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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 Junbiao Liu

Rutile is mostly produced from placer sands. Its beneficiation from primary deposits has rarely been investigated. However, there is interest in primary deposit because of the depletion of sand deposits. The Zaoyang deposit in China is the only rutile primary deposit currently mined. The plant employs a Tabling-Magnetic process which recovers only 20% Ti02 at a grade of 87%. This study shows that significant improvement on the recovery (52% at the same grade) can be achieved. This study includes a detailed mineralogical examination and the development of a processing flowsheet of the ore. The gangues are primarily amphiboles, garnets, zoisites, and chlorites. The liberation of rutile occurs at about 200 mesh. Gravitational, flotation, and magnetic separations are all employed in the process developed, depending on the mineral characteristics and experimental results. The flotations circuit utilizes benzyl arsonic acid to float rutile and sodium fluosilicate to depress the gangues. This is a new reagent scheme for rutile flotation.

Jan 1, 1989

By J. T. I. Poijärvi

The smelter off-gas cleaning and the weak acid treatment at Outokumpu Harjavalta Metals Oy are presented and described in this paper. The smelter consists of the copper and nickel smelters and the acid plant of three separate acid plants two of which are double contact and one single plant and of one liquid sulphur dioxide plant. The preliminary cooling and flue dust separation of the smelter off-gases from the copper and nickel flash smelting furnaces and converters in the waste heat boilers and in the hot electrostatic precipitators are described. The final cooling and cleaning of the gases in the scrubbers at the sulphuric acid plant and the treatment of the weak acid in the vacuum and in the submerged combustion evaporators for the removal of impurities are pre¬sented as well as the treatment of the condensates from the evaporators. The attention is paid to the generation of sulphur trioxide in the smelter off-gas and to the treatment of that in the weak acid bleed-off and to the utilization of the treated acid.

Jan 1, 1992

By Eva B. Kisvarsanyi

An Early Proterozoic orogenic terrane of metasedimentary and metaigneous rocks underlies Nebraska, Kansas, and Missouri. Middle Proterozoic epizonal terranes of anorogenic granite and rhyolite, a known metallogenic province partly exposed in southeastern Missouri, overlap the orogenic terrane on the south. These Proterozoic terranes, covered by less than 1,000 meters of Phanerozoic strata, contain a virtually untapped source of mineral wealth and are one of the last frontiers for geologic exploration in the continen-tal United States. Petrographic study of subsurface samples is a powerful tool in the identification of favorable host rocks for a variety of ore deposits.

Jan 1, 1987

By Hsing Kuang Lin

Ferric chloride leaching w.as applied to a complex sulfide ore from Tok, Alaska to dissolve zinc, lead, silver and copper. Gold in the leaching residue, as well as in the ore, is found to be refractory to the conventional cyanidation process. Roasting, pressure oxidation and elemental sulfur removal followed by cyanidation were tested to improve gold dissolution. Also tested were thiourea leaching and high-pressure cyanidation. The readsorption of dissolved gold by carbonaceous matter in the chloride leaching residue was analyzed. Based on the experimental results, factors causing difficulty of gold dissolution from the leaching residue are discussed.

Jan 1, 1989

By V. Jiricny

There is a growing need to process galvanized steel scrap from automobiles, etc., in order to remove the zinc coating that otherwise causes problems in remelting of the scrap in electric arc furnaces. One approach that has moved to the pilot plant stage is that of Metal Recovery Technologies, Inc., of East Chicago (MRI). That company leaches the zinc fiom the scrap with a sodium hydroxide solution. The leached and washed scrap can then be returned to the steel industry. What is left is a sodium hydroxidelzincate solution which must be processed to recover the zinc and the NaOH. Presently, this is done by MRI using electrodeposition on planar electrodes at moderate current density and the resulting zinc is in the form of fine powder which is hard to process into, say, zinc for galvanizing. MRI has supported an investigation of a novel electrode, the spouted bed electrode (SBE), for zinc electrodeposition. In laboratory cells, zinc particles with low porosity have been grown up to 3mm in size. Microanalysis of the deposited zinc showed low level of impurities. DC energy consumption values were usually in the range of 2-2.5 kWg which is well below the energy consumption of the existing cells (and of present-day cells for electrowinning from acid sulfate electrolytes). These results were achieved at current densities (few thousand A/m2) that are much higher than possible with conventional electrodes. Discussion is provided of the scale-up of the cell to a commercial scale.

Jan 1, 1998

By Gerald Onyedika, Tochi Onwumere, Martin Ogwuegbu

"The kinetic study for the leaching of iron from cassiterite ore in KOH solution was studied. The effects of KOH concentration, particle size and reaction temperature on the leaching rate of iron were also examined. The results of leaching studies showed that the leaching of iron from cassiterite ore in KOH solution is significantly influenced by the reaction temperature, KOH concentration, and decrease in particle size. The study showed that 90.62% of iron ore was leached in 8M KOH solution at 80°C within 120 minutes. The experimental data were well evaluated using the shrinking model for surface chemical reaction and diffusion control through the product layer. The activation energies for the iron ore dissolution using the two models were calculated to be 32.06KJmor1 and 97.97 KJmor' respectively.IntroductionIn recent times, there has been increasing attention on the kinetic study of mineral dissolution. In most of these studies, the experimental results were analyzed with a suitable shrinking core model under the assumption that the ore is a homogeneous spherical solid phase [1-4]. A study of the dissolution kinetics of a Nigerian cassiterite ore by hydrochloric acid showed that increase in the hydrochloric acid concentration is accompanied with increase in the amount of cassiterite ore dissolved at various times [4]. The optimal concentration was found to be 4.0M HCl, after which there was a decline in the amount of the ore dissolved, which showed that the concentration of the reagent has a significant effect on the leaching rate of the ore. Also in studying the effect of stirring speed on the rate of cassiterite ore dissolution while keeping other conditions constant for 120 minutes, the result showed that the rate of cassiterite ore dissolution was dependent on the stirring speed over a range of 0 to 630 rpm. Above 360 rpm, the stirring speed no longer had any effect on the solid dissolution. The dissolution rates of cassiterite were analyzed using a suitable shrinking model. The results showed that the reaction was controlled by the diffusion of tin through the porous product layer, a reaction order with respect to hydrogen ion concentration of 0.92 M and activation energy of 50.05KJmor'. In another kinetic study on the leaching of a low grade niobium-tantalum ore with concentrated KOH solution the effect ofreaction temperature, KOH concentration, agitation speed, particle size and alkali-to-ore mass ratio on the dissolution rate of niobium were examined [5]. The result of niobium leaching from low grade niobium-tantalum ore with concentrated KOH, solution at different agitation speeds showed that the dissolution rate increased with increase in agitation rate. In the case of particle size effect, the results show that small particles require much shorter time for complete dissolution than the large ones."

Jan 1, 2013

By J. David Chapman

There are a variety of choices of materials for mineral extraction processing. Traditionally, end users have used metallic piping for fluid handling and little is known about the advantages (or limitations) of non-metallic piping systems. This presentation will review custom FRP pipe systems and their use in severe corrosive and erosive process streams. These systems can be designed to various pressure and temperature ratings and different components (such as resin and glass type) can be varied to suit the process conditions

By E. J. Peuraniemi

Primary copper production using suspension smelting techniques like Outokumpu Flash Smelting always causes some dust formation. Flue dust particles are formed when sulphide feed material reacts violently with oxygen inducing particle disintegration and total desulphurisation of fragments. In the process, flue dust follows the off-gases to the heat recovery boiler (HRB) where its sulphation takes place because of prevailing conditions. Sulphation releases heat and causes also a drop in particle melting temperature and, further, particle sticking to the walls and heat exchange tube banks. Sulphation of synthetic CU20 particles were examined using a laboratory scale fluid-bed reactor. This study aims to a better understanding of flue dust behaviour in a HRB and, thus, to a better operational practise and design of a HRB. The effect of PSO/PO2 -ratio and temperature on the sulphation kinetics were tested. Standard chemical analysis, light optical and scanning electron microscopy with energy dispersive spectroscopy were used to examine the samples.

Jan 1, 2001

By D. P. Cook, Jr. Jones, J. W. Evans

"It is well understood that the flow of liquid metal in the mold region of the caster can have a notable effect on the overall solidification behavior in aluminum casting. Previously our group has characterized the flow in this region in a water model, using particle imaging velocimetry. The flow is significantly effected by the specifics of the metal delivery system, i.e. size, geometry, used during the cast. Recently, a time-averaged 3D numerical model of the nozzle, combo bag and sump region has been developed and its validity has been tested against experimental data. Cases were run for different sized combo bags as well as bags that have been blocked. The results show satisfactory agreement between the physical and mathematical models.IntroductionFluid flow in the head of an electromagnetic (EM) and direct chill (DC) ingots has been shown to effect many important operational parameters in casting such as superheat removal, macrosegregation, and hot cracking. In most cases, the momentum from the nozzle is diverted through a delivery system, termed a bag, before entering the mold region. The specific geometries of the bags vary widely from operator to operator suggesting that there is still some question as to the optimum design. Several studies [1-4] have been carried out to understand the influence of the bag design on the solidification behavior in aluminum casters. However, few studies have included numerical prediction with experimental verification. Unfortunately, many simulations performed today still do not accurately account for flow in such devices.Recently, a significant amount of research into the flow resulting from the metal delivery systems has been performed [5-8]. The thrust of this research has been characterizing the flow patterns by a measurement technique called particle imaging velocimetry. The data suggest that the method of delivering the liquid metal into the mold region has a significant effect on the nature of the flow. With a detailed set of quantitative data from a water model, a numerical model can be built and tested to ensure a proper description of the flow field. The computational model used in these simulations is designed to represent a laboratory scale model of a caster in which ""combo"" bags were simulated. Such bags are mostly of a densely woven glass fiber material with low permeability to aluminum. ""Windows"", of a more open weave, permit aluminum to flow from the bag, see Fig. I. Two different sized combo bags were modeled, each subject to two different outflow window configurations. Furthermore, experimental measurements [9] were used to validate the model results."

Jan 1, 1999

By P. F. Stratton, M Huggahalli, N Saxena

"Several studies have been carried out to determine how the optimum atmosphere conditions in the heat treatment of metals can be established for a given product by using different gas injectors and varying atmosphere flow rate and composition. The most common approach taken to gain insight into furnace atmospheres has been to use commercial computational fluid dynamics codes and examples of their use are shown. However, the complexity of these codes, the difficulty in establishing boundary conditions, their cost and computational demands limit their usability in solving day-to-day production problems.A simplified, web-based model of a furnace atmosphere is described where the conservation equations are solved to determine the composition profiles of the atmosphere in the furnace. Although the model is restricted in scope to certain types of furnace, it is shown to give better results than CFD when boundary conditions are uncertain. The application of the model to the understanding of existing furnace conditions and to determining ways of optimising the use of gases are discussed. IntroductionThe important role of protective atmospheres during heat treatment of metals, furnace brazing of assemblies and soldering of printed circuit boards is well established. The atmosphere in the furnace prevents air ingress and oxidation of the parts, helps flush away any flux or binder from braze and solder pastes and provides an important mode of heat transfer [1]. In a batch furnace having typically one or two gas injectors, the gas utilisation and process can be optimised by minimising air leaks and mantaining atmosphere homogeneity with fans or other atmosphere circulation techniques. In a continuous furnace, however, atmosphere optimisation is more difficult as furnace inlets and exits can also let in air. The atmosphere requirements of different stages of heat treatment, brazing or soldering vary [2]. Achieving these atmospheres in different sections of the open-ended furnace is a relatively complex task. Methods such as atmosphere zoning and the use of physical curtains and gas injectors have evolved with time, though it is hard to predict how effective these techniques will be for a given furnace and process. Experts in the field tend to rely on experience and rules-of-thumb rather than scientific method to achieve the required results."

Jan 1, 2001

By Susanne Pignolet-Brandom

Reflected light microscopy, and scanning electron microscope energy dispersive spectroscopic analysis and backscatter electron images were used to determine if a "slick dross" with undesirable handling properties has an assemblage of phases distinct from normal dross. This study has found that in the normal dross the most abundant lead phases are lead sulfide and lead metal and the most common copper phases are copper-iron sulfide and copper sulfide. In the slick dross, the most abundant copper phase is copper-lead sulfide and the most common lead phases are copper-lead sulfide and lead sulfide. The resulting mineralogical information has provided additional insight into the causes of the handling problem and the reaction mechanism for the formation of normal and slick dross

Jan 1, 1988

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By V. M. Sokolov, Jr. DuPlessis

The technology for recycling fine wastes, grinding sludges or swarf, and solids such as slag that contain a high content of metallic material needed improving. The objective was to produce a master alloy that met the tight requirements of the Western manufacturers and achieve improved yields of the valuable elements, nickel and cobalt, to over 90%. The alloys from the production of Alnico. magnets were chosen for this work. A process is proposed .that is able to recycle all kinds of Alnico wastes. This process is able to reduce all detrimental elements, which are contained in the wastes, to within acceptable levels. Molybdenum, if present, is an exception. Depending on the levels of contamination of undesirable elements different recycling strategies are proposed. The majority of the wastes can be recycled by melting and refining with a liquid slag layer using unique melting furnaces that are relatively unknown in Western nations. The proposed technologies allow the reelamation of over 95% of the cobalt and nickel from any kind of Alnico waste, and there are no limitations on the proportion of different kinds of wastes in the charge. The proposed processes and technologies could also be applied to the recycling of grindings, turnin

Jan 1, 2000

By J. Howarth

Two electrochemical processing methodologies have been used to electrogenerate bromine-laden solutions for gold-leaching purposes. In the first process, a laboratory-scale cell in which the anode and cathode compartments were separated by a cation-exchange membrane was employed. The bromine produced by electrolysis of a 4% bromide solution was used to leach gold from a low-grade ore. The pregnant leach solution was then returned to the cell to recommence the cycle. High current efficiencies (90-93%) were maintained over six cycles. In the second process, an undivided hypochlorite generating cell (Chloropac"') was used to generate bromine from a simulated leach solution. Electrolyses were performed on a pilot-scale (100-150 gallons) with solutions containing different levels of bromide ion. The current efficiencies were also high (80-90%) and unaffected by the bromide concentration (over the range 2.5-5%) provided the electrolysis was run to low conversion « 15%). The Chloropac module was capable of delivering 0.6 kg bromine per hour at a power cost of $0.09 per kg. Using these figures, a detailed economic assessment for a 1000 metric tonnes (MT) per day gold ore processing plant was made. Electrolytic regeneration of bromine in a gold leach/recovery circuit dramatically improves the process economics over cyanidation.

Jan 1, 1991

By Guo Xueyi

The electrochemical couple behavior of manganese dioxide with ferrous/ferric ions in acidic chloride medium was investigated, It was proven that the dissolution of Mn01 is due to the electrochemical couple reaction between MnO2/Mn2+ and Fe2+/lFe3+ in the solution, The driving force for the process originates from the rest potential difference of the two couples. The reduction of Mn02 is controlled by clectrochemical kinetics, whereas the conversion of F e2+ to Fe3+ is limited by diffusion, The factors such as the Mn2+, Fe2+, Fe3+, Cl concentration, pH of the solution and the temperature, have much influence on the kinetics of the couple process, This study will be useful to elucidate the mechanism for the leaching of manganese nodule from the deep ocean as well as manganese dioxide ores in land,

Jan 1, 2003

By Ann M. Hagni

Microscopic and sub-microscopic gold commonly occurs in the sulfides pyrite (FeS2) and arsenopyrite (FeAsS). To recover refractory gold from pyrite and arsenopyrite, these sulfides are roasted to create porosity and permeability prior to cyanide leaching. A new technique of adding Ca(OH)2 and roasting. lime roasting. is being tested for retention of contaminant sulfur and arsenic and effectiveness of gold extraction. The lime roasting of pyrite at 500°C contains anhydrite (CaS04). oldhamite (CaS). calcium sulfite (CaS03). hematite (Fe2O:J), magnetite (Fe304). and minor amounts of pyrrhotite (Fe1.xS) and pyrite. At 600°C. 650°C and 700°C. the main constituents are anhydrite. oldhamite. and hematite. At 750°C. 800°C. and 850°C. anhydrite and hematite are the predominant phases with minor oldhamite. The roasted arsenopyrite at 450°C contains arsenic sulfides. calcium sulfite. hematite. and minor oldhamite. magnetite. and pyrrhotite. At 650°C. 700°C, 750°C. and 800°C, anhydrite, oldhamite. arsenic sulfides, and hematite are present. At 850°C. the same minerals are present with only minor oldhamite. The textures indicate excellent porosity and permeability at high temperatures. At lower temperatures, rims of low porosity and permeability surround many of the pyrite and arsenopyrite particles, and the complete oxidation process from pyrite to pyrrhotite to magnetite to hematite can be observed in individual particles. Additional process mineralogy techniques employed in this study are electron spectroscopy for chemical analysis (ESCA) and cathodoluminescence microscopy (CIM) in the determination of the calcium-sulfur-oxygen phases. Automated scanning electron microscopy-energy dispersive spectroscopy was utilized to analyze particles for gold content. Reflected light microscopy (RIM) revealed arsenopyrite and pyrite encapsulated in quartz particles of the gold-bearing concentrate, gold roast calcine, and cyanide leach residue.

Jan 1, 1991

By Thierry De Nys

A direct leaching process of sulphidic zinc-based concentrates in aqueous sulphuric acid solutions has been developed by the V.M. R & D Department. By a very accurate control of the oxidation potential of the leach solution, this process enables a separate recovery of the zinc, copper, silver, lead and sulphur of the concentrate and makes it extremely attractive for treating more complex ores. The iron, solubilized during leaching, is eliminated out of the zinc solution by means of the V.M. goethite process. Alternative flow sheets for a conventional zinc electrolysis plant are presented.

Jan 1, 1990

By David Van Aken, Arpana S. Murthy, Simon Lekakh, Von L. Richards

"Three heats of 17-4PH stainless steel: with zero, three percent, and seven percent cobalt addition were melted in a 45kg (1 00lb) induction furnace under argon; and cast into no-bake molds and preheated investment shell molds. Specimens were sealed into quartz tubes under vacuum, and homogenized at 1200°C from 2h to 72h. Computational thermodynamics and optical microscopy were used to predict and characterize the microstructures. The lath martensite packet size and the amount of 8-ferrite were observed to be inversely related. A compromise between decrease in segregation and increase in lath martensite packet size was chosen for the optimum homogenization treatment. The specimens were austenitized, quenched, and characterized for retained austenite using x-ray diffraction. Age hardening kinetics were studied at 454°C (850°F), 468°C (875°F), and 482°C (900°F); and, the activation energies for precipitation of copper were calculated. Tensile properties and Charpy V-notch impact energies were measured in the peak aged condition. Fracture surfaces were observed using scanning electron microscopy and Energy Dispersive Spectroscopy. The addition of cobalt was found to be beneficial for the improvement of strength as well as notch toughness.IntroductionSegregation in the as-cast condition is one of the drawbacks of metal casting. This paper presents a study on the homogenization treatment of 17-4 PH cast stainless steel and the effect of cobalt addition on tensile properties and Charpy V-notch toughness. Lattice dilatation studies show that additions of up to 6% Co to iron has a negligible effect on the lattice parameter, whereas both the modulus of elasticity and shear modulus increase with increasing cobalt additions5• An ordering reaction has been reported in cobalt-containing, maraging steels and contributes to the hardening during ageing1-4• Although, cobalt addition in maraging steels has been extensively researched, and has been reported to be beneficial; it has not been explored much in other age-hardening stainless steel systems. In a previous study, the addition of 3% Co in cast 17-4 PH martensitic age-hardenable steel was found to improve the strength and elongation while maintaining the charpy V-notch toughness6."

Jan 1, 2011

By Thomas E. Weyand

Prior to 1975, lead-based paints were commonly used in protecting steel structures. Because of the toxic effects of lead on human health and the environment, their use has been significantly reduced. However, problems with these paints persist when they are removed during normal maintenance by pneumatic blasting with mineral abrasives. Technologies are developed to contain the spent abrasive and paint during blasting operations. This paper reports on A study to identify beneficial reuses for the spent blasting material. Nine samples were gathered from different projects within Pennsylvania. The samples were thoroughly characterized with regard to composition, morphology, and EP and TCLP leach test performance. Potential reuse applications will be reviewed with regard to technical adequacy, economics, and environmental constraints.

Jan 1, 1992