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By Victor Lenher

The interest shown recently in selenium and tellurium has brought many requests for an assembling of the analytical chemistry of these two elements. The intention of this paper is to discuss all of the chemical principles utilized in the detection and quantitative determination of these elements, as well as to describe the works methods actually followed by producers of tellurium and selenium in the United States. These methods have been furnished by S. Skowronski of the Raritan Copper Works, H. D. Greenwood of the United States Metals Refining Co., F. F. Colcord of the U. S. S. Lead Refinery, and E. W. Rouse and A. E. Hall of the American Smelting and Refining Company. Occurrence Selenium is found associated with sulfur, to which in many respects it is quite similar. Occasionally deposits of native sulfur, notably those in the Lipari Islands, Kilauea, and Japan, show a red-brown coloration, I which is readily distinguished from that of other sulfur; this red-brown * sulfur contains a small amount of selenium. Not infrequently, the , sulfides of the heavy metals are accompanied by selenium and tellurium, • presumably as selenides and tellurides. The Scandinavian pyrite, which is one of the large sources of European sulfuric acid, when roasted has fur- - nished a large part of the selenium that has come to the United States; it I was in flue dust from the roasting of Scandinavian pyrites that the element was discovered by Berzelius in 1817. Greek and Spanish pyrites also

Jan 1, 1923

By R. Gilman Brown

INTRODUCTION. MINES are interesting by reason of what they have done for man, or of what has been done for them by nature. Not all are interesting on both scores. Many profitable mines are commonplace to the geologist; and many presenting unique geological conditions have been sad failures commercially. The Standard group at Bodie has produced in 25 years, $14,500,000, paying $5,000,000 in dividends.' On the other hand, this output has been mined (almost wholly above the 1,000-ft. level) from a system of more than 100 veins, ranging in thickness-from 0.5 in. of "specimen rock" to 30 ft. of clay and quartz; distributed through a zone about 2,000" ft. in width, and representing from three to five distinct periods of formation. This group, therefore, by reason of its industrial record as well as its geological features, may fairly be regarded as doubly interesting. The Bodie district occupies an island of recent (Tertiary) hornblende-andesite, surrounded by a complex of igneous rocks and breccias. It lies at the summit of the eastern foot-hills of the Sierra Nevada mountains, and within the Great Basin, a few miles from its western edge, marked here by Mono lake on the line of the Great Fault. The average elevation of the outcroppings of the veins may be taken at about 5,700 ft. The andesite projects from south to north in a great tongue, 12,000 ft. long and 5,000 ft. wide, reaching an extreme height at the northern end of perhaps 1,000 ft. above the adjoining small canyons. These separate it from the main mass of the foot-hill

Jul 1, 1907

Because common salt, sodium chloride, is necessary to all animal and much plant life, it is probably the most widely used of all mineral commodities, except for water. Nevertheless, of the total salt consumed, only 7% is used for food, including animal food. Two-thirds of the total is used as chemical raw material, principally for making such basic chemicals as chlorine, caustic soda, and soda ash. Other uses are for road thawing (16%) and water softening. Some 162.5 million tons of salt were used, worldwide, in 1972 (Table 15.4F.1). Production is from bedded salt deposits, salt domes, and evaporation of brines, including solar evaporation of seawater. Production is worldwide from at least 20 countries, of which the United States, China, USSR, the United Kingdom, and West Germany are the leaders. Consumption increases about 7 % annually. Reserves are plentiful: Other important sodium salts are soda ash (sodium carbonate) and salt cake (sodium sulfate). Soda ash comes mainly from the Solvay process (70% ) , which uses salt, limestone, and ammonia as raw materials. A large and growing portion of United States production is from mining large bedded deposits of trona, a natural hydrated sodium carbonate and bicarbonate found in Wyoming, and from brine evaporation in California. Soda ash is used for glassmaking, phenol, soap, detergents, and bleaches. Half of the United States salt cake used is a byproduct from rayon manufacturing. The other half comes from brines and playa lakes in California, Texas, and Wyoming. Salt cake is used mainly for papermaking. ACKNOWLEDGMENT Appreciation is expressed to William B. Dickson, president, Salt Institute. [ ]

Jan 1, 1976

By J. A. Snyder, W. L. Finlay

G. Edmunds—Solid solubility is considered to be of either the interstitial or the substitutional type. Is it possible, in a binary alloy as the simplest case, that some of the solute atoms are present in the normal lattice sites (substitutionally or filling lattice vacancies) while simultaneously others are in interstitial positionss One might even ask whether a distribution of the two types may be the normal situation. H. M. Meyer—Metastable states of interstitial atoms occupying vacant lattice sites possibly occur as well as of substitutional atoms squeezed in between regular matrix positions. However (as we know since Hume-Rothery), the solute atoms choose between the two kinds of solutions; consequently, every solute will be unequivocally either substitutional or interstitial in the equilibrium state of the solid solution. M. Balicki—In view of the fact that the authors apparently correlate the analysis of the alloys at the ingot stage with the properties exhibited at the testing stage, I would like to ask whether this is a fully justifiable procedure. In other words, how good are their determinations of solute concentration for correlating them with the mechanical properties. The answer to this question may explain some of the divergencies. Assuming good enough homogenization of the samples and exact determination of mechanical properties the position of the plotted experimental points will depend solely upon the accuracy of composition determination. If this is not accurate, say due to loss or pickup of elements during processing from the ingot to the testing stage, or due to a systematic error in the method employed for obtaining solute concentration data, the points will deviate from their true position and may align themselves along a different curve than the one expected. H. V. Kinsey—We have been studying the creep-rupture properties of titanium-base alloys at 1000°F. In the course of this work, anomalies in behavior of the alloys that would suggest that the material under test was becoming stronger as the test progressed have been observed. If this was so, the most likely explanation that we could think of was that the test bars were absorbing oxygen and nitrogen from the air during the test and were thereby becoming strengthened. In an attempt to determine the strengthening effect of absorbed oxygen and nitrogen the following experiment was conducted. A length of cold-rolled titanium was supplied by the E. I. du Pont Co. Two test bars, having a 1/4 in. diam gauge length, were prepared from this material. One bar was tested in the as-received condition. The second bar was heated in air at 1550°F for 100 hr and subsequently air cooled prior to testing. A testing temperature of 1000°F was employed. The results of these tests are tabulated in table 11. In the author's opinion, is it reasonable to assume that the bar that was exposed to air at 1550°F for 100 hr was stronger because it absorbed oxygen and nitrogen from the air during this heat treatment? W. L. Finlay (authors' reply)—Direct experimental evidence for or against Mr. Edmunds' interesting suggestion will probably never be available. It seems possible, however, that mixed interstitial-substitutional solid solution might well occur with interstitial elements. The less likely possibility of interstitial solution of a normally substitutional element like copper in aluminum was recently discussed at length by the

Jan 1, 1951

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By E. A. Gulbransen, K. F. Andrew

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH'S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.' The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By Jan Wolski

Today's rapidly shrinking world requires a common language of measurements, a consistent system which could be used by everyone. The S.I. system of units is generally accepted as such and is already in use by a great majority of nations in the world. The change to S.I. units is also slowly taking place in U.S. engineering practice. The transition period is difficult and long because it takes time to get familiar with the new system, to start "feeling" values in new units. Instruments, formulas, computer programs, survey grids, etc. have to be converted or exchanged. The transition period should be used not only for substitution of units, but also for rationalization of presently used calculation methods. This paper examines the major parameters of mine ventilation from the above point of view and discusses a system which is much simpler and more consistent than the American Unit System still in use in the United States. In October 1979, the Society of Mining Engineers of AIME decided to introduce the S.I. unit system in all its publications including the periodical "Mining Engineering", and since February 1980 the system has been used consistently, not only in SME publications but in all conferences and meetings organized by this Society. The authors have no intention of explaining the details of the S.I. system in general. Any reader can find this information in many available publications and conversion tables, and in particular in the ASTM Standard for Metric Practice, E380-79. A comparison is made between various units used in mine ventilation from the past and those presently in use. This will allow an easy translation from one system to another, important when reading publications from abroad. S.I. and customary U.S. formulae are shown side by side for easier visualization of similarities and differences. Recommendations for the necessary steps in order to switch from American to S.I. units conclude the paper.

Jan 1, 1982

By A. A. Terchick, J. C. Anderson, D. T. King

During 1972-1973, U.S. Steel acquired an existing southern West Virginia high volatile coal mine property including a 150 tph heavy media feldspar jig preparation plant. Expansion of production from the property required an increase in plant capacity to 300 tph, replacement of the feldspar jig with a hydrocyclone circuit, and inclusion of a water clarification thickener system. The rugged and restrictive nature of the terrain adjacent to the plant facility indicated prohibitive construction costs and severe site congestion would be encountered if a conventional water clarification thickener were installed. A high-loading, small-volume thickener, developed initially for the sugar beet industry by the Enviro-Clear Co. of New York, was investigated by U.S. Steel Research for possible coal preparation application, utilizing bench scale and small scale pilot plant evaluation methods. Results of testing at existing U.S. Steel preparation plants indicated predictable successful application of the Enviro-Clear thickener, so a 35-ft-diam unit was installed. The two-phase thickener system, utilizing presettled bottom sludge as a filter-clarification media, has successfully performed since commissioning in April 1973, producing clarified water competitive with conventional thickener systems with freedom from usual thickener operational problems.

Jan 1, 1976

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By William M. Agar

Now that both the national and state legislatures are seeking ways of reducing expenses, the appropriations for geological investigation and for the study of mineral resources have been greatly reduced and in some cases entirely stopped. Is this policy justified? The sums saved by these reductions are always small. If the work accomplished by these surveys has no intrinsic value to the community, but is only an interesting way of spending some of the people's money when that money is plentiful, there should be no surveys at any time. If, on the other hand, they perform a necessary function, it is indeed foolish and short-sighted to save these paltry sums to the detriment of the community. It is not my purpose to undertake a general justification of geological surveys. Rather, 1 wish to call attention to the work of one state survey that has been discontinued, and to indicate ways in which the work was valuable to the people, even though that state's mineral resources are not very important, and why it should be continued. Though at one time in Connecticut's history iron mining and smelting were important, and copper was mined in appreciable quantities in two localities, it is many years since it could be regarded as a mining state. At present Connecticut stands far down among the states in the value of its mineral products. Granite for architectural and structural purposes, trap rock, clay, agricultural lime, feldspar and quartz, together with a few other nonmetallic minerals, are produced in appreciable quantities, but the natural resources of the state consist at present much more largely in its attractive scenery, woods, lakes, shore line, and in the opportunities that these offer for rest and recreation. Is the prosecution of geological work in such a state a waste of the taxpayer's money? Or can it be that though it was formerly valuable, the work is now completed? The only way to answer these questions is to review the geological work done in the past and to consider the type of information the people want, as reflected in the requests that have been received by the director of the survey in the last few years. There have been two periods during which Connecticut has supported geological work within its borders. The first began in 1835 when Percival

Jan 1, 1935

By William M. Agar

Now that both the national and state legislatures are seeking ways of reducing expenses, the appropriations for geological investigation and for the study of mineral resources have been greatly reduced and in some cases entirely stopped. Is this policy justified? The sums saved by these reductions are always small. If the work accomplished by these surveys has no intrinsic value to the community, but is only an interesting way of spending some of the people's money when that money is plentiful, there should be no surveys at any time. If, on the other hand, they perform a necessary function, it is indeed foolish and short-sighted to save these paltry sums to the detriment of the community. It is not my purpose to undertake a general justification of geological surveys. Rather, 1 wish to call attention to the work of one state survey that has been discontinued, and to indicate ways in which the work was valuable to the people, even though that state's mineral resources are not very important, and why it should be continued. Though at one time in Connecticut's history iron mining and smelting were important, and copper was mined in appreciable quantities in two localities, it is many years since it could be regarded as a mining state. At present Connecticut stands far down among the states in the value of its mineral products. Granite for architectural and structural purposes, trap rock, clay, agricultural lime, feldspar and quartz, together with a few other nonmetallic minerals, are produced in appreciable quantities, but the natural resources of the state consist at present much more largely in its attractive scenery, woods, lakes, shore line, and in the opportunities that these offer for rest and recreation. Is the prosecution of geological work in such a state a waste of the taxpayer's money? Or can it be that though it was formerly valuable, the work is now completed? The only way to answer these questions is to review the geological work done in the past and to consider the type of information the people want, as reflected in the requests that have been received by the director of the survey in the last few years. There have been two periods during which Connecticut has supported geological work within its borders. The first began in 1835 when Percival

Jan 1, 1935

By J. R. Lucas, R. L. Frantz

Mine sealing programs for the alleviation of acid mine drainage were begun by the Federal Government in the '30's. As part of an acid mine research project to The Ohio State University, a field test was undertaken to determine the effectiveness of mine seals for reducing mine acid. Details of the tests made at the McDaniels mine show the feasibility of air-sealing and flooding an acid-producing drift coal mine. Work by the University continues. The Federal Government undertook in the early thirties an extensive mine sealing program for the alleviation of acid mine drainage. In the states of West Virginia, Ohio, and Pennsylvania many general summaries have been made on this program but no critical evaluation with supporting data has been found on the effectiveness of mine seals for reducing mine acid. Because of this it was decided to undertake a field testing program as part of an acid mine research project of the Engineering Experiment Station, The Ohio State University. The objective of this phase of the project was to develop and install a field research laboratory for acid mine drainage studies. Specifications for such a mine laboratory were developed and resulted from the following considerations: 1) Size and preservation—the test mine shou1d be of limited size to permit frequent and detailed examinations; it should be in a reasonably sound condition to permit safe entry. 2) Isolation—the mine should be physically separated from all other mines. 3) Openings—a minimum number would be desirable to reduce the sealing problem. 4) Structure—the mine especially near the openings should be structurally sound. 5) Acid production—the mine should be producing significant quantities of acid. After considerable searching, the McDaniels mine was selected in the Hocking coal field in Vinton County just above Lake Hope State Park in southeastern Ohio. The small drift mine in the middle Kittaning coal consisted of two small rooms with one mine opening about 6 ft above a seasonal stream bed. Before it was finally decided to seal the mine, a short study was made of the acid drainage over several months. Fig. 1 shows a plot of acidity (milligrams per liter), flow (gallons per minute), and acid production (pounds per day) vs time over the sampling period. Because the coal was overlain with a porous sandstone, the mine drainage was consistent the year around even though the mine was

Jan 1, 1961

By C. A. Hartnagel

In 1939 the production of crude oil in New York totaled 5,105,000 bbl. This marks the third consecutive year production of crude oil has exceeded 5,000,000 bbl. and only once has this total been surpassed—in the year 1882, three years after the discovery of oil in Allegany County, when the annual production was more than 6,000,000 barrels. The most gratifying feature of the industry was the increased demand for lubricants, which resulted in advanced prices for crude. From a price at the beginning of the year of $1.68 per barrel, six advances totaling 82c brought the year's closing to $2.50 per barrel. A further increase in price on Jan. 1, 1940, to $2.75 per barrel places the local industry in a strong position for the year's operations. Most of the oil production of the state is now obtained by water-flooding, and the industry is practically stabilized. No new pools have been discovered in over 25 years, and border drilling indicates little prospect of extending the boundaries of the fields beyond their present limits. Deep drilling to the Oriskany sandstone in and close to the present oil fields hay failed to find oil in substantial amounts. Altogether, the oil pools of New York have produced during the 60 years that they have been exploited approximately 125,000,000 bbl. of oil. Following the flush production of 1882, the annual production gradually dccrcased and the year 1912 marked an all-time low of only 782,000 bbl. In 1919, as a result of flooding operations, a definite upward trend in oil production was recorded. During that year also the production of oil by water-flooding methods as approved by Legislative action. In the 21-yr. period beginning with 1919, oil production in the state ha.: totaled 60,338,000 bbl. Thus it will be seen that by the aid of flooding methods nearly as much oil has been produced in the last 21 yr. as in the preceding 40 yr., although the Iatter period included the flush production in 1882. As there is little hope of extending the area of the present producing oil fields of the state, producers and refiners are concerned regarding the future life of the fields. It is encouraging to observe that earlier esti- Published by permission of Director of New York State Museum, Albany, N. P. Summarized at meeting; manuscript received at the office of the Institute March 20. 1940.

Jan 1, 1940

By C. A. Hartnagel

In 1939 the production of crude oil in New York totaled 5,105,000 bbl. This marks the third consecutive year production of crude oil has exceeded 5,000,000 bbl. and only once has this total been surpassed—in the year 1882, three years after the discovery of oil in Allegany County, when the annual production was more than 6,000,000 barrels. The most gratifying feature of the industry was the increased demand for lubricants, which resulted in advanced prices for crude. From a price at the beginning of the year of $1.68 per barrel, six advances totaling 82c brought the year's closing to $2.50 per barrel. A further increase in price on Jan. 1, 1940, to $2.75 per barrel places the local industry in a strong position for the year's operations. Most of the oil production of the state is now obtained by water-flooding, and the industry is practically stabilized. No new pools have been discovered in over 25 years, and border drilling indicates little prospect of extending the boundaries of the fields beyond their present limits. Deep drilling to the Oriskany sandstone in and close to the present oil fields hay failed to find oil in substantial amounts. Altogether, the oil pools of New York have produced during the 60 years that they have been exploited approximately 125,000,000 bbl. of oil. Following the flush production of 1882, the annual production gradually dccrcased and the year 1912 marked an all-time low of only 782,000 bbl. In 1919, as a result of flooding operations, a definite upward trend in oil production was recorded. During that year also the production of oil by water-flooding methods as approved by Legislative action. In the 21-yr. period beginning with 1919, oil production in the state ha.: totaled 60,338,000 bbl. Thus it will be seen that by the aid of flooding methods nearly as much oil has been produced in the last 21 yr. as in the preceding 40 yr., although the Iatter period included the flush production in 1882. As there is little hope of extending the area of the present producing oil fields of the state, producers and refiners are concerned regarding the future life of the fields. It is encouraging to observe that earlier esti- Published by permission of Director of New York State Museum, Albany, N. P. Summarized at meeting; manuscript received at the office of the Institute March 20. 1940.

Jan 1, 1940

By W. T. Lundy

THE forms in which sulphur is commonly found-native sulphur, sulphides of many metals and sulphates-are widely distributed throughout the world. The two first mentioned are the principal sources of sulphur. Substantial amounts of sulphur in some form are recovered from gases from industrial plants and from gases from smelters treating other minerals. In recent years, plants have been installed in the United States to recover sulphur in elemental form from sour gases."' The amount of sulphur so produced is small at the present time but undoubtedly will increase in the future. The recovery of sulphur from gases is not covered in this chapter, which is confined to: (1) native sulphur deposits of Texas and Louisiana; (2) those of Italy; (3) other scattered deposits of native sulphur; and (4) pyrites deposits found in many countries of the world.30 Sulphur, a nonmetallic element, occurs normally in well developed bipyramidal or tabular crystals of the orthorhombic system, as well as in stalactitic and earthy masses. The mineral has a distinctive yellow color, which may be dark and discolored by impurities; the streak is white; the luster is resinous; and the fracture is conchoidal to uneven. Sulphur is translucent to opaque; has a hardness of 1.5 to 2.5, a specific gravity of 2.05, and an atomic weight of 32.06.16 The molecular weight of the solid is expressed by the symbol SS and that of the liquid and vapor ranges from S2 to S8, depending on the temperature. Sulphur melts at a temperature between 2340 and 248°F, depending on its crystalline state, to a liquid of dark amber color, the boiling point of which is 832°F. The viscosity near the melting point is about that of water and increases to 50,000 times that of water at a temperature of 380°F, subsequently falling rapidly to a low figure at the boiling point. Crystallization changes slowly from rhombic to monoclinic above 205 °F and in cooling the transformation is reversed. The mineral is a very poor conductor of heat and electricity; it is insoluble in water and nearly all acids and is soluble in cold carbon bisulphide and carbon tetrachloride. It ignites in air at a temperature of 478°F, burning with a distinctive blue flame with evolution of sulphur dioxide.47

Jan 1, 1949

By Kalervo Rankama

UNTIL a few years ago, geological mapping, the study of ore boulders, and different geophysical methods were the principal means used in the systematic search for mineral deposits covered by a layer of disintegration products or soil. These methods have been developed to a high stage of perfection as far as the geometrical definition of the conductor is considered. Use of geophysical methods in prospecting is based on the fact that an ore body differs from the country rock not only geologically but also in its physical properties. The general drawbacks and complications included in the use of geophysical methods are well known to everyone who has been using them, so need not be entered into here in detail. One of the more important ones is the fact that geophysical methods are unable to furnish information concerning the chemical composition of the ore bodies responsible for the indications. Further, the ores of many metals, such as silver, gold, beryllium, zinc, mercury, tin, lead, vanadium, antimony, chromium. molybdenum, tungsten, manganese, cobalt, nickel, and the platinum metals cannot be directly located by known geophysical methods, owing to lack of physical characteristics suitable for distinguishing them from the country rock. Thus it is quite natural that efforts have been made to develop direct methods for prospecting and locating ore bodies of the elements named. Known as chemical, biogeo-chemical, and geobotanical methods of prospecting, these have been much improved during recent years. A brief review of these methods and of some results obtained with them will be presented in the following, on the basis of available information and my own experience.

Jan 1, 1947

By Minoru Sasabe, Mayurni Sorneno, Kazuhiro Goto

I) The Object of the Present Experiment. When the oxygen chemical potential in the gas phase is changed, the oxygen chemical potential in the liquid metal or in the liquid oxide phase will be subsequently changed. The object of the present experiment is to develop a method of measuring the change in the chemical potential of oxygen in liquid metals and in liquid oxides with respect to time, when the oxygen potential in the gas phase changes. II) The Experimental Method. The following types of the oxygen concentration cells with the solid electrolyte of Zr0z-CaO are used: KAZUHIRO GOTO, MemberAIME.MINORU SASABE,and MAYUMl SOMENO are Associate Professor, Research Associate, and Professor, respectively, Department of Metallurgical Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo, Japan. Manuscript submitted March 12, 1968, EMD. Igas phase liquid Ag or Pb ZrO2-CaO electrolyte!, The measured reversible electromotive force can be expressed by the next equation, provided that the transference number of the oxygen anion in the electrolyte is unity: E = RT/nF log (at electrode I)/P~ (at electrode 11) where is the electromotive force, R is the gas constant, T is absolute temperature, n is valence of oxygen anion, and Pq is the oxygen pressure at the electrodes. As shown in the previous work1 of the authors, the electromotive force is determined by the difference in the chemical potential of oxygen at the vicinity of the interfaces between the solid electrolyte and the electronic conductors used for the two electrodes. Fig. 1 shows the two kinds of the cell assembly used to measure the change of the chemical potential of oxygen in liquid metals and liquid oxides with respect to time. In both cases, the change of the oxygen pressure in the gas phase is measured by the independent oxygen concentration cell located above the

Jan 1, 1969

By H. W. Kropholler, L. A. Cramer, E. T. Woodburn, J. C. A. Greene

A generalized mathematical structure is proposed whereby internal species mass flows within a flotation network are defined uniquely by a matrix of enhancement factors. An element of the enhancement factor matrix is defined as the ratio of the mass flow of that species leaving a given cell in the concentrate to the species mass flow leaving the same cell in the tailings. To predict the enhancement factors, knowledge of flotation kinetics effects is required. Recently experimental data has become available relating to the performance of industrial flotation circuits which indicate that the discrete or discrete-distributed kinetic schemes are capable of reasonably effective simulations. These simulations show the importance of including froth effects. The prediction of performance of networks from small-scale batch tests on flotation streams shows that the model for the froth phase used in the simulations does not scale-up well and that aeration effects are also difficult to predict. The network analysis should be useful in differential flotation of complex ores and it is disappointing-in this context that little information on the kinetics of activation and depression is available.

Jan 1, 1976