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By P. T. Velu, R. G. Reddy

"The use of emf measurements to derive classical thermochemical data has been in use for many years. The reaction associated with electrochemical process is harnessed in a galvanic cell and energy involved measured in terms of electromotive force. The property requirements of sensor electrodes used differ for various aqueous, molten salt and solid electrolyte systems. The electrodes for molten salt electrolytes need special care for construction. This paper describes the studies carried out using an Ag/ AgCI reference electrode. This electrode was used to measure the solubility of compounds in molten salt electrolytes. The results obtained using this electrode are in excellent agreement with the values from chemical analysis method.I. IntroductionThe technique of obtaining a metal from its oxides by electrolysis is more than a century old process now. In these processes, it has been well established that for halide electrolytes, only the dissolved oxides are available for the dissociation at the electrode to release the metal during electrolysis. Therefore, the solubility of metallic oxides in the molten salt electrolytes is an important parameter which determines the economical and technical viability of these processes. The widely used molten salts systems in halides are fluorides and chlorides. The fluoride electrolyte system is used in our present study.The viability of obtaining aluminum alloys by in-situ electrochemical processing has been outlined in our earlier publications[1-8]. Studies on the solubility of various alloying element compounds is a part of our ongoing research efforts for the direct production of Al-Li alloys. As mentioned above, the solubility of lithium oxide and lithium carbonate compounds in molten fluoride electrolyte system have studied using EMF technique. The change in potential of the molten electrolyte was measured by a working electrode against the reference electrode with the addition of lithium compound."

Jan 1, 1997

By Susumu Imashuku

A pseudoternary phase diagram of the BaO?ZrO2?ScO1.5 system is established and the conductivities of the scandium-doped barium zirconate are measured in wet conditions. According to the phase diagram, the molar fraction of scandia in the barium zirconate phase that equilibrates with the cubic zirconia (ZrO2) and scandia (Sc2O3) phase is 0.03. On the composition line, where the molar fraction of barium oxide (BaO) is 0.50, the solubility of scandia into barium zirconate is 0.27 as a molar fraction of scandia. At around 500 °C, the conductivities of scandium-doped barium zirconate are estimated to be almost same as that of yttrium-doped barium zirconateThe activation energies for bulk proton conduction in scandium-doped barium zirconate (0.57 eV for BaZr0.90Sc0.10O3-d) are higher than that of yttrium-doped barium zirconate (0.44 eV for BaZr0.90Y0.10O3-d). In addition, the bulk conductivity of scandium-doped barium zirconate in this study is 10 times higher than the reported conductivities in the temperature range of 75 °C to 300 °C.

Jan 1, 2006

By Shunsuke Yagi

A surface alloying technique was investigated using alternating pulsed electrolysis in an aqueous solution containing a single metal component for the formation of an Fe-Cr layer on an iron substrate. In the process, the iron substrate was dissolved during each anodic polarization of the pulsed electrolysis, providing iron ions in the vicinity of the substrate, while the Fe-Cr alloy was electrodeposited during subsequent cathodic polarizations. A bright, flat, and crack-free Fe-Cr layer with a composition gradient was obtained using a solution containing a trivalent chromium component and a complex forming agent together with some supporting or buffering salts.

Jan 1, 2006

By A. Rawat

The removal of oxyanions of arsenic present in mine process water and drinking water to a regulatory level is a challenging problem. Recently a patented adsorbent lanthanum oxide has been developed which has shown strong specificity for the anions of arsenic. In this paper the kinetic and thermodynamic aspects of arsenic adsorption on to lanthanum oxide are discussed. Adsorption tests were performed at different temperatures using synthetic solutions of arsenic of varying concentrations. From the kinetic data and adsorption isotherms thermodynamic properties such as Gibb's free energy, standard enthalpy of adsorption, standard entropy, isosteric heat of adsorption and activation energy were determined. The results showed that temperature had a positive effect on the rate and degree of adsorption:The activation energy decreased with increase in the initial concentration thus indicating solute-solute interactions in the system. Also, the isosteric heat was found to decrease with increase in the adsorption density implying a heterogeneous adsorbent surface.

Jan 1, 1998

By Joseph D. Lessard

A process simulation of the conversion of molybdenum disulfide concentrates into molybdenum dioxide via the Looping Sulfide Oxidation process has been performed using HSC 7.1 thermodynamic software. By decoupling molybdenite conversion and molybdenum oxidation, Looping Sulfide Oxidation changes the paradigm by turning molybdenite processing into an energy generator while producing a molybdenum dioxide, which has a lower vapor pressure and lower oxygen content than molybdenum trioxide. The Looping Sulfide Oxidation process selectively produces molybdenum dioxide over molybdenum trioxide. This process uses a stoichiometric mixture of oxygen and molybdenum trioxide as oxidants in the conversion of the molybdenum sulfide to the molybdenum oxide. The model simulates the two reactor scheme required by Looping Sulfide Oxidation and incorporates thermodynamic equilibrium simulations performed in FactSage 6.3.1 thermodynamic software. Energy capture is also maximized with heat exchanger systems to transfer heat released in reactions to preheat air.

Jan 1, 2014

By Gus Van Weert

The cost of oxygen is a major and common factor in the hydrometallurgical processes developed or proposed tor the oxidation of refractory pyrites. This cost involves charges for the generation and the transfer of the 02 to the mineral slurry. Bio-oxidation faces considerable design demands which require large scale equipment to be resolved. Nitric acid assisted oxidation offers low cost oxygen units; this method of pyrite oxidation deserves a closer look for large scale plants treating pyritic gold ores and concentrates.

Jan 1, 1990

By Masayuki Kudoh, Tohru Maruyama, Yohichi. Ito

When hypo-peritectic carbon steel is quenched during unidirectional solidification, the region of fine columnar grain is observed. It is classified into two coexisting phases. One is coexisting phases of liquid, delta and gamma in the upper part of the region, and the other is coexisting phases of delta and gamma in the lower part of the region. To form the coexisting part of the three phases means that solidification in this experiment proceeds in non-equilibrium state. The size of the narrow side of one fine columnar grain coincides with the arm spacing of a primary dendrite and this result is the same as the hyper-peritectic carbon steel. However, the boundary of the fine grain in the hypo-peritectic carbon steel is formed in different location from that of the hyper-peritectic carbon steel. The former is formed in the skeleton of the dendrite, while the latter is formed in the interspacing of the dendrite. The region of the fine grain changes suddenly to that of the coarse grain when the delta phase in the coexisting part of two phases disappears completely. Therefore, the delta phase in the hypo-peritectic carbon steel might prevent the growth of gamma grain. In order to recognize it, ferrite formers such as Mo, V and Ni are added in the sample. Then, the longitudinal length of the fine columnar grain extends in the sequence of the no addition, Mo, V and Nb.

Jan 1, 2000

By Xiaobing Yang, Abhishek Lahiri, Animesh Jha

"In the FFC-Cambridge process, the cathodic dissociation of oxide and CO/CO2 production on carbon anode is the basis for metal production in a CaCl2 bath. By using an inert intermetallic anode, the CO2 evolution can be eliminated altogether with acceleration in the electro-reduction kinetics. At present the process suffers from slow reduction kinetics of TiO2 to Ti metal, which can be enhanced significantly by the incorporation of alkali species in the TiO2 pellet at the cathode and in the CaCl2 bath in the presence of an intermetallic inert anode. Nearly full metallization with greater than 99% of Ti metal containing 1500 ppm of oxygen is possible to achieve in less than 16 hours of electro-reduction. Analyses of phase composition and the microstructures morphology in fully metallized pellets revealed the presence of localized solidified Ti layer, indicating that fast reduction process also involved formation of liquid phase as middle stage reaction. In addition, in situ creation of porosity and maintain higher current level during electrolysis process were two key factors to fully reduction of TiO2.IntroductionDuring cathodic dissociation of TiO2 in a CaCl2 bath and anodic evolution of CO2 on a carbon anode, which is the basis for the FFC Cambridge process [1], the rate of metallization slows down due to the formation of CaTiO3 at the reaction interface. Calcium and alkaline earth perovskites are known for their poor electrical conductivity which adversely affects the overall electro-reduction. One of the ways to increase the porosity is via the addition of polyethylene precursors in the pellet or by directly starting from perovskite [2, 3]. The experimental evidences shown in the literature confirm although the speed of reaction increases, but a complete or near complete metallization is not possible by enhancing the in-situ porosity alone, as the insulating perovskite is very slow to decompose under the equilibrium that prevails in the cell. Plethoric evidences on carbon anode show with the current decrease gradually, and finally stabilize at a very low value between 0.2 and 0.4 A, which is a testimony of the presence of perovskite insulating barrier in the current path. Our aim in this paper is to demonstrate the mechanism of enhanced electro-reduction when alkali ions are present in the oxide pellet at cathode and in the bath. We also show for the first time the use of an intermetallic anode for Ti-metal production using the FFC Cambridge process."

Jan 1, 2009

By Gudrun A. Saevarsdotti

For decades tile aluminium industry has been practicing gas treatment of aluminium melts. This treatment is of great importance because of its influence on 'impurity" and inclusion removal from the melt. The gas-melt interaction is greatly influenced by the gas composition, melt temperature etc. This paper gives an overview of the interaction between argon-chlorine gas mixtures and the aluminium melt. It covers the thermodynamics of the reaction between the chlorine and a number of different elements commonly found in liquid aluminium, and discusses the behaviour of reaction products in the melt. The paper reports an experimental study of the behaviour of the chlorine-molten aluminium interface, using sodium contaminated aluminium melt with and without the addition of grain refiner.

Jan 1, 1996

By Leonid N. Shekhter, Corby G. Anderson, Esra Cankaya-Yalcin, Daniel G. Gribbin, Joseph D. Lessard, Larry F. McHugh

"A new process for smelting copper, Looping Sulfide Oxidation™ (LSO™) significantly and positively alters the smelting energy balance. This process uses copper oxide in conjunction with air for the desulfurization of copper and chalcopyrite concentrates. Copper oxide is regenerated in a flash type furnace and then ""looped"" back for the oxidation of the copper concentrate. Heat and material balances show that the Looping Sulfide Oxidation™ process requires significantly lower net energy than conventional technology. This process produces anode copper and higher S02 content off-gases for efficient formation of sulfuric acid. Additionally, the process yields slags with lower copper solubility as compared to the conventional technology.IntroductionBased on the positive results from LSO™ investigations [1], further lab investigations into co=on sulfides and metal oxides were performed. It was discovered that chalcopyrite (CuFeS2) is oxidized with copper (II) oxide. In this reaction over 98.5% of sulfur was removed as S02, while a significantly improved energy balance was observed. This paper intends to analyze both the conventional flash smelting process and the newly developed Looping Sulfide Oxidation™ process, comparing heat and material balance results. LSO™ yields improvements to the energy footprint for copper, opening the door to new copper processing opportunities."

Jan 1, 2013

By Hui Zhang

The leaching behavior of palladium powder in aqueous solutions containing NaCI or N'H4Cl was investigated. Cupric ion was used as an oxidant for the dissolution reaction. The effect of a number of leaching parameters such as temperature, concentration, stirring speed and surface area on the leaching rate was studied. The leaching system containing chloride and cupric ion was found to be very effective for the dissolution of metallic palladium. Based on the experimental results the overall leaching rate was believed to be controlled by a chemical reaction step. The dissolution rate of palladium was found to be first order with respect to the concentration of cupric ion and second order with respect to the concentration of chloride.

Jan 1, 1996

By Yuanbo Zhang, Zhixiong You, Li Qin, Guanghui Li, Tao Jiang

Low-grade manganese oxide ore is generally characterized by high iron content. In this work, sulfidation roasting of an iron-rich manganese oxide ore with elemental sulfur was characterized. The experimental results indicated that manganese dioxide can be selectively reduced over iron oxide by using elemental sulfur. The manganese phases in roasted product included low-valence manganese oxide, manganese sulfide and manganese sulfate, while those of iron mainly depended on the sulfur addition. Iron oxide would only be reduced or sulfidized at larger sulfur additions. The effect of roasting temperature and S/Mn mole ratio on the phase transformations was also investigated; extractions of Mn/Fe by sulfuric acid were evaluated. An extraction of Mn greater than 95% was obtained while that of Fe was controlled less than 10% under the optimal conditions.

Jan 1, 2016

By James C. Sever

Two green field magnesium reduction plants are under consideration using dolomite as the raw material. The Calix calciner was independently selected for both plants. The unique design of this calciner is detailed and the advantages defined for the specific application. The low carbon foot print of this unit combined with the ability to capture food grade carbon dioxide makes this an environmentally proactive approach to carboniferous ore calcination.

Jan 1, 2015

By Takeshi Ohgai, Hisaaki Fukushima, Tetsuya Akiyama, Joon-Seo Ki

"Recently, an intensive attention has been paid to the electrodeposition of Zn-Cr alloy in the field of the production of super-highly corrosion-resistant alloy plated steel sheets for the next generation. In this study the electrodeposition of Zn-Cr alloys from the sulfate baths was conducted to investigate the codeposition mechanism of Cr with Zn. As a result, Cr was codeposited with Zn at higher current densities in both polyethyleneglycol(PEG)-free and PEG- containing baths. However, PEG made it possible to reduce Cr+ to the metallic state and Cr existed in the form of Cr(III) hydroxide in the deposits obtained from PEG-free bath. The measurements of the partial polarization curve of Zn and the pH in the cathode layer revealed that PEG acted as a polarizer to shift the cathode potential to the reduction potential of the composited hydroxides of Zn and Cr formed due to the pH rise in the cathode layer.1. IntroductionRecently, much attention has been paid to the electrodeposition of Zn-Cr alloys because of its application to the production of super-highly corrosion-resistant alloy plated steel sheets for the next generation1Hl_ Some researches have already tried to commercialize this type of steel sheet. High corrosion-resistance of this steel sheet is brought about by codeposited Cr in the alloys. According to Piontelli's classification5l concerned with metal deposition from aqueous solution, Cr belong; to an inert metal and its deposition is associated with a large amount of hydrogen evolution. Therefore the current efficiency for Cr deposition is extremely poor. It has been also reported that Cr is unable to codeposit in the electrodeposited Zn film in the absence of a certain additive in the solution. 0-compounds group colloids7l, ether group organic compounds8), 9>, peptide based compounds10l, etc., have been found to be effective additives to induce the codeposition of Cr with Zn. However, few studies have been made on the codeposition mechanism of Cr with Zn. In this research, the fundamental electrodeposition behavior of Zn-Cr alloys from sulfate baths was investigated to clarify the codeposition mechanism."

Jan 1, 1998

By Itsuki Uehara, Hiroyuki T. Takeshita, Tetsuo Sakai, Nobuhiro Kuriyama, Hideaki Tanaka

"AB5 type hydrogen storage alloys (A: rare earths, B: transition metals) are extensively applied to a negative electrode of a nickel metal hydride (Ni-MH) rechargeable battery for portable electric equipments, electric vehicles, hybrid vehicles etc. Performance of a hydrogen storage alloy electrode is affected by various factors, microstructure and surface composition of the alloy and structure of the electrode as well as composition of the alloy. Control of those factors enables us to commercialize the Ni-MH battery in various field.IntroductionA Nickel-metal hydride (Ni-MH) battery has been extensively developed because of (1) good compatibility with a nickel cadmium (Ni-Cd) battery, (2) high energy density (1.5-2 times higher per unit volume than a Ni-Cd battery) and high dischargeability, and (3) low environmental pollution. The charge/ discharge reactions can be written as [l, 2,3]:(+) Ni(OH)2+OH- = NiOOH+H2O+e· (E=+0.490V NHE),(-) l/6LaNi5+H2O+e-· = 1/6LaNi5H6+OH- (E=-0.828V NHE),where E° is a standard potential of an electrode vs. normal hydrogen electrode (NHE). Because of the above advantages of a Ni-MH battery, the battery have been widely used as a power source of portable computers, cellular phones, electric vehicles (Toyota ""LAV4L EV"", Honda ""EV Plus"" etc.) etc. Some hybride vehicles (Toyota ""Prius"" and Honda ""INSIGHT"") and fuel cell vhehicles (Toyota ""FCEV"") are power-assisted by a high-power Ni-MH battery. In 1999, the production of Ni-MH batteries reached 870 million cells in Japan. Most of commercialized NiMH batteries are incorporated with rare-earth-based AB5-type hydrogen storage alloy as a negative_ electrode. The production of rare-earth-based alloy is estimated to be approximately 8000 tons.The battery performances of the Ni-MH battery, for example, capacity, durability (cycle life), dischargeability (kinetics) and selfdischarge, ate closely related to the metal hydride· (MH) electrode, especially, the hydrogen storage alloy in the electrode. Substitution of alloy components, heat treatment, and surface treatment in order to change surface and bulk structure of hydrogen storage alloys have been examined by us and many reseachers in order to improve the performances of MH electrodes. This paper is a review of our and their efforts to improve performances of MH electrodes."

Jan 1, 2000

A new technology for the treatment of copper nickel-containing concentrate after high-grade matte flotation to blister copper with the production of liquid silicate slags in a vertical autogenous unit with upper oxygen blow has been considered. The copper and nickel behavior in the process of sulphide copper concentrate interaction with silicate melt containing oxide copper has been studied. The general mechanisms of such interaction are found.

Jan 1, 2003

By S. K. Kawatra, T. C. Eisele

"Recent advances in microbiology have made the application of biotechnology to metallurgical processes possible. Hydrometallurgy stands to gain the cost from the use of microorganisms, as they are useful for both dissolution aids and for removing metals from solution. The development of genetic engineering techniques promises to greatly increase the importance of bioprocessing of metals and minerals by the year 2000.In this paper, the basic effects of microorganisms on metallurgical processes are reviewed, and the applications which are currently either in use or near being used are presented. Representative data collected at Michigan Technological University is also given.IntroductionMany hydrometallurgical operations exist which are thermodynamically possible, but which are industrially impractical due to slow kinetics, high reagent costs, or the need for a highly corrosive environment. However, recent discoveries in microbiology indicate that in many cases these difficulties can be reduced greatly by the action of bacteria and other microorganisms (1-8).A major advantage of using living organisms in hydrometallurgy is that once the culture is established the microorganisms produce their own reagents either from the material being processed or from low-cost nutrient supplements. They thus allow extremely complex chemical reactions to be carried out at reasonable cost. The major drawback of using microorganisms is their inability to tolerate extremely high temperatures, excessive concentrations of toxic metals, or very highly acidic, alkaline, or corrosive conditions. However, the complex reactions which bacteria make possible frequently eliminate the need for such extreme conditions. Also, in recent years a number of organisms have been isolated from such exotic environments as hot springs and deep-ocean vents which can tolerate temperatures higher than was previously thought possible for any organism, and can catalyze a number of metallurgically important reactions (8)."

Jan 1, 1988

By M. J. Adam

As part of its research programs, the Bureau of Mines is investigating the partitioning of complex sulfide minerals to simpler sulfide phases by sulfidation reactions. Partitioning in this manner can afford opportunity to improve selective extraction of mineral constituents of value. This report describes research involving the sulfidation partitioning of the mineral pentlandite, which is an important source of Ni in primary production. For the laboratory studies, the pentlandite was synthesized in nominally equiatomic proportions of Ni and Fe. Elemental Ni, Fe, and S powders were blended, compacted, and sealed under reduced He pressure in vitreous silica tubes. The tubes were heated under controlled conditions at SOD? C for 24 h. The product was verified by X-ray diffraction and chemical analysis to consist essentially of (Ni,Fe)9S8. Small samples of the (Ni,Fe) S were encapsulated with sulfur in silica tubes at reduced He pressures and heated for 1 to 24 h at specific temperatures between 400? and 600? C, both below and above the boiling point of sulfur (_445° Cl. Reaction rate increased with temperature. Within this temperature range, partitioning to individual Ni and Fe disu1fides proceeded to essential completion according to the reaction

Jan 1, 1988

By Terry Gerritsen

Electrode control systems regulate power by physically positioning electrodes. Due to the size and weight of the electrodes, this is a slow process where power fluctuations of less than a few seconds are not fully corrected. Nickel laterite AC furnaces operating in high voltage, shielded arc mode typically incur frequent power variations of approximately +I- 20% around the power set point. To provide enhanced power control, Hatch has recently supplied, at commercial scale, a thyristor-switched reactance system called an SPLC. The SPLC incorporates predictive control software to operate furnaces at the maximum transformer rating by reducing the large power swings experienced without the SPLC. The resulting higher average power enables higher production, without increasing transformer or power plant capacity. A 60 MW production version of the SPLC has been commissioned on Falconbridge Dominicans's laterite nickel furnace, yielding excellent results with a 3 to I reduction in power fluctuations. Keywords: SPLC, AC Power Supply, Electric Furnace

Jan 1, 2004

By Jiang Fan, Liu Shi, Wang Haigang

Winter-time natural convection in gravel embankments has been suggested as a technique to provide passive cooling and thereby avoid thaw-settlement of roadways located in permafrost areas. Numerical simulation by finite volume method on the proposed model is perf9rmed using the software FLUENT. A gravels model, in which the embankment is composed of stones and air, has been adopted to investigate the temperature and velocity fields in embankment. Simulation results show that in summer, a weak clockwise circulation of the pore air extending throughout most of the embankment. The pore-air motion is very weak which results in relatively straight horizontal isotherm lines. And heat transfer is mainly maintained through conduction. But in winter, pore-air velocities are higher and multiple vortexes are formed in the embankment. Natural convection then becomes the dominant influence on the isotherm shapes within the embankment. As a result of low ambient temperatures exerted on the embankment surface during winter months, an unstable air density gradient develops within the embankment. This convection increases the heat flux out of the embankment. Therefore, the winter-time convection can further reduce the temperature of the foundation soil beneath the open-graded embankment. In addition, the effects of the size of the stones within the embankment have been analyzed and compared in the gravel model. It shows that in winter, 200mm stones lead to stronger vortexes in the embankment compared with those of 60mm stones. Consequently, the zone oflow-temperature beneath the embankment is extended.

Jan 1, 2004