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By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By Brandon R. Ball

An investigation of the effects of ozone and ozone-induced hydroxyl radical on reducing whole effluent toxicity is described and discussed relative to the application of ozone for industrial water treatment. Results from operation of an ozone system treating industrial effluent from a lead and zinc mine in Colorado are presented. The mine discharges 1,000 gpm of wastewater into a tributary of the Arkansas River and has historically exceeded Whole Effluent Toxicity (WET) limits and on occasion has exceeded numeric limits for copper, ammonia, and cyanide. Based on results of a Toxicity Identification Evaluation (TIE) conducted on the effluent and individual process waste streams, the source of effluent toxicity is believed to be primarily associated with organic reagents used in the milling process. Based on test results, an applied ozone to COD ratio of 3: 1 by weight and a contact time of 30 minutes was found to be effective for reducing whole effluent toxicity at pH 11 but not at pH 7, indicating oxidation by hydroxyl radical to be the dominant mechanism responsible for toxic-ity reduction. At an applied ozone to COD ratio of 3:1 and a pH of 11, toxicity was improved from 0 percent survival to 100 percent survival for Ceriodaphnia dubia and fathead minnow (Pimephales promelas) based

Jan 1, 1996

By William C. Spindler

Five industrial installations of large lead-acid battery energy storage systems in operation in the United States, West Germany and the 'Republic of South Africa will be described. One example is for a deep mine shaft in which air ventilation and personnel evacuation require the highest reliability for emergency power. The battery system is designed for additional cost-effective benefits of peak load lopping and reactive power control. Commercially available lead-acid batteries of the following types are in use1 traction, truck, submarine, high power, and gel. Electrode grids of both the calcium and antimony alloy types are used. Applications include deep and shallow cycling as well as float and intermittent use. The advantages of sealed lead-acid batteries in UPS (uninterruptible power source) systems are well established throughout the world, and such system suppliers could readily develop markets for industrial emergency and peak power lead-acid storage battery installations.

Jan 1, 1990

By Soumendra Basu, Uday Pal, Yang Yu, Srikanth Gopalan, Karl Ludwig, Deniz Cetin, Jacob Davis

"A limiting factor for Solid Oxide Fuel Cell (SOFC) performance is the oxygen reduction reaction (ORR) at the cathode surface. Changes in the surface composition and structure on annealing at 800°C has been studied, since these can influence the ORR. Idealized single crystals of cathode materials La0.8Sr0.2MnO3 (LSM) and La1-xSrxCoyFe1-yO3 (LSCF) were grown as heteroepitaxial thin films on lattice matched single crystal substrates. Changes upon heating the films to operating temperature and pressures were characterized using various synchrotron x-ray techniques. Total Reflection X-ray Fluorescence (TXRF) measurements, which probe compositional changes, were made at high temperature in real time. The LSM surfaces were found to develop manganese enrichment when heated. Highly strontium doped LSCF were found to develop strontium-rich surfaces. HArd X-ray PhotoElectron Spectroscopy (HAXPES) was used to investigate the electronic structure of the materials. Highly strontium doped LSCF precipitates a surface strontium phase that contains both oxide and carbonate contributions.IntroductionSolid oxide fuel cells (SOFCs) are chemical to electrical energy conversion devices that could potentially reshape how energy demands are fulfilled. SOFCs have a potential efficiency over 70%, fuel flexibility, low emissions, and low degradation over long time scales. Commonly, SOFCs are operated at high temperatures (above 800°C). At these temperatures expensive housing is needed to contain an operating stack as well as coatings to contain the oxidation of the metallic interconnects. Lowering the temperature of an operating device would allow for more conventional materials to be used, thus lowering overall cost. Understanding the reaction kinetics of the oxygen reduction reaction at the surface of the cathode is vital to designing a system that will perform well at lower temperatures. A commercialization goal is to reduce operating temperatures without sacrificing performance.In order to exploit the advantages of SOFCs, an understanding is needed of the surface chemical states of cations on the surface of the cathode and how this relates to the oxygen reduction reaction (ORR):"

Jan 1, 2014

By H. Kamiya, H. Hasegawa, M. Nojiri, S. Matsui, Y. Fukuda, M. Tsukada

"The present paper focuses on the action mechanism of anionic polymer dispersants in dense Si3N4 and SiC suspension. An atomic force microscope (AFM) was used to determine the relationship between the macroscopic suspension viscosity and the microscopic adsorbed structure of a polymer dispersant at the solid / liquid interface. The surface interactions within the suspensions were analyzed in various dispersant pH and additive conditions. The addition of an anionic polymer dispersant decreased Si3N4 and SiC suspension viscosity and increased electro-steric repulsion force on the non-oxide surface in solution at pH> 6 which was the isoelectric point of the materials. It was assumed that the increase of repulsive force was promoted by a hydrophobic adsorption of polymer dispersant on the non-oxide particles.IntroductionThe surface of silicon nitride and silicon carbide powders in a water suspension system has quite a complex molecular structure. In the case of Si3N4, hydroxyl and ammonium groups form on the surface and the pH of the suspension is increased from neutral to about 10 due to surface oxidation. The particle surface is negatively charged in alkaline solutions (pH=10), because the isoelectric point of silicon nitride exists in the pH range from 5 to 6. However, in spite of charging the negative surface charge, an anionic polymeric dispersant is generally used for the reduction in slurry viscosity.In dense SiC suspensions, an anionic polymer dispersant is generally used in order to disperse aggregates and reduce the suspension viscosity, too. Since an anionic dispersant is used in alkaline solutions higher than the isoelectric point of silicon carbide, the dispersant adsorbed on the negative charged surfaces of SiC.Few researchers have discussed and estimated the adsorption mechanism and structure of anionic polymeric dispersants on silicon nitride and silicon carbide surfaces. This is because it is difficult to observe the structure and measure the interaction at the solid/liquid interfuce directly. However, new developments in surface-force measurement technology have enabled the determination of non-DLVO type interaction for analyzing aggregation behavior2. The use of the AFM for analyzing the effects of various surfactants and co-polymers on colloidal dispersions and solid surfaces has also begun to rapidly expand to characterize the interaction between solid surfaces."

Jan 1, 2000

By Patrick R. Taylor

This investigation studied the inflight calcination kinetics of nuclear waste simulant using a thermal plasma reactor. A series of experiments were performed to determine the conversion of insoluble aluminum compounds to the soluble compounds and the decomposition of complex organic and nitrite compounds present in the simulant waste. Thermodynamic calculations based on free energy minimization were performed to establish a theoretical basis for this investigation. A kinetic model to describe the conversion of gibsite to sodium aluminate has been proposed. The products of the calcination were characterized using XRD, Gas Chromatography, and chemical analysis by ICP. The results of this investigation indicated 85% gibsite conversion to sodium aluminate, 90% of nitrate decomposition, 52% TOC decomposition and 90% conversion of chromium to soluble compounds. A process is identified for inflight calcination of wastes. Key words: Plasma, waste, simulant, calcination

Jan 1, 1996

By James P. Bennett

The successful reuse/recycling of refractory materials after removal from industrial service is limited because of contamination, the low value of spent materials, the low cost of virgin raw materials, the lack of driving forces such as regulations or taxes, and low disposal costs. Most spent refractory is disposed in landfills. Concerns over future liability for waste materials, corporate images, and IS0 14000 have helped to encourage recycling at some companies. The recycling practices and application for spent refractory materials at facilities successfully recycling used refractory materials will be discussed, with emphasis on similarities.

Jan 1, 2002

By Lijuan Li, Zheng Lu, Xin Xia, Qijie Zhai, Qingchun Li

"Pulsed current and pulsed magnetic field have been applied to the bainite transformation of Cr5 steel. Three groups of experiments were conducted. In the first group, ordinary resistance furnace was used for heat treatment. The Cr5 specimens were rapidly heated up to austenitization temperature 940 °C, held for 20 min, air cooled to bainite transformation temperature 350 °C, held for 10, 20, or 40 min and then air cooled to room temperature. The second and the third group shared the same temperature-time curve with that of the first group, but their heat resources came from the Joule heat produced by pulsed current. 1.5 T pulsed magnetic field was exerted on the third group specimens when they were held at 350 °C, but the second group specimens did not undergo the treatment of magnetic field. It was found that both pulsed current and pulsed magnetic field obviously retarded the bainite transformation. The phenomena were discussed in terms ofliterature results.IntroductionApplying pulsed current and pulsed magnetic field technology are very pronnsmg ways to change the microstructure of materials by affecting the phase transformation process. People had found that pulsed current dramatically influences the behaviors of materials, for example, electromigration effect [l], the solidification of metals and alloys [2, 3], electroplasticity [4, 5], crystallization of amorphous alloys [6], healing of metal materials [7] and so on. As to pulsed magnetic field technology, a lot of effort had been spent on grain refinement in solidification of metals [8, 9], recrystallization of cold-worked metals and alloys [10] and Fe-based alloys solid-state phase transformation [11, 12]. Though application of pulsed current and pulsed magnetic field technology have proliferated in recent years, investigation on their effects on solid/solid phase transformation, especially bainite transformation, is lacking. The aim of this paper is to show the effects of pulsed current treatment (C-T) and the combined treatment of pulsed current and pulsed magnetic field (CM-T) on bainite transformation of commercial Cr5 steel"

Jan 1, 2014

By E. Kuzeci, R. Kammel

"Lately various voltametric methods have gained increased attention as an analytic tool in hydrometallurgy. Voltammograms with mercury drop electrodes or glassy carbon electrodes provide information about the electrocrystallization of cathodic deposits and allow calculation of kinetic data by means of characteristic parameters like the peak potential and peak current and their variation with the voltage scanning rate.Cyclic voltammograms are also suitable for identification of reaction sequences. Voltammograms with carbon paste electroactive electrodes containing metal sulphide additions reveal information about the dissolution behavior. The stripping voltammetry can be applied to analyze metal ions and organic additives (e. g., thiourea) in extreme low concentration. Typical application of the various methods studied with microcomputer controlled measurement system are explained by examples selected from copper hydrometallurgy.IntroductionThe use of electroanalytical methods in metallurgical process control can be dated back to the starting period of industrial copper refining, when the deposition of the metal ions was followed electro-gravimetrically by weighing the electrode with deposits (1). The principles of metal deposition and dissolution have not changed but the methods to follow these phenomena were subjected to noticeable developments and especially the introduction of polarographic investigations by Heyrowsky (2) has greatly contributed to the progress in electro-analysis. A review about the fundamental work on the electrochemical kinetics in earlier time is compiled in a monograph of Vetter (2). With the steady improvements in the instrumental techniques, it is nowadays possible to apply several current and potential modulations for measurements with improved selectivity and sensibility. There is however, still a lack in theoretical interpretation of the data obtained. More theoretical information are already available for linear voltametric methods for systems where reduced as well as oxidized species are dissolved in the electrolyte (4, 5). Some recent investigations have also shown the reliability of these techniques to study electro-crystallization (6, 7). Main fields of the application in the hydro - and electro-metallurgy are:"

Jan 1, 1989

By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By M. Pineau, G. A. Monteith, M. Laliberte, G. Houlachi

Conventional physico-chemical treatment methods, either hydroxide or sulfide precipitation, can hardly achieve a high removal of selenium from the liquid effluents which can be generated in some metallurgical operations. In weak acid solutions, selenium exists mainly as anionic species (selenite Se03-2 and selenate SeCV2) which, therefore, cannot precipitate as metal hydroxide or metal sulfide compounds. At the same time, neither selenite nor selenate form stable precipitates with the common cations (Ca, Mg, Fe, etc.) that are typically used in water treatment. At Noranda Inc., CEZinc Division in Valleyfield, Canada, the introduction of new discharge requirements for effluent toxicity initiated a R&D program which resulted in the full-scale implementation of a new treatment method for selenium removal. The goal of this paper is to present this new method which is now being patented by CEZinc. The process chemistry will be presented along with pilot-scale developments and full-scale operational results.

Jan 1, 2000

By Michael J. Nicol

This paper summarizes some of the results of a study of the reactions involved in the Caron leaching process and identifies the roles of the major dissolved species in the kinetics of dissolution of iron alloy particles formed during reductive roasting. Using rotating disk electrodes and synthetic leach solutions, the reduction of water with the evolution of hydrogen was found not to occur on a dissolving iron surface under typical leach conditions. It has been established that the oxidative dissolution is governed primarily by a reaction involving reduction of Co(III) to Co(II) ions. The reduction of oxygen was also found to make a significant but largely indirect contribution to the kinetics of the dissolution process. The dissolution rates of various iron-nickel-cobalt-copper alloys which simulate the dissolving alloy particles in a Caron plant were measured in synthetic leach solutions under aerobic and anaerobic conditions. The initial dissolution rates of iron, nickel and the iron alloys were found to increase in the presence of thiosulphate, whereas the thiosulphate had a negative effect on the dissolution rates of cobalt and copper. It is shown that the eventual passivation of the iron occurs sooner in solutions rich in Co(II) ions. Whilst these conditions are present in the quench slurry, on-site measurements have shown that due to the very high concentration of reduced dissolved species, passivation does not occur until the slurry is strongly aerated. In the light of these fundamental findings, options for optimizing the rate of dissolution and minimizing the extent of passivation of the iron and iron alloys are discussed. Keywords: Ammonia, leaching, alloy, kinetics, passivation.

Jan 1, 2004

By K. R. Robilliard

An outline is given of the problems facing tlile lead and zinc industry from the viewpoint of the range of residues currently produced from electrolytic zinc, blast furnace and other processes. Smelting approaches available using top submerged lancing technology are discussed and analysed. Pilot plant results for a range of lead and zinc-bearing materials are presented.

Jan 1, 1992

By Cody Burcher-Jones

The recovery of rare earth elements (REEs) through heap leach/in situ techniques from so-called ion adsorption clays (IACs) is attractive due to their inherent simplicity. However, the underlying mechanisms of these processes are poorly understood. In this study, the deportment of REEs in a typical IAC material has been investigated and was found to concentrate in the phyllo-layers of the clays, especially hallyosite, and was readily desorbed by various ion-exchange reagents indicating various potential routes to liberate them. Here we are reporting the use of seawater (0.5 M NaCl), spiked with various amounts of (NH4)2SO4, and found better extraction using a reagent mixture than NaCl on its own. Further, the leaching of REEs from a bed of clay material was investigated over time to understand the rate of transport through the stagnant material. Results indicate that REE release is likely to be controlled by diffusion through the clay material, while desorption in agitated systems is rapid. A degree of fractionation between different REEs can be observed during diffusion. Nonetheless, the successful operation of in situ leach operations for this type of material would depend primarily on how easily solution cocktails can be made to flow through the bed material.

By Jennifer Murphy, Brad S. Schake, Karol Holmes, John R. FitzPatrick, Mike H. West

"The separation and purification of uranium from either nitric acid or hydrochloric acid media can be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps.We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (1 DO-gram) flow experiments, using depleted uranium, were done after the small-scale evaluation of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos.Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process.Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail."

Jan 1, 1996

By Linfeng Zhou, Rong Sun, Guanghui Li, Zhiwei Peng, Tao Jiang

Dust, or airborne particulate matter, from metal smelting can be either mechanically or thermally generated and it negatively affects the indoor air quality as well as the fugitive emissions from the plant. The thermally generated dust is often referred to as fume and it is typically generated whenever liquid metal comes into contact with air. For practical reasons, such as vehicle access, etc. it is often difficult to collect 100% of the fume. It is therefore highly desirable to develop processes and optimize operational procedures so that fuming can be kept to a minimum. In this series of experiments, the mechanism of active oxidation and fume formation from liquid silicomanganese under an impinging air jet in the temperature range 1400-1600°C has been explored. Characteristic properties of the fume have been established; particle diameter, shape, size distribution, and elemental composition are reported. The oxidation process is described in terms of vaporization, oxidation and agglomeration. In the boundary layer, two competing mechanisms seem to be operative in parallel: a direct oxidation of Mn vapor, and a two-step oxidation of silicon. The thermodynamic and kinetic conditions governing the two mechanisms are discussed.

Jan 1, 2016

By C. H. Tsau

The intermetallic compounds of Ni-25Al-xFe, x is 20-40 at.%, were prepared by arc melting and drop casting into ingots, and were rapidly solidified into ribbons by melt spinning. The microstructure evolution of these alloys with varied Fe content were examined by the x-ray diffraction, optical microscope, scanning electron microscopy and transmission electron microscopy. The results reveal that two phases, {y'} and {B} phases, are existing in the alloys with low Fe content, and the microstructure changes from the mixture of y' and {B} phases to a single 0' phase when the Fe-content reaches to 40 at.%. Also, the formation of y' phase will be suppressed by rapidly solidified process. For annealing both of the melt-spun and the cast specimens, a disorder 0 phase was revealed in both of the ribbon and the cast ingot of Ni-Al-Fe alloys with higher Fe content. In addition, increasing the increment of iron which substituting nickel in this alloys results in increasing the lattice parameter of both {y'} and{B} phases.

Jan 1, 1992

By David Tisdale, Phillip Mackey, Nagendra Tripathi, Matthew Kreuh, Pascal Coursol

Xstrata Nickel’s Sudbury smelter operation is based on fluid bed roasting of Ni-Cu sulphide concentrate, followed by electric furnace reductive smelting and Peirce-Smith converting to produce a Bessemer matte for electro refining, along with sulphuric acid produced from smelter gas. While the site dates back to the 1930s, the present smelter configuration has been operational since 1978, and currently has a nominal capacity of about 67,000 tpy of contained nickel and is investigating options to expand in future up to 85,000 tpy. As part of a review of plant capacity options, a new metallurgical model of the plant was developed in order to examine a number of processing alternatives. Based on the METSIM™ platform, the present model includes the ability to examine the impact of a number of plant parameters on potential plant performance including; for example, the following: percent of sulphur elimination in roasting, matte grade, degree of matte metallization, temperature, coke requirements, sulphuric acid production, CO2 emissions and overall energy requirements. The process model also includes a number of special features adopted; for example, approaches to effectively model the complex Ni-Cu-Co-Fe-S-O matte system. This paper provides a description of the model and gives an overview of the results. As well as presenting the results of the present study, the applicability of this modeling approach to pyrometallurgical systems in general is also briefly discussed in the paper.

Jan 1, 2009

By L. Petitnicolas

The experimental study of nitrogen absorption and its removal from a liquid Ni-20%Cr alloy at 1873 K has been undertaken, using an experimental, apparatus based on the Sieverts technique in order to determine the solubility of nitrogen in the alloy. as well as the kinetics of nitrogen transfer across the gas/melt interface. Experiments show that nitrogen solute equilibrium content can be calculated using the Sievens law. Measurements point out the nitrogen absorption reaction rate to be well described by first order kinetics, whereas experiments on nitrogen removal reveal that the rate is better expressed using a second order equation.

Jan 1, 1996

By R. J. McClincy

The potential techniques for the direct smelting of copper sulfide concentrates to blister copper were evaluated from the standpoint of commercial application. Many existing smelters are adaptable to direct smelting practice but only with improved control of metallurgical performance. Modified and innovative procedures for slag cleaning and metal refining, prerequisites to direct smelting, are presented and discussed. The ability to smelt directly to blister copper using existing equipment and eliminating the need to convert matte offers ,significant advantages to traditional smelting practice from the viewpoint of cost, 'S02 control, and process simplicity.

Jan 1, 1983