal resistance of drilled shaft foundations. These load testing methods provide the advantage of confirming design assumptions as well as improving the reliability of the foundation design. The potential cost savings from the application of these methods for mid to large size projects is self-evident. For example, in a recent project in Northern Nevada, an O-cell test on a 6.9 ft diameter, 114.8 ft length drilled shaft imposed an initial cost of $125k to the project, resulting in a 15% reduction on the total foundation cost; equivalent to $1.3 million in overall savings (Pease, 2014). However, the costs of implementing such methods on smaller projects can be prohibitively expensive (Hagerty et al, 2016). Despite the clear advantages of drilled shaft load testing, the current practice is not without limitations. Performing load tests on large-diameter drilled shafts with high capacities is a challenge considering the significant loads required to fully mobilize the capacity of such foundations. In some cases, the feasibility of these tests is impractical because the associated initial cost is not guaranteed to outweigh the final savings. As a result, large scale load tests are sometimes ruled out from the design phase of projects. Furthermore, in the majority of load tests the magnitude of loads applied are specifically selected to not approach failure, so the shafts can be used in the future foundation system (i.e. production shafts). This practice of field testing restricts our knowledge of the true capacity of the drilled shaft at failure; hence the nominal resistance remains unknown.

Jan 1, 2018

By J. Drimmer

The past several decades have seen the rapid expansion of multinational mining companies? exploration and production activities around the globe. This trend has resulted from a number of factors, including increased demand for resources as a result of worldwide economic growth, the diminishment of known and proven reserves, rising commodity prices, technology improvements, and the liberalization of investment regimes in developing countries with significant natural resources. With those opportunities, however, come associated risks and significantly increased legal compliance obligations that may be imposed by various bodies. That includes domestic regulations, as well as foreign civil and criminal laws with extraterritorial reach. A failure to adhere to those laws can have dire consequences, including substantial monetary fines and penalties, severe damage to a company?s reputation, and even jail time for individual company employees.

Jan 1, 2010

By Carlos de F. Gontijo

The flotation of quartz particles was studied over the particle size range from 0.5 µm to 1000 µm and for advancing water contact angles between 0º and 83º. Flotation was performed in a column and in a Rushton turbine cell. Particle contact angle threshold values, below which the particles could not be floated, were identified for the particle size range 0.5~1000 µm, under different hydrodynamic conditions. The flotation response of the particles, either in a column or in a mechanically agitated cell with a similar bubble size, was comparable. Turbulence plays a role, as does bubble-particle aggregate velocity and bubble size. The stability of the bubble-particle aggregate controls the maximum floatable particle size of coarse particles. For fine particles, the flotation limit is dictated by the energy required to rupture the intervening liquid film between the particle and bubble. Flotation of very fine and large particles is facilitated with small bubbles and high contact angles. These results greatly extend our earlier observations and theoretical predictions.

Jan 1, 2014

By Siegmund Babendererde, Jan O. Babendererde

Extruded Concrete Lining combines technological and financial advantages. The tunnel lining is reliably embedded in the surrounding ground as the fluid concrete is extruded at constant pressure directly behind the TBM supporting the exposed surface. Ground deformation from the TBM passage can be compensated and the ground will be pre-stressed by the extrusion process. Developments in concrete technology permit high speed tunneling by use of a slip formwork attached to the TBM. Realised projects in Milano (Italy), Lyon (France), Frankfurt (Germany) and Akima (Japan) will be demonstrated.

Jan 1, 2001

By AN. Kumar

Two fabrication stages in the manufacture of pipelines are identified as causing significant deterioration of the steel plates, namely cold bending and welding. The objectives of this work include quantitative assessment of the degradation of the quality of the steel plate by the loss of fracture toughness, and an estimation of the safe working pressure. The study was conducted on three API grade steels: X42, X46 and X60. After cold bending by the UO technique, various welding technique were employed for joining of the bend plates along the pipe length. A crack-tip opening displacement parameter (CTOD) was used at the onset of initiation and at the first load maxima as the criterion for assessing the toughness degradation under various fabrication stages and regime (such as WZ, HAZ and parent body). In addition, strength, hardness and impact energy values were determined to check the degree of degradation. Microstructural and microfractographic investigation of the fractured samples were also carried out in the scanning electron microscope (SEM). X60 grade steel plate suffers from CTOD toughness loss by around 38 and 55% after welding and cold bending, respectively, for the conditions studied. A combined effect of the two stages results in a loss in toughness by around 70% for the same steel. In X42 grade, the loss in impact energy ranges from 78 to 35 J due to electrical-resistance welding study (ERW). Crack resistance curves are also obtained for the steels to study the crack growth resistance behaviour and to supplement the information on crack initiation behaviour. The orientation of the pearlite banding, as observed on the fracture plane with respect to notch front and applied loading direction appears to have a strong influence on the microvoid-coalescence mechanism of fracture as well as the toughness values. An integrated analysis of the performance of pipelines, considering all these key factors, is discussed.

Jan 1, 2005

By A. N. Kumar

Two fabrication stages in the manufacture of pipelines are identified as causing significant deterioration of the steel plates, namely cold bending and welding. The objectives of this work include quantitative assessment of the degradation of the quality of the steel plate by the loss of fracture toughness, and an estimation of the safe working pressure. The study was conducted on three API grade steels: X42, X46 and X60. After cold bending by the UO technique, various welding technique were employed for joining of the bend plates along the pipe length. A crack-tip opening displacement parameter (CTOD) was used at the onset of initiation and at the first load maxima as the criterion for assessing the toughness degradation under various fabrication stages and regime (such as WZ, HAZ and parent body). In addition, strength, hardness and impact energy values were determined to check the degree of degradation. Microstructural and microfractographic investigation of the fractured samples were also carried out in the scanning electron microscope (SEM). X60 grade steel plate suffers from CTOD toughness loss by around 38 and 55% after welding and cold bending, respectively, for the conditions studied. A combined effect of the two stages results in a loss in toughness by around 70% for the same steel. In X42 grade, the loss in impact energy ranges from 78 to 35 J due to electrical-resistance welding study (ERW). Crack resistance curves are also obtained for the steels to study the crack growth resistance behaviour and to supplement the information on crack initiation behaviour. The orientation of the pearlite banding, as observed on the fracture plane with respect to notch front and applied loading direction appears to have a strong influence on the microvoid-coalescence mechanism of fracture as well as the toughness values. An integrated analysis of the performance of pipelines, considering all these key factors, is discussed.

Jan 1, 2005

By J. F. Brune, A. Verma

"Face ignitions in underground coal mines are a major risk for underground mining operations, as they can lead to methane or coal dust explosions. The 2010 disaster at the Upper Big Branch Mine resulted in 29 fatalities due to a methane and coal dust explosion initiated from a face ignition. Much research has been conducted to mitigate face ignition hazards, from water sprays to installing passive and active explosion barriers. Despite the increased use of water sprays in U.S. coal mines, there have been more than 50 documented face ignitions in the U.S. underground coal mines since 2010, indicating that this hazard still prevails. This paper will examine the statistics of face ignitions and gas explosion in U.S. coal mines based on MSHA data. It will study factors contributing to these face ignitions and outline best practices for their prevention based on experience and practices worldwide. INTRODUCTION Methane and coal dust explosions are one of the major causes of coal mine disasters in the U.S. and around the world. Such disasters have resulted in the large number of fatalities and loss of mine infrastructure. The recent explosion at the Soma coal mine in Turkey has caused the death of 301 miners (Mining Turkey, 2014). As documented by U.S. Mine Safety and Health Administration (MSHA, 2015a), the U.S. coal mining industry has also experienced several catastrophic mine explosions with accidents at Upper Big Branch mine, Darby mine, Sago mine and Jim Walter Resources No. 5 mine in the last decade, causing the deaths of almost 60 miners. Every explosion requires a source of ignition, the right amount of fuel and oxygen. In underground coal mines, methane acts as a fuel while ventilation air acts as a source of oxygen. The source of ignition may vary from spontaneous combustion, electrical equipment and switchgear, mechanical heat sources, face ignitions due to friction rock-on-rock or from cutter bits and lightning strikes. Under the right conditions, energy of less than 0.3 mJ is sufficient to ignite methane-air mixtures (James, 2007) that can result in a catastrophic explosion. Much research has been done to mitigate the methane explosion hazard by proper dilution, continuous monitoring of methane and elimination of ignition sources. Historical studies indicate that face ignitions are the major cause of explosion in underground coal mining operations worldwide (Belle, Carey, and Robertson, 2012). Statistics shows that most mine disasters were started from a small face ignition, which turned into a major explosion fueled by additional methane and coal dust (Belle et al., 2012). To investigate face ignition hazards, researchers must study potential ignition sources as well as potential explosive atmospheres near mechanical coal cutting operations. Statistical analysis of U.S. coal mine face ignitions reported by the U.S. Mine Safety and Health Administration (MSHA, 2015b) shows that several factors are responsible for face ignitions."

Jan 1, 2016

By D. N. Hedges

This paper discusses the actual recovery and installation of a longwall in a bituminous coal mine in western Pennsylvania. The coal bed mined is in the Lower Freeport seam, which averaged 1.07 m (42 in.) in height locally. Drainage from the mine is about 13.25 ML/day (3.5 million gal per day) of water. This water deteriorates the mine's predominately fire clay bottom making it extremely difficult to move equipment. Support removal is accomplilshed by pulling the 5.44 t (6 st) shields out under their own hydraulic power and transporting them by track 8.05 km (5 miles) to the next longwall panel. This paper also discusses the changes that will be made to aid in the succeeding longwall recoveries and installations.

Jan 1, 1985

By D. D. Tannant, H. Ozturk

Thin spray-on liners are increasingly being used as rock support in underground mines. The adhesive strength between the liner and the rock surface is an important design parameter. Adhesion tests were conducted to assess the impact on adhesion of the presence of oil, water, and dust on a substrate, and the roughness and grain size of different substrates. Other factors such as curing time, loading rate, and liner thickness were also considered. Adhesion was measured using a pull test of a 33 mm diameter elevator bolt attached to an over-cored section of liner with strong epoxy. Most tests were performed using Tekflex liner material, although five other liner products were also tested. Adhesive strengths of about 2 MPa can be achieved with Tekflex under optimal conditions. Long-term creep tests showed that the adhesive strength could drop by at least 50% when the liner carries load for about a month. Where the rock surface is contaminated with dust or the rock is weak in tension, it may be difficult to reach adhesion strengths of 1 to 1.5 MPa. As the thickness of the liner increases, the adhesive strength to a substrate appears to decrease.

Jan 1, 2007

By Don Houston

Vertical crater retreat mining (VCR) requires initiation methods that minimize debris in the borehole. The use of detonating cord and shock tube detonators eliminates debris that could interfere with subsequent loading operations and avoids the cost of using drilling equipment to clear the debris. The explosive must not be sensitive to the strength of detonating cord used, otherwise timing will be affected. “Slicing and Dicing” of product before “Air mailing” down boreholes may facilitate loading, especially in wet holes, and can result in product surrounding the detonating cord. Cord sensitivity testing confirmed that having the detonating cord surrounded by product significantly increases the likelihood of an energetic reaction. Careful formulation and testing, based on a thorough knowledge of the application and the role of ingredients in affecting performance, ensures reliable initiation and avoids cord sensitivity. The use of certain metallic nitrate salts, even in relatively small amounts, was found to significantly increase the cord sensitivity of watergel formulations. Evidence of increasing cord sensitivity includes increasing amounts of damage to product and packaging, to ejection of product from the test pipe, then cracking of the pipe, followed by deflagration then detonation of the product. Predictably, the likelihood of an energetic reaction increases with product temperature, cord strength, and borehole diameter, while it is inversely related to product density.

Jan 1, 2002

By I Jabouri

There are many physical factors that can affect the self-heating rate of coal. The presence of seam gas has often been referred to as inhibiting coal self-heating due to the limited access of oxidation sites created by the presence of the gas adsorbed on the coal pores. Similarly, the presence of bed moisture in the coal also acts as an inhibitor of oxidation by blocking access of air into the pores. Gas drainage of a coal seam prior to mining removes both gas and moisture from the seam. Bulk coal self-heating tests in a two-metre column on both gassy, as-mined and gas-drained, dried high volatile bituminous coal show that removal of gas and moisture from the coal accelerates the rate of self-heating to thermal runaway from 8.5 days to 4.25 days, from a start temperature of 30¦C, with an airflow of 0.25 L/min. The corresponding gas evolution pattern for each of these situations is different. Therefore, it is necessary to take this change in coal condition into consideration when developing a spontaneous combustion management plan.

Jan 1, 2005