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By Edouard Asselin, Guikuan Yue

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe( II )-Fe(III)-H2S04 solution at 25°C and 70 °C. Results from the calculation ofspeciation in the above solution reveal that, at both 25 °C and 70 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible potential of the ferric/ferrous couple based on the Nemst equation. Exchange current densities of the ferric/ferrous couple were obtained by extrapolating the cathodic linear Tafel line to the reversible potential and are on the order of 10-7·10-6 A/cm2 at 25°C and 10·6-10-5 A/cm2 at 70 °C, respectively. The transfer coefficients were about 0.35-0.38 at 25°C and 0.35-0.45 at 70 °C. Polarization plots of CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 ·c and at 70 °C. Based on the obtained exchange current densities, the rate constant k, was calculated and is on the order of 10-1 cm/s at 25 °C and 10 1 cm/s at 70 °C.IntroductionChalcopyrite is the most abundant copper mineral in nature, accounting for about 70% of copper reserves in the world [I]. In recent years, the metallurgical industry has been searching for a hydrometallurgical process as an alternative to pyrometallurgical treatment due to high emissions of S02 and capital costs associated with smelting. Activity in this area has increased recently due to some inherent advantages associated with hydrometallurgical processing, such as the possibility of treating low-grade ores (increasingly more abundant in the case of copper) and easier control of waste, with the attendant benefits to the environment [I]. Chalcopyrite is highly refractory under most hydrometallurgical conditions, owing to the formation of an anodic passivation layer on the chalcopyrite surface which renders the process kinetics very slow. Most of the currently proposed processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Sulfuric acid is preferred over all other leaching reagents in terms of cost, environmental friendliness, and ease of its regeneration during electro-winning. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale,"

Jan 1, 2012

By Y. Fukunaka, M. Niinae, E. Kusaka, T. Kuzuya, R. Ishii

"Samarium oxalattr particles was precipitated in oxalic acid aqueous solution from samarium-loaded D2EHPA solution emulsified with a conventional impeller. The calculated fractional precipitation of samarium oxalate was reasonably compared with the value determined by chemical analysis. Morphological variation of oxalate precipitate particles was then examined with H2C2O4 concentration in aqueous solution, Sm(III) and D2EHPA concentrations in organic phase. The needle-like precipitate was identified as Sm2(C2O4)3 10H2O by XRD. Precipitates obtained at higher H2C2O4· or Sm(III) concentration greatly decreased the length of major axis of precipitate, while those at higher D2EHPA concentration increased it. The oxalate was further precipitated under ultrasonic irradiation. However, the morphological variation caused by theses processing variables was not so evident under ultrasonic irradiation as in an impeller or shaking mixer.IntroductionThe materials processing of the rare earth elements must be reviewed from the scope of industrial ecology, since they have the potential applications of magnetic materials as well as secondary battery in developing programs of the electric vehicle. The technological trend to develop the electric vehicle may greatly influence the concept of materials processing, since the global· environmental problem must accommodate with the sustainable development for mankind. The recycle design must be a key issue in the materials science and engineering.Solvent extraction provides a unique separation technology -in this sense. Doyle (1)(2) reported the integrating solvent extraction with processing of advanced ceramic materials, whose chemical composition and microstructure must be precisely controlled. In her paper, the higher productivity inherent to the present process superior to hydrolyzing metal alkoxides was emphasized. Oxalic acid has been used as precipitant for rare earth purification process, since rare earth oxalate has a very small solubility in water and can be easily decomposed to oxide. It is thus suitable for precipitation stripping agent in cationic exchange type extracting system (i.e. D2EHPA, VA-10, PC-88A and so on)."

Jan 1, 2000

By T. Wang, R. G. Reddy

"The corrosion of stainless steel SS316L in a low melting point novel LiNO3-NaNO3-KNO3- NaNO2 eutectic molten salt mixture was investigated at 695K. After long-term isothermal dipping corrosion experiments, the SS316L samples were analyzed using scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS) to determine the topography and corrosion products. Dense and protective lithium iron oxide scale formed on the surface and prevented the SS316L sample from further severe corrosion. Therefore, SS316L is considered to be suitable construction material for solar thermal energy storage materials containers.IntroductionMolten salt mixtures have been considered as potential candidates for thermal energy storage and heat transfer media in solar energy applications. To apply the molten salt in the energy transfer process, the standard pipes made of stainless steel must be utilized to carry the molten salt mixtures in parabolic trough system of solar power production. The pipes encounter continuous flow of hot and cold molten salt every day. Thus corrosion of stainless steel in molten salt mixtures becomes extremely essential for the long-term utilization of the thermal energy storage media. The corrosion of passivity materials inside high temperature molten salt systems have been studied which gives fundamental understanding of basic mechanism about the corrosion process [1-8].The corrosion behavior of Fe-Ni-Cr alloys in an equi-molar LiNO3–NaNO3–KNO3 mixture was studied [9]. According to the XRD analyses, the major phases in the oxide scales were identified as LiFeO2, Fe3O4 and Cr2O3. A HITEC® salt mixture (NaNO3–NaNO2–KNO3) was also tested as a corrosion medium for stainless steel [10] and the corrosion rate was found to be affected by the protective oxide layer. In most cases, the alloys having more than 10wt% chromium show high resistance to corrosion in molten salts."

Jan 1, 2014

By Christian M. Sagedahl

The stringent environmental regulations for air pollution regarding emission control, along with the need of dry concentrates to feed autogenous smelting processes, are enhancing the development of cleaner technologies. Indirect drying of concentrates by a Kvaemer steam dryer is a technology with promising results, reducing dust entrainment to the exhaust gas stream and leading to smaller dust separation units. The Kvaemer dryers are designed for a very high availability, a high-energy efficiency, low amount and velocity of exhaust gases, no SO2, CO or CO, emissions combined with a wide range of satisfactory operating conditions and low total operational costs.

Jan 1, 1999

By Ji-He Wei

The ESR of Cu-Cr-Zr alloy has been experimentally investigated. The remelting experiments have been carried out with different slag fluxes in the Cal, + Nal, CaF2 + ZrO2 and CaF2 + NaF + ZrO2 systems on an ESR furnace of 25kg capacity; using a water-cooled copper mould of 96.5 mm diameter, with the forged square bar electrodes of 50x50 mm2. The slag amount was taken to be 1.5 kg. The remelting current and voltage used were 1600-1800A and !5-25K, respectively. The influence of the slag composition on the stability of the remelting process and the losses of alloying elements (2r and Cr) has been considered and examined. The technologies of hot working and heat treatment of the ES ingot have been described and discussed. Some physical properties of the slag in a CuF2 + NaF + ZrO2 system and the remelted Cu-Cr-Zr alloy have been determined. The results indicated that with the slag flux of CaF2 + NaF + l0 mass % ZrO2 and the other operation parameters employed, a high quality ingot of Cu-Cr-Zr alloy may be obtained at the considerably high yields of Zr and Cr by means of ESR. For the remelted Cu-Cr-Zr alloy with a specified composition of 0.5 mass % Cr and 0.1 mass % Zr, the appropriate electrical conductivity, hardness and softening temperature are as high as 45-46S/m, HRB 82-84 and 550°C. respectively. The properties of the Cu-Cr-Zr alloy products are in accordance with and superior to the requirements and specifications of ISO5l82-l99l(E).

Jan 1, 2000

By W. G. Davenport

This chapter demonstrates how our matrices can be used for controlling a flash furnace. Specifically, it shows how we can determine the adjustments in industrial oxygen, air, oil and flux input rates that will; (a) correctly alter product temperatures and compositions to newly targeted values (b), maintain set-point product temperatures and compositions with varying feed compositions and feed rates. It also discusses corrective actions that might be taken when furnace temperature and matte grade unexpectedly change.

Jan 1, 2001

By Ray Y. Lin

Chemical vapor deposition of tungsten carbide on the surface of steel has been investigated at temperatures between 400 and 550C in an atmosphere containing tungsten hexafluoride, hydrogen and benzene. The tungsten fluoride flow rate was maintained at 20 ml/min. The hydrogen flow rate was at 100 ml/min. The benzene concentration varied from 1.15 to 5.56% in the reaction gas. It was observed that the higher the temperature, the faster the deposition rate for tungsten carbide. But the dependence of the deposition rate on the benzene concentration was not systematic. From the x-ray diffraction analysis, it was observed that W, W2C and WC are all presented in the coating. The amount of each phase presented in the coating depends on the temperature and, to a less extent, on the benzene concentration. The microhardness measurement has also been done for all CVD carbide coatings obtained in this study.

Jan 1, 1992

By Masao Suzuki

Over 5 million cars are scrapped yearly in Japan. After dismantling. scrapped automobiles, they are put into a shredder for differential recovery of ferrous and nonferrous metals. The residue, which is called shredder dust, runs over 1.2 million tons per year. This paper reports a entire sequence of scrapping. cars. in Japan with the following sections: (1) production and scrapped car management, (2) material composition, (3) dismantling, (4) shredder plant, (5) differential recovery of metals including specific gravity separation and newly developed color separation.

Jan 1, 1995

By Fan Jiang, Haigang Wang, Shi Liu

"This paper describes several applications of Electrical Capacitance Tomography (ECT) in gassolid two phase flows. A new image reconstruction algorithm was evaluated by both simulation and experiments. It is then applied to the online measurement of solids distributions in square circulating fluidized beds (CFBs) and good results were obtained. From the measurement of solids distributions in the bottom zone of a CFB, a bubbly fluidization pattern is identified. A cross-correlation technique was combined with the solids concentration measurements to obtain the flow rate through the dip leg of the cyclone, i.e. the circulating rate of a test CFB. The same· technique was applied in a dense phase pneumatic transport pipe provides the solids concentration, and the flow rate of a wavy gas-solids flow.IntroductionElectrical capacitance tomography (ECT) has been developed for imaging multiphase distributions in the 90's of the ·last century. It is a non-intrusive method. The principle of ECT can be firefly described as follows:Firstly ECT uses a number of electrodes to surround the measuring zone, depicted by Fig. I. The capacitances between the electrodes are measured in turn and an array C is obtained that contains a total number of m independently measured capacitances. Meanwhile the measuring zone is virtually divided into a grid of n pixels, represented by an array G, named the image vector, the gray level of each pixel represents the local value of the concentration of the material. As the material distribution will be reflected by the capacitances between each pair of electrodes, such distributions can be reconstructed according to the measured capacitance, a process called image reconstruction. A common image reconstruction method is called linear-backprojection (LBP). It linearize the relationship between the dielectric distributions in the measuring zone and the capacitances between the electrodes as the following:"

Jan 1, 2004

By Raj P. Singh

Applications of cementation in the recovery of metal ions from process solutions have been known for a long time. Cementation reactions involve electrochemical precipitation of a noble metal from solutions of its salts on a more electropositive metal which, in tum, progressively dissolves. For example, addition of zinc metal powder in a solution containing zinc and cobalt ions would allow for the precipitation (separation) of cobalt according to the following chemical reaction. This paper pertains to the recovery of cobalt from cobalt process solutions via a cementation reaction on aluminum shavings (metal scraps from cans etc). Specifically, we report on the characterization of cobalt process solutions, a by-product obtained from cobalt chemicals, and the kinetics of cobalt, nickel and manganese cementation from process solutions on aluminum shavings.

Jan 1, 2000

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would, be reduced at the new smelter to about a half of the sum of those from previous two smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive off gases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

By John M. Gaines

Lead concentrates from the Viburnum Trend in Southeast Missouri are sintered, prior to smelting, to bind the particles together, homogenize the feed, and reduce the sulfur content. About 20% of the sinter at some plants is classified as bad sinter. A total of 130 samples of good and bad sinters were studied by reflected light microscopy, scanning electron microscopy-energy dispersive analysis, and electron microprobe analysis to characterize their differences in mineralogy and textures. Good sinters consist predominantly of hardysonite, franklinite, lead silicate matrix, and large crystals of calcium-magnesium-iron silicate, together with minor amounts of lead oxides, lead-zinc silicate, metallic lead, specular hematite, magnetite, lead-iron-bearing zincite, and zinc-lead-magnesium-bearing wustite in a tightly intergrown mesh of crystals and with an evenly distributed porosity of about 15-20%. Bad sinters contain larger amounts of lead silicate matrix, galena, metallic lead, and lead oxides, but smaller amounts of hardysonite, franklinite, and calcium-magnesium-iron silicate, lack intimate intergrowth of the phases, and have lower (0-5%) and unevenly distributed porosity.

Jan 1, 1992

By Susumu Okabe, Etsuji Kimura

"The Mitsubishi Continuous Copper Smelting and Converting Process is the typical applications of injection metallurgy to nonferrous metallurgical operation, where the top blowing multiple lance system is employed for the continuous feeding of the raw materials and reaction gases into the molten bath. This results in an effective dispersion of the reactants into a strongly agitated bath. These are considered as the major advantage of the process with respect to the high production efficiency. On the other hand, however, the strong agitation may cause a considerable amount of refractory wear, and the melt splash generated by the lancing may also have negative effects on the productivity, i.e. the increase in the refractory wear, the metal loss, the heat loss, and the accretion growth, etc. Therefore, the optimization of the blowing condition as wen as furnace design is very important to achieve a stable and efficient operation, and fundamental understanding of the injection, agitation, and splashing is badly needed.In this paper, fundamental aspects of the Mitsubishi Process regarding injection, especially splashing phenomena, are discussed. The splashing on a vertical plane caused by the top blowing gas injection onto liquid surface was investigated through physical model study. As a result of the study, the splashing rate on the furnace wan was wen correlated with the physical properties of the bath materials, gas velocity, cavity shape, lance/wall distance and ceiling position. Obtained equations were compiled in a computer program and have been successfully applied to the evaluation of the furnace design. IntroductionInjection metallurgy is an application of gas/solid-in-liquid dispersing operation to the metallurgical processing, and has been widely adopted in various fields in order to improve their efficiency or productivity. The dispersed small particles of gas or solid materials in the liquid phase result in increased interface area, and injected momentum causes an agitation and enhanced heat and materiel transfer. Typical examples of injection metallurgy are LD converter for steel making, PS converter, Noranda process, Isasme1t for copper making, and Mitsubishi Material's continuous copper smelting and converting process, and so on."

Jan 1, 1996

By Patrick R. Taylor

Ilmenite concentrate and methane are fed to a non-transferred arc thermal plasma reactor to produce a powder that is primarily TiC and Fe. This material has promising characteristics for powder metallurgy applications. Free energy minimization plots were used to predict the feasibility of the reaction. An estimate of the optimum molar ratio between the ilmenite concentrate and methane was made based on the mineral composition. Argon-helium mixtures were used as plasma gases. The effects of power input level, carrier gas flow rate, powder feeding rate, and methane-ilmenite molar ratio were studied and the behavior of the system characterized. Two different powder injection angles were tried. A mathematical model to describe the temperature profiles in the reactor was formulated and solved. The product has been characterized by x-ray diffraction and atomic absorption. A conversion of 97 % of Ti to TiC was achieved. It was found that minor amounts of titanium oxides, iron carbide and free carbon are also present. TEM and SEM were used to study the morphology.

Jan 1, 1996

By Donald R. Fosnacht

An investigation was initiated to obtain the scope of the problems associated with recycling various waste oxide materials generated at Inland Steel and to identify and? test techniques that could possibly aid in increasing the amount of waste oxide materials recycled to primary. operations. Based on the results of this work, several new techniques were developed ?and tested on ?a plant or laboratory scale. These include the use of cold-bond agglomeration methods for producing waste oxide agglomerates for use as a cooling agent or scrap substitute in steelmaking operations, and the use of various techniques for beneficiating blast furnace flue dust and soaking pit rubble so that the upgraded materials can be utilized in sinter plant or ironmaking operations. The physical and chemical characteristics of the waste oxide materials and the results of the laboratory and plant testing are discussed in this paper.

Jan 1, 1985

By W. D. Cho

Fast dissolution of nonmetallic inclusions such as alumina particles in molten slags has been required in secondary steelmaking -ladle and tundish - to minimize the amount and the size of nonmetallic inclusions in steel products. In the present work, the dissolution behavior of alumina particles in molten CaO-A12O3 and CaO-A12O3-SiO2 slags at the temperatures between 1450 and 1550°C have been investigated in terms of kinetics and mechanism. Alumina particles were added directly into the slags and the variation of the particle size with time was determined using optical and electron microscopies. The conventional types of slag for ladle and tundish were included in the dissolution study. The effects of Al2O3, Siq, CaF2 and MgO contents on the dissolution rate of alumina particles have also been determined. The diffusion boundary layer between alumina particle and bulk slag phase has been observed and analyzed using SEM and EDS. Based on the analysis of kinetic data and the boundary layer, the dissolution mechanism has been discussed.

Jan 1, 2002

By Michael L. Sorokin

The behaviour of cobalt during processing of nickel raw material is analysed within the Ni-Co-Fe-S-O-SiO2 system using the computer model. For this purpose the thermodynamic parameters for "three-suffix" Margules's equations in Co-Fe-S and Co-Fe¬Ni-O-S1O2 systems were computed! Phase and iso-activity diagrams for Co-Fe-S system, and phase diagrams for the systems Co-O, Co-Fe-O, Co-Ni-O, C-oO=SiO2 and Co-Fe-O¬SiO2 are calculated using the developed computer programs and identified parameters. The diagrams are used to analyze cobalt behaviour at smelting and converting.

Jan 1, 1995

By C. F. Feng, L. Froyen

"In-situ processes have emerged as new and promising techniques for metal matrix composite fabrication. They offer significant technical and economic advantages over conventional processing. One of the in-situ processing routes that have been used is reactive free sintering of a mixture of powder reactants. However, materials synthesised via this route are always porous because of density differences between reactants and products. An example are the porous Al/(TiB2+Ah03) MMCs obtained by heating powder mixtures of Al+ Ti02+B with Ti02 and B in stoichiometric ratios for forming TiB2• In this study, porous Al/(TiB2+Ah03) composites were further processed by hot-pressing at temperatures above 600°C. This processing cycle was designed so that the composites could be densified. Furthermore, the reaction kinetics of the in-situ processing are studied by means of DSC analysis measured at different heating rates. The activation energies of the three intermediate steps that are involved in the reactive processing for preparing AV(TiB2+Alz03) MMCs are determined to be 923 kJ/mole, 241 kJ/mole and 235 kJ/mole respectively.XRD proved that the hot-pressed products consist of Al, TiB2 and Al203- Properties of the products are assessed by microstructural characterisation (LOM, SEM and EDS), microhardness, Young's modulus and bending tests. The results show that good microstructures, elastic properties and strengths, as well as acceptable ductilities were achieved. For the composition 79.74wt% Al-15.95wt% Ti0z-4.31wt% B, after the reactive free-sintering and hot-pressing cycles, Young's modulus is 105 GPa, bending strength is 509 MPa and maximum strain is 5.0%; for composition 88.73wt% Al-8.87wt% Ti0z-2.40wt% B, they are 89 GPa, 311 MPa and 8.2% respectively. It can be seen that the properties of products can be tailored by adjusting the relative amounts of reactants in green samples. Furthermore, for comparison reasons, Al and a binary system Al-Ti02 were identically processed as the ternary systems. Their microstructures and properties were studied."

Jan 1, 1998

By Katsutoshi Inoue

Pectic acid gel crosslinked with epichlorohydrin was found to have very high selectivity to lead(II) and iron(III) ions over zinc(II) ion compared with commercial weakly cation exchange resins containing the same carboxylic functional groups, suitable for removing small amount of impurity metal ions from waste zinc plating solutions. In order to lower the cost, new adsorption gel was prepared from orange juice residue containing pectic acid by crosslinking with epichlorohydrin, which was also found to be suitable for removing these impurities. Further, very cheap adsorption gels was prepared not only from orange but also from apple juice residues by a simple method through just saponificating pectin substances contained in these residues into pectic acid by calcium hydroxide followed by water washing and drying. These adsorption gels exhibited excellent adsorption behaviors for removing the impurity metal ions away from zinc.

Jan 1, 2003