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By C. E. Lundin

The Ce-H system was investigated in the temperature range, 573° to 1023°K, and the pressure range, 10-3 to 630 Torr, as a function of 'composition up to 72 at. pct H. Families of isothermal arid isopleth curves were plotted from the pressure-terr~perature-composition relationships. From these curves the solubility relationships were determined for the system. The isopleths are analytically represented by equilibrium dissociation pressure equations. The relative partial molal enthalpzes and entropies of solution of hydvogen in the systerrz were calculated fronz the dissociation pressure equulions and are tabulated. The integral free energies, enthalpies, and entropies of mixing in the Ce-H system were determined from the relative partial quantities and are also tabulated. The standard free energy, enthelpy, and entvopy of reaction of the dihydride phase at kcal per kcal per mole H2, and ?S° = -34. 1 cal per deg mole H2, respectively. The equilibrium dissociation pressure equation in the two-phase region is: UNTIL recently very little was known of the detailed solubility and thermodynamic relationships of the Ce-H system. Two previous investigations1,2 are noteworthy. However, significant discrepancies and omissions exist on analyzing them. The work of Mulford and Holley1 on cerium did not clearly delineate the boundaries of the two-phase region, Cess - CeH2-x. The plateau partial pressures were not thoroughly defined and were considerably displaced in pressure compared to those from the work of Warf and Korst.2 These latter authors concentrated their studies primarily from 823° to 1023°K in the pressure range of 1 to 760 Torr. No data were determined to outline the regions of primary solid solubility and the hydride phase. Also the establishment of the plateau partial pressures was rather limited in scope. In neither work was a treatment conducted of the relative partial molal enthalpies and entropies of solution of hydrogen in the single-phase regions and the integral thermodynamic quantities of mixing throughout the system. Therefore, it was the objective of this research to determine the complete equilibrium solubility relationships and thermodynamic data for the system by pressure-temperature-composition studies. EXPERIMENTAL PROCEDURE The cerium metal for this study was donated by the Reno Metallurgy Research Center of the Bureau of Mines. Total impurity content was 0.13 pct with only 60 ppm O. The metal was checked metallographically and contained only minor amounts of second phase compared to cerium from other sources. Specimen preparation was done in a dry box flushed with argon gas. The surface of a small rectangular piece of cerium (about 0.2 g) was filed with a clean, mill file. Final weighing was done in a tared enclosed vial containing argon gas. The specimen was then loaded quickly into the reaction chamber which was purged several times with high-purity hydrogen gas and then allowed to pump to about 10-6 Torr. The furnace was heated to the reaction temperature and the run started. The equipment used to conduct the hydriding was a Sievert's-type apparatus. Basically it consisted of a source for pure hydrogen, a precision gas-measuring burette, a heated reaction chamber, a McLeod gage, and a mercury manometer. Pure hydrogen was supplied by the thermal decomposition of uranium hydride. The 100-ml precision gas burette was graduated to 0.1-ml divisions and was used to measure the quantity of gas and admit it to the chamber. The reaction chamber was a quartz tube. Prior to each run, the cerium specimen was wrapped in a tungsten foil capsule to prevent reaction of the cerium with the quartz. Control of the temperature was achieved within ±1°K. Pressures in the manometer range were measured to ±0.5 Torr and in the McLeod range (10-3 to 5 Torr) to ±3 pct. The compositions of hydrogen in cerium were calculated in terms of hydrogen to cerium atomic ratio. These compositions were estimated to be ±0.01 H/Ce ratio. The technique used to study the equilibrium pressure-temperature-composition relationships of the Ce-H system was to develop experimentally a family of isothermal curves of composition vs pressure. The range of pressure through which each isotherm was developed was from 10-9 to about 630 Torr in the temperature interval, 573° to 1023°K. RESULTS AND DISCUSSION The hydriding characteristics of cerium are iso-morphous with those of the elements of the light-rare-earth group (lanthanum, cerium, praseodymium, and neodymium) wherein the region from the dihydride to trihydride is continuously single phase.' The structure of this phase is fcc.3 The heavy rare earths form a trihydride,2 which is hcp, separated by a two-phase region from the fcc dihydride phase. The Ce-H system is represented by the family of experimental isotherms in Fig. 1. Due to the small scale required to draw the curves, the experimental points are omitted; however, a total of 240 experimental data points were taken to prepare these curves. The solubility relationships can be deduced therefrom. Three distinct regions of partial pressure and composition can be seen. The region of cerium solid solution is represented by the rapidly rising isotherms in the dilute composition range. In accordance with Gibbs Phase Rule only one solid phase, the cerium solid so-

Jan 1, 1967

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET's and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.' More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET's. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET's with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

The STATE MINERAL SUMMARIES publication provides estimated data and summaries of mineral activities at the State level for 1993. Most of the estimates are based on nine months data. Individual State summaries are published separately as State Mineral Industry Surveys and copies can be obtained from the appropriate State mineral officer. In an effort to facilitate the rapid dissemination of information and publications produced by the U.S. Bureau of Mine, an electronic document dissemination system is now available for use. MINES FaxBack is a simple-to-operate automated fax response system that operates 24 hours a day, seven days a week. All a user needs is access to a fax machine with a touch-tone telephone. MINES FaxBack can be accessed by calling (412) 892-4088, using the touch-tone telephone attached to the user's fax machine. After calling MINES FaxBack, the requester is guided by a series of voice messages to assist in ordering the desired documents.

Jan 1, 1994

By Charles F. Jackson

Gold mining is a subject that not only appeals to the popular imagination but has vital importance to the world's economic structure. However, a discussion of the use of gold as a medium of exchange, and a basis for credit between nations and for monetary systems is not within the scope of this paper. The importance of gold in carrying on the commerce of the world, the present supply and rate of production, the probable trend of future production, the probable future requirements, and related subjects have recently received much attention from bankers and economists, and many articles on these subjects have been published. During slack periods of base-metal production due to falling prices, accompanied by scaling down of base-metal mining operations and often by the closing down of at least some mines, there usually result revival of interest in gold mining, search for previously undiscovered deposits, and reopening of some old gold mines.

Jan 1, 1932

It is probably safe to say that, as the economic well-being of the mining industry goes, so goes the fortunes of mineral explorationists. And in 1977 the industry was not well at all. The year-long depression of the copper industry, marked by layoffs, temporary shutdowns, and mine closures, provided an appropriate background for the collapse of the nickel market, passage of a surface mining law that will affect the hard-rock industry in ways that are yet unclear, and the threat of operating under a new set of rules brought on by reform of the Mining Law of 1872.

Jan 5, 1978

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1&apos;2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:&apos; Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal&apos;3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.&apos; Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.&apos; The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of &apos; However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-&apos; have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h&apos;) formed by the reaction where, accorhng to the notation of Kroger and Vink,6&apos;7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i&apos; and Fe3&apos; ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.&apos;-&apos; A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i&apos; and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By M. C. Malamphy

A general description of the activities and results of bauxite investigation by the Bureau of Mines at its bauxite project in Saline and Pulaski Counties, Ark., has been given in Report of Investigations 4251. The tactual data obtained during the project are reported in a series of Reports of Investigations beginning with No. 4251, of which this is the twelfth. The data are accompanied by maps showing the location of holes drilled and the deposits developed. Each area upon which work was done is reported by half townships. Each bauxite deposit investigated was assigned a name and a number for ready reference and identification, and its location and name are shown on the appropriate halt-township map. The description of each half township is followed by a description of each deposit developed in that halt township. The 14 half-township maps and 77 detail maps of the bauxite deposits in this series of reports give the locations and numbers of all the holes drilled on the project except the deep holes drilled to test the geophysical anomalies. The locations of those holes show on figure 13 in volume 1. The descriptions of the deposits developed are followed by complete detailed logs of the drill holes. Many of the widely spaced exploratory holes did not discover bauxite of minable thickness and grade. The pertinent information obtained from the widely spaced exploratory drill holes has been summarized and tabulated, and a table for each half township is given with the discussion covering that area.

Jan 1, 1948

EdgaR S. Cook, Pottstown, Pa.:—Many friends and acquaintances seem to be under the impression that the Warwick Iron & Steel Co. received a&apos; license from Mr. Gayley, free of cost, as an inducement to adopt the process. This impression is not correct, since the license was paid for, and I think it was the first payment that Mr. Gayley received for the use of his process. As president of the Warwick Iron & Steel Co., I am responsible for its earnings, and with only the experience at the Isabella furnaces as a guide, the directors of the company considered that there was a great risk in expending the large sum of money required for the plant. They, however, acted favorably upon my recommendation, and to this extent I am responsible for the installation at the Warwick furnaces. I made the best agreement possible with Mr. Gayley, and naturally our company received certain advantages. It will be contrary to all experience if subsequent plants do not show some improvements and economies in construction. It is to our indirect benefit that all subsequent licenses granted by Mr. Gayley should be charged at a much higher rate than we paid; and I trust that he will see to it that all such licenses granted, especially to companies making merchant iron, shall be at a maximum figure. The Warwick Iron & Steel Go. is not interested in any way in exploiting the merits of the Gayley dry-blast process; on the contrary, looking at the subject from a narrow and selfish standpoint, it is to the advantage of our company that no merchant blast-furnace competing with our iron-product should be equipped with a dry-blast plant. There is a clause in the contract with Mr. Gayley, whereby our company agrees to furnish him with all the data derived from the operation of the dry-blast plant, and that he or his

Jan 1, 1909

By Edmund S. Leaver

The selection of a process for treating a gold ore is governed primarily by the characteristics of the ore under consideration. The form in which the gold occurs, its mode of association with other minerals, and the size and surface condition of the gold particles are important factors which influence materially the choice of procedure for recovering gold. A knowledge of these characteristics may be obtained by microscopic and chemical methods combined with experimental testing. Cyanidation and amalgamation, either alone or in conjunction with flotation and gravity methods, are peculiarly adapted to the treatment of gold ores, especially those of relatively low grade. Gold alloys readily with mercury provided both present clean surfaces. The presence of oils and grease, antimony and arsenic minerals, or soluble sulphides have a harmful effect. Very small, flaky particles of gold frequently are lost in amalgamation because of noncontact with the mercury. Fine gold in pyrite, or gold having rusty or contaminated surfaces, is often lost for the same reason. Grinding or some form of abrasion sometimes removes surface films of iron oxide or substances of a similar nature, and alkalies or other chemicals are used to remove grease. Gold is readily soluble in cyanide solution, and this method of treatment is particularly effective in the recovery of gold from the tailings resulting from other types of concen¬tration procedure. Cyanide solutions must contact the gold to insure recovery, and the porosity of the ore treated and the fineness of grinding required are important governing factors. The use of lime in cyanidation is necessary to protect the cyanide, to precipitate undesirable substances, and to settle slimes. Certain substances in ores are harmful in cyanidation; chief among them are those that combine with cyanide, forming cyanides, and carbon which precipitates gold from solution. Arsenic and antimony are also harmful if present in sufficient quantity. These and other difficulties encountered in cyaniding certain ores often are overcome by roasting prior to leaching. Zinc dust is used almost universally for precipitating precious metals from cyanide solutions. The refining and melting of the product may be accomplished by oxidizing the zinc before melting it in graphite pots with fluxes, although sulphuric acid is now used largely to remove the zinc before melting. Straight cyanidaticn practice is being replaced by flotation as a major process, followed by cyanide leaching of the tailings, but amalgamation is still needed as a primary process for the recovery of coarse gold before either flotation or cyanidation.

Jan 1, 1935

By Joan Weinberg

The economy continued to expand during the third quarter, as real GNP rose at a seasonally adjusted annual rate of 3.8%, up from 2.5% in the second quarter (table 1). Continued job gains (see below), higher incomes, and an increase in installment debt, resulted in a nearly 20% increase in consumer spending on durable goods. Consumer expenditure on nondurables fell slightly, while spending on services continued at a moderate pace. Nonresidential fixed investment climbed nearly 24%, as producers purchased more durable equipment. Residential fixed investment was adversely affected by rising interest rates, which slowed new home construction from January to August, 1987 to a rate 11.2% below a comparable period in 1986. Net exports of goods and services deteriorated slightly, after three consecutive quarters of improvement. The volume of net exports has risen 15% for the year, contributing to economic and employment growth, but large price increases on imports have slowed the improvement in the nominal trade balance. Although U.S. goods have declined in price relative to foreign goods because of the devaluation of the dollar, faster growth in exports is hampered by austerity programs in developing countries, and emphasis in Germany and Japan on curtailing inflation and fiscal deficits.

Jan 1, 1987

By Edmund S. Leaver

The selection of a process for treating a gold ore is governed primarily by the characteristics of the ore under consideration. The form in which the gold occurs, its mode of association with other minerals, and the size and surface condition of the gold particles are important factors which influence materially the choice of procedure for recovering gold. A knowledge of these characteristics may be obtained by microscopic and chemical methods combined with experimental testing. Cyanidation and amalgamation, either alone or in conjunction with flotation and gravity methods, are peculiarly adapted to the treatment of gold ores, especially those of relatively low grade. Gold alloys readily with mercury provided both present clean surfaces. The presence of oils and grease, antimony and arsenic minerals, or soluble sulphides have a harmful effect. Very small, flaky particles of gold frequently are lost in amalgamation because of noncontact with the mercury. Fine gold in pyrite, or gold having rusty or contaminated surfaces, is often lost for the same reason. Grinding or some form of abrasion sometimes removes surface films of iron oxide or substances of a similar nature, and alkalies or other chemicals are used to remove grease. Gold is readily soluble in cyanide solution, and this method of treatment is particularly effective in the recovery of gold from the tailings resulting from other types of concentration procedure. Cyanide solutions must contact the gold to insure recovery, and the porosity of the ore treated and the fineness of grinding required are important governing factors. The use of lime in cyanidation is necessary to protect the cyanide, to precipitate undesirable substances, and to settle slimes. Certain substances in ores are harmful in cyanidation; chief among them are those that combine with cyanide, forming cyanides, and carbon which precipitates gold from solution. Arsenic and antimony are also harmful if present in sufficient quantity. These and other difficulties encountered in cyaniding certain ores often are overcome by roasting prior to leaching. Zinc dust is used almost universally for precipitating precious metals from cyanide solutions. The refining and melting of the product may be accomplished by oxidizing the zinc before melting it in graphite pots with fluxes, although sulphuric acid is now used largely to remove the zinc before melting. Straight cyanidation practice is being replaced by flotation as a major process, followed by cyanide leaching of the tailings, but amalgamation is still needed as a primary process for the recovery of coarse gold before either flotation or cyanidation.

Jan 1, 1935

By Eric R. Bauer

This Bureau of Mines manual is intended to provide a better understanding of ground movement and the technology available for measuring it, The manual deals with convergence, strata separation, lateral roof movement, stress, and support load in underground mines. The instruments that measure these ground control parameters are described in detail. Step-by-step procedures for selecting the appropriate instrument are presented, which consider such factors as approximate cost, installation procedures, data collection, and data interpretation; and an instrument selection worksheet is provided to facilitate the instrument selection process. Actual instrument case studies and a list of instrument suppliers are presented in the appendixes.

Jan 1, 1985

Consumption and intensity of use trends for twelve metals, by industrial end use, were estimated for 1972 through 198Z. The trends were then forecast through 1993 using standard statistical methods. The intensity of use measure selected is the quantity of metal consumed per constant dollar output of a specific industrial sector. The metals studied were aluminum, chromium, cobalt, copper, lead, manganese, nickel, the platinum-group metals, tin, titanium, tungsten, and zinc. Average annual growth rates for the following four of the twelve metal increased from 1972-82 as follows: aluminum, 1.00 percent; platinum-group metals (consisting of platinum, palladium, and iridium), 8.83 percent; titanium, 7.82 percent; and tungsten, 6.09 percent. Consumption. for the remaining eight metals decreased at average annual rates ranging from 0.58 percent (copper) to 5.37 percent (manganese).

Jan 1, 1986

By A. R. T. Denues

This investigation was made under a cooperative agreement between the United States Department of the Interior, Bureau of Mines, and the Pittsburgh Testing Laboratory. Funds were supplied by the Chile Exploration Co., whose executive offices are in New York City. The support, cooperation, and services of these agencies made the work possible and are acknowledged gratefully. The writer wishes to express his particular indebtedness to the staff of the Explosives Division of the Bureau of Mines for services and assistance, particularly Dr. Wilbert J. Huff, consulting explosives chemist, J. C. Holtz, J. E. Tiffany, and A. B. Coates; to F. O. Gardner, treasurer of the Pittsburgh Testing Laboratory; to G. B. Holderer, consulting engineer in connection with liquid-oxygen explosives for the Chile Exploration Co.; to the Enos Coal Mining Co. of Oakland City, Ind., particularly to G. H. Utterback of the staff of the mine for providing facilities that made field tests possible; and to full-time assistants J. W. Rothhaar and J. G. P. Weinheimer and to W. S. Hiller, part-time assistant, who were employed under the cooperative agreement.

Jan 1, 1940

By R. T. Jones

The largest known platinum group metal (PGM) deposit in the world is the Bushveld Complex in South Africa, with the Great Dyke in Zimbabwe also being one of the biggest. It is therefore not surprising that the majority (just over 5 million troy ounces or 156 metric tons per annum) of the world&apos;s platinum is produced in Southern Africa. Primary smelting of ore concentrates is carried out in that region by five companies, namely Anglo Platinum, Impala Platinum, Lonmin Platinum, Northam Platinum, all of South Africa, and Makwiro Platinum in Zimbabwe. The only other primary smelter of platinum group metals is Stillwater Mining of Montana, USA, although very significant quantities of PGMs are produced as co-products by Norilsk Nickel of Russia. Smaller (but still significant) quantities of PGMs are produced by Falconbridge and Inco of Canada, also as co-products from nickel sulphide smelting. There are many similarities between PGM smelting and nickel sulphide smelting, and the range of technologies in use includes six-in-line rectangular electric furnaces, three-electrode circular AC furnaces, Peirce-Smith converters, and Anglo&apos;s ACP (based on Ausmelt technology). PGMs are also recovered from residue materials using DC arc furnace technology.

Jan 1, 2005

By Robert S. Hedin

Passive methods of treating mine water use chemical and biological processes that decrease metal concentrations and neutralize acidity. Compared with conventional chemical treatment, passive methods generally require more land area, but use less costly reagents and require less operational attention and maintenance. Currently, three types of passive technologies exist: aerobic wetlands, organic substrate wetlands, and anoxic limestone drains. Aerobic wetlands promote mixed oxidation and hydrolysis reactions, and are most effective when the raw mine water is net alkaline. Organic substrate wetlands promote anaerobic bacterial activity that results in the precipitation of metal sulfides and the generation of bicarbonate alkalinity. Anoxic limestone drains generate bicarbonate alkalinity and can be useful for the pretreatment of mine water before it flows into a wetland. Rates of metal and acidity removal for passive systems have been developed empirically by the U.S. Bureau of Mines. Aerobic wetlands remove Fe and Mn from alkaline water at rates of 10-20 and 0.5- 1.0 g. m-2? d-1, respectively. Wetlands with a composted organic substrate remove acidity from mine water at rates of 3-9 g. m-2? d-1?. A model for the design and sizing of passive treatment systems is presented in this report.

Jan 1, 1994

By F. F. Netzeband

This report relates to the sulfur industry of seven States--Arkansas, Kansas, Louisiana, Mississippi, Missouri, Oklahoma, and Texas--and is part of a national study of the sulfur industry by the Bureau of Mines. Markets as used 1n this report are divided into two components for individual analysis--(1) supplier markets which include regional Frasch and byproduct sulfur producers and (2) consumer markets which include processors and manufacturers requiring sulfur in their operations. The term sulfur as used in this report includes brimstone, native sulfur, elemental sulfur, or sulfur equivalents.

Jan 1, 1964