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By T. T. Chen

Raw anode slimes consisting primarily of PbSO4, AgCuSe, Cu3Se2, Cu2-x Se, Cu2O, CuSO4.5H2O, Sn arsenate and Sb-Bi-As oxide are batch-leached with electrolyte-O2 to dissolve Cu. During this process, Cu2O and CuSO4.5H2O are solubilized and the Cu in the selenides is leached with the formation of Ag2Se and Se. A small amount of Cu remains in the Ag2Se, Sn arsenate and Sb-Bi-As oxide. The decopperized slimes are repulped in Na2CO3 solution to convert most of the PbSO4 to NaPb2(CO3)2(OH). The Sn arsenate and Sb-Bi-As oxide partly react, but the Ag2Se is not significantly affected by the Na2CO3 solution. The NaPb2(CO3)2(OH) intermediate phase is dissolved in acetic acid to leave a final product consisting of Ag2Se, Se, Sn arsenate and Sb-Bi-As oxide, together with small amounts of PbSO4, NaPb2(CO3)2(OH) and various gangue constituents.

Jan 1, 1993

By Mitsuru Tanahashi

In order to develop an effective process for the production of from metallurgical-grade one (MG-Si), the oxidation removal of boron from molten MG-Si was investigated at a solar-grade silicon (SOG-Si) 1773K by the following two CaO-saturated CaO-CaF2 flux treatment processes. I) Boron removal by flux addition onto the molten M6-8 followed by oxygen gas injection into the melt (Two-stage connecting process). II) Boron removal by simultaneous injection of flux powders and oxygen gas into the molten MG-Si (Simultaneous injection process). These processes can establish the special condition of both high basicity of the flux and the high oxygen partial pressure at the boron removal reaction sites. Through these processes, especially by the simultaneous injection Process using a flux powder injection equipment, the boron content in MG-Si can be efficiently reduced. The obtained results clarified that both processes should be conducted for a time period as short as possible by using as much flux as possible. By repeating the simultaneous injection process for 60 s three times under the optimum operating conditions determined in the present study, the boron content in MG-Si can be reduced from 14 to 4.7 mass ppm.

Jan 1, 2003

By Mitsuru Tanahashi

In order to develop an effective process for the production of a solar-grade silicon (SOG-Si) from metallurgical-grade one (MG-Si), the oxidation removal of boron from molten MG-Si was investigated at 1773 K by the following two CaO-saturated CaO-CaF2 flux treatment processes. I) Boron removal by flux addition onto the molten MG-Si followed by oxygen gas injection into the melt (Two-stage connecting process). II) II) Boron removal by simultaneous injection of flux powders and oxygen gas into the molten MG-Si (Simultaneous injection process). These processes can establish the special condition of both high basicity of the flux and the high oxygen partial pressure at the boron removal reaction sites. Through these processes, especially by the simultaneous injection process using a flux powder injection equipment, the boron content in MG-Si can be efficiently reduced. The obtained results clarified that both processes should be conducted for a time period as short as possible by using as much flux as possible. By repeating the simultaneous injection process for 60 s three times under the optimum operating conditions determined in the present study, the boron content in MG-Si can be reduced from 14 to 4.7 mass ppm.

Jan 1, 2003

By Hirofumi Tai, Masafumi Morishita, Toshiya Miyake

"In order to prevent corner cracks on cast steel slab and bloom, solidification delay at the corners should be controlled at the proper level. For this purpose, controlling the heat flux from the molten steel to the solidified shell at corners is essential. In this paper, optimization of the submerged nozzle was studied based on flow and solidification analysis.First, for the slab caster, the submerged nozzle shape was optimized. The improved nozzle was tested in actual casting and completely succeeded in preventing corner cracks. It was clearly demonstrated that the solidification delay and the corner cracks were strongly affected by the spouting stream from the submerged nozzle.For the bloom caster, on the other hand, the setting angle of the nozzle was optimized. Numerical simulations demonstrated that the spouting stream from the nozzle causes solidification delay, impinging at the corners under electromagnetic stirring conditions. Optimization of the setting angle of the nozzle is a possible means to reduce the solidification delay at the corners for the bloom caster.Related to the numerical analysis of flow and solidification, the effect of the critical solid fraction at the tip of the dendrite structure on the solidification under electromagnetic stirring conditions was studied."

Jan 1, 1999

By Uday B. Pal

In the electrochemical vapor deposition (EVD) process, gaseous cation precursors are passed over one side of a porous substrate, and oxygen is passed on the other side of the substrate. The gases diffuse and react within the porous substrate, and the pores get filled with the desired solid oxide. Subsequent solid state electrochemical transport through the solid oxide in the pores continues the reaction, and the film grows over the porous substrate. The EVD process has been used to deposit lanthanum chromite interconnection films and yttria stabilized zirconia electrolyte films over porous air electrodes. The EVD growth of these solid oxide films is found to be parabolic in nature, which indicates that the solid state transport (diffusion) of ions through the film controls the growth. This solid state transport can be analyzed using Wagner's treatment of the electrochemical transport. Conductivity measurements and the information on the defect structure of the oxide can be combined with the EVD growth rate measurements to calculate the solid state transport properties (transport numbers and partial conductivities) of the rate-controlling minority species in the oxide. Using this approach, the EVD growth of other electronic, mixed conducting and ionic solid oxide films can also be analyzed.

Jan 1, 1992

By Nils Eivind Kamfjord, Halvard Tveit, Ingeborg Solheim

"Because of its negative environmental effect the attention towards NO emissions increases. This again leads to new demands from the authorities for better surveillance and control of emissions. Earlier and recent industrial measurements towards FeSi- and Si-metal furnaces reveal quite high NO-emission. The NO is believed to be produced in the combustion zone above the furnace surface, mainly as thermal NO.In order to expand the knowledge on NO-formation in silicon metal production, a pilot scale experiment in a 440 kVA silicon furnace has been carried out. The experimental set-up was designed with a view to be able to copy and manipulate the formation mechanisms for NO by controlling the flow of false air into the off-gas system.The resulting NO-values corresponding to the different air inlet to the furnace top, show significantly differences between the different air inlet geometries.IntroductionNOx is the common notion for the two gases nitric oxide (NO) and nitrogen dioxide (NO2). Since combustion of fuels, such as gasoline, diesel, bio diesel, propane, coal, and ethanol, forms NOx the dominating contributors to NOx emissions are the on-/offshore transportation industry and power generation based on fossil fuels [1]."

Jan 1, 2012

By Takamitsu Nakasuga, Haiping Sun, Kyushu University, Katsumi Mori

"The kinetic behavior of reduction of chromite ore by liquid iron containing carbon and silicon has been investigated under various experimental conditions to clarify the reduction mechanism. It was found that the reduction rate of chromium ore by liquid Fe-C alloy was very slow. In addition, when carbon and silicon coexisted in the iron melt, silicon was found to preferentially oxidized to form silica, which favored for the fonnation of liquid slag and the rate of reduction was considerably accelerated. The similar effect was obtained by the addition of some fluxes, such as SiO2, Na2B407, CaO-SiO2, which also promoted the formation of a liquid slag and thus the reduction rate in the early stage also increased.IntroductionThe reduction of Cr2O3 is a basic reaction for production of ferro-chromium from chromite ore and for chromium recovery from the slag fonned during the decarburization period of a stainless steel-making process. The reduction of chromite ore consumes much energy and its reaction rate is not so high. Thus, in order to increase the reduction efficiency, it is strongly desired to clarify its reduction mechanism from the practical and the theoretical points of view."

Jan 1, 2000

By Berndt Moeller

Mercury-cell chlor-alkali production plants generate mercury contaminated wastewater streams from which mercury must be precipitated and filtered, resulting in a sludge containing 2% mercury (designated KI06) that cannot be landfilled in the United States without treatment. REMERC is a chemical treatment process used to recover 99% of the mercury from wastewater sludge generated at these plants. The process uses leaching to oxidize mercury compounds to mercuric chloride, washing and filtration to separate mercuric chloride from the treated sludge, and cementation to reduce the mercuric chloride to metallic mercury. Mercury not recovered in cementation is recycled to the wastewater process for precipitation and filtration. Treated sludge contains less than 260 ppm total mercury and 0.2 ppm TCLP, meeting the USEPA low mercury subcategory specifications that allow landfill disposal. REMERC uses readily available chemicals, is straightforward to control and inexpensive to operate, has no mercury emissions to air, and recovers metallic mercury. REMERC enabled significant cost savings including lower solids disposal costs, recovery and reuse of metallic mercury in the chlor-alkali process, and ability to treat non-wastewater sludge. No new EPA permits were required. REMERC was shown to be a viable process for recovery of metallic mercury from K106 designated sludge.

Jan 1, 2003

By J. C. Riani

The release of heavy metals into the environment is increasing among others due to human activities such paint and pigment industries, tanneries, and metal finishing industries. Among metal releases, chromium is notable because this metal is carcinogenic. Thus, the aim of this work is to use an ion exchange system composed of one cationic resin column and one anionic resin column in order to adsorb the chromium (III, VI) from chromium electroplating effluents with the objective of recycling the water. The methodology consists of chromium adsorption tests using the ion exchange resins system with Purolite the 850 (polystyrene matrix, functional group quaternary amine) and Purolite C 150 (polystyrene matrix, functional group sulfonic acid). The contaminated solutions were passed through the columns with the assistance of peristaltic pump. Samples of the outgoing solution were taken in order to control the conductivity and pH and analyze the metals. The effects of the feeding outflow on the chromium adsorption were evaluated. The results show that the quality of the water collected at the end of the process is within the Brazilian standards about the discarding of toxic substances in the environment (CONAMA 357/05). This makes possible the recycling of water into the process and also its discharge in the rivers.

Jan 1, 2006

By K. Osseo-Asare

Rate laws for the hydrogen reduction of metal ions are typically of the form: [r = -d[M(II)]/dt = k[M(II)]xPy2H] where k is an apparent rate constant, [M(II)] and PH2 represent dissolved metal concentration and hydrogen pressure respectively, while x = 0 - 1 and y = 0.5 - 2. Half-order dependences have been reported for some M(II)/H2 systems; however, no satisfactory explanations have been offered. In an effort to bridge this gap in our understanding, the published precipitation rate data (for M(II) = Cu(II), Ni(II), and Co(II)) are reviewed (with emphasis on the reported reaction orders) and compared with the corresponding but limited electrochemical polarization data. Based on the available literature on the electrochemical kinetics of the M/M(II) and H2/H+ systems it is demonstrated theoretically that, under certain conditions (e.g., in the presence of electron-conducting solids), the rate of the M(II)/H2 reaction can be expressed as: [-d[M2+]/dt = k[M2+]2/1P2/12H] It is concluded that electrochemical processes probably play an important role in the hydrogen reduction of metal ions, especially for systems that involve heterogeneous catalysis.

Jan 1, 2003

By Renaud Metz

The DOPA process (Direct Oxidation of a Precursor Alloy) was used to prepare ceramic powders based on doped SnO2 and ZnO. The DOPA process consists essentially in the direct oxidation of a homogeneous precursor alloy. A unique advantage of this process is its rather benign environmental impact since no dangerous reactants are used and no harmful by-products are generated. Only oxygen and the alloy metals participate on the chemical reaction to produce the multi-component oxide. Homogeneous alloys of niobium, cobalt and chromium doped tin have been prepared. The molten metal alloy is atomised in air using a double fluid nozzle to produce metallic powders. A subsequent thermal treatment is carried out to fully oxidise the sprayed metal alloy powders. These raw powders are used to prepare a ceramic powder through a mill homogenisation and atomisation process. The ceramic powder is then uniaxially compacted in disc shape and sintered in an oxidising atmosphere. The resulting sintered bodies are metallised on their flat faces and the cylindrical surface is passivated using lead free glass enamel. These ceramics present excellent semiconducting properties with non-linear (non-ohmic) characteristics. The DOPA process is found to be an attractive procedure to obtain ceramic powders for the preparation of SnO2 varistors.

Jan 1, 2006

By Marco A. S. Aguiar, Luis G. S. Sobral, Vânia Mori, Paulo A. Medeiros da Silva

"Copper occurs in the crust of the earth, predominantly, as sulphides. Among the copper sulphide minerals, the chalcopyrite is the most abundant and the most refractory to the conventional oxidative processes. This work aims at developing an electrolytic process for treating a copper sulphides flotation concentrate, more precisely chalcopyrite (CuFeS2) and bornite (Cu5FeS4) in the percentages of 70 and 30%, respectively.This paper presents a low-cost operational electroleaching process for treating copper sulphides flotation concentrates, with a high chalcopyrite content. This research practical work aims at improving the copper extraction from that sulphide mineral, in a relatively short time with low-operating cost taking into consideration the influence of a cationic surfactant. The electrolyte of the electrolytic reaction system was a 2,0 mol.L-1 NaCl solution containing CTAB, a cationic surfactant. The electroleaching system contains one DSATM (dimensionally stable anode) anode and two nickel or copper foams (threedimension electrodes. During the electroleaching process the chloride ions are oxidized to chlorine at the anode surface, which in contact with the aqueous phase generate enough hypochlorite ions to oxidize chalcopyrite.The copper ions released from the chemical oxidation process are reduced at the cathode surface as metallic copper."

Jan 1, 2008

By C. A. Morais

The present work describes the development of an efficient and relatively simple process to obtain high grade CeO2 from a mixed rare earth chloride solution. The process involves cerium oxidation and precipitation by addition of a KMnO4-NaCO3 solution. The experiments were carried out at room temperature (25 1° C). The results indicated that the major parameters affecting cerium recovery are the molar ratio of KMnO4/Ce, the initial acidity of the chloride feed solution and final pH of Ce(OH)4 precipitation. In strong acid solutions (pH < 1), the oxidation of Cl to Clo took place in addition to the oxidation of Ce(III) to Ce(IV), so increasing the permanganate consumption. Conversely, low acidity (pH >3) led to coprecipitation of the other rare earth elements. Under the selected conditions, cerium was selectively precipitated as ceric hydroxide, together with some manganese dioxide. Further purification was carried out by the dissolution of Ce(OH)4 in HCl, followed by precipitation as cerium carbonate. The filtrate was neutralised with a Na2CO3 solution in order to recover the associated rare earth elements for further separation. The final product, assaying 99.7 % CeO2, was obtained with a recovery of nearly 100%.

Jan 1, 2003

By V. L. Richards, S. N. Lekakh, S. A. Dutler

"This study presents determination on the thermal properties of investment casting shell molds used in casting process modeling. Superheat and latent heat from solidification and cooling of a casting can either be accumulated by ceramic shell for thin-walled casting or transfer to environment for massive casting. Heat capacity and thermal conductivity both play important roles in casting solidification. Thermal properties of ceramic shell depend on shell composition and fabrication techniques as well as thermal history during shell preparation process due to multiple phase transformations. Inverse modeling was combined with corrected Laser Flash method to determine the applicable thermal properties of the shell during casting solidification. Pure nickel was poured into ceramic shells containing two thermocouples and experimental cooling curves were obtained. These curves were then fitted to the model by adjusting temperature dependent heat capacity and thermal conductivity.IntroductionCasting solidification in investment casting shell affected by shell thermal properties including specific heat capacity and thermal conductivity. For relatively thin walled casting, most of the melt superheat and part of latent heat are accumulated by the shell. This process is mainly controlled by shell heat capacity. In the case of massive casting, significant part of latent heat transfers to environment through the shell so that this process is mainly controlled by shell thermal conductivity."

Jan 1, 2012

By Steven Wright

The extent and the rate of reduction of slags produced from the smelting of recycled lead batteries were investigated under laboratory conditions using graphite as reductant. Simultaneous reduction of PbO, Fe2O3, Sb2O3 and As2O3 occurred at temperatures of 1180 and 1200°C, with Sb and As reporting to the metal phase while the PbO content of the slag was above 2 wt%. Fuming of As from the metal occurred at lower concentrations of lead in the slag. Discard slags with low levels of As, Pb and Sb were produced. Arsenic levels were reduced to less than accurately measurable by ICP analysis, and Sb levels in the final slags were in the range of 0.1 to 0.2 wt%. The kinetic data obtained were analysed and compared with other measurements on lead oxide containing slags. The results showing a dependence of the reduction rate on the oxidation state and the basicity are consistent with other studies on well characterised industrial and. synthetic lead slags. These results indicate that when carbonaceous reductants are used, the rate of interfacial reactions play an important role in enabling the production of environmentally acceptable discard slags.

Jan 1, 1994

By David Ellis

The next generation of Reusable Launch Vehicle (RLV) will utilize regeneratively cooled combustion chamber liners in the engines. The current design calls for using a new Cu-8 at. % Cr-4 at. % Nb (Cu-8 Cr-4 Nb) alloy for the liners. Work is ongoing to characterize the thermophysical and mechanical properties of the alloy from - 253 to 800°C, the temperature range to which the alloy will be subjected during service. The alloy has been commercially produced in quantity for NASA. The powder size has been characterized and the microstructure examined. The powder was extruded into bar using a commercial extrusion press. In addition, samples have been hot isostatically pressed (HIPed) at NASA Glenn Research Center. Both processing methods produced fully consolidated material. Transmission electron microscopy (TEM) revealed highly faulted Cr2Nb and some elemental precipitates. Cryogenic tensile testing showed the extruded specimens had significantly higher strengths than NARloy-Z (Cu-3 wt % Ag-0.5 wt % Zr) even after being subjected to a simulated braze cycle. The Young&apos;s moduli (Cu-8 Cr-4 Nb) were lower than NARloy-Z. The lower moduli is highly beneficial for reducing thermally induced stresses in rocket engine combustion chamber liners and similar applications.

Jan 1, 1999

By Paul Dewison

For nine years, from mid-1987 to mid-1996, the copper market enjoyed what appeared to be an endless boom in which prices were much higher relative to production costs than for most other base metals. After the boom ended abruptly mid-1997 with the Sumitomo affair, copper was burdened by an overhang of new projects that promised to swamp demand in what, with the Asian financial and economic crisis of 1997, had become a considerably worse consumption environment. Now, demand prospects do not look so bad. If, as we suspect, we will be dealing with a more rational market in the future, it becomes all the more important to forecast accurately the prospects for consumption. In this paper, we present a new methodology for copper demand forecasting. The methodology forms the backbone of the demand-side analysis for the multi-client study entitled "Long Tenn Outlook for Copper", co-authored by Metalica Ltd. and Bloomsbury Minerals Economics (BME). Key components of the methodology are as follows. (1) Relate demand to economic structure. (2) Focus on products rather than refined consumption. (3) Apply a consistent products/applications analysis to all countries and time series. (4) Incorporate scrap market dynamics within the analytical framework.

Jan 1, 1999

By Norihiro Murayama

The hydrothermal syntheses of zeolites from coal fly ash were carried out using NaOH and KOH as an alkali source. The cation exchange capacity (CEC) and the ion exchange selectivity were investigated for the zeolites synthesized by a hydrothermal treatment. The effective usage of the zeolite as a cation exchanger was considered from the viewpoint of engineering. Zeolite P, HS (hydroxysodalite) and K-CHA (potassium-chabazite) are mainly formed as zeolite species in NaOH or KOH solution at 393K. The zeolite P and K-CHA have a large exchange capacity as a cation exchanger. The cation exchange isotherms of various monovalent and divalent cations with various zeolites are investigated. The order of selectivity of the zeolites is as follows, NH4+> K+> Li+.For the divalent cation, the largest removal amount is obtained for Pb2+ in the low equilibrium concentrations below 0.2mmol/dm3, and almost perfect removal can be achieved for Pd2+. The order of selectivity of zeolites in low concentration is expressed in the following order; Pb2+> Co2+> Cd2+> Ca2+> Mg2+> Ni2+. Ii is considered the zeolites obtained from coal fly ash can be used as an excellent cation exchanger.

Jan 1, 2006

By S. Sugiyama, M. Kiuchi

"New metal working processes, such as the mashy-state mixing, mashy-state forging, mashy-state rolling and mashy-state extrusion are developed and applied to manufacture the so-called particle reinforced metals, fiber reinforced metals, particle reinforced cladding metals and so forth. These metal-ceramics composites are made of metal sheets, metal powders, ceramics particles and ceramics fibers. The mashy-state processes are also used to work those composites into bars, wires, tubes, plates, sheets, machine parts and other products. The working conditions necessary to manufacture sound composite products are clarified and the mechanical properties of the products are investigated. Through the investigation, it becomes clear that the mashy-state processes are useful and effective to manufacture metal-ceramics composites. It is al so known that these processes may be applied in various ways to development of new metal matrix compounds. IntroductionThe so-called metal-ceramics composites and processes to manufacture them are now being widely investigated in order to comply with increasing demands for new materials with novel and excellent mechanical properties and functions. The metal-ceramics composites are expected to have superior characteristics with respect to the elastic modulus, hardness, anti-wear resistance, high temperature strength and other mechanical properties to those of conventional metallic materials.The present authors ha v e been investigating into new metal working processes which are based upon the characteristics of metals and their alloys in the mashy-state. In the mashy-state, the metal (or alloy) includes both of the solid and liquid components. According to the fact that the partial melting takes place and the liquid component usually exists at grain boundaries, the metal in the mashy-state has quite different mechanical properties from those of the metal in the solid-state. Because of that the bonding force among grains is very weak due to the partial melting occurred at grain boundaries, the mashy metal has distinctively low flow-stress and high deformability. The mashy metal splits into grains or particles and sticks to others very easily. It is so soft as to be stirred up just like a lump of sherbet, but it is sufficiently viscous to be mixed up with other materials, such as ceramics particles and ceramics short-cut fibers."

Jan 1, 1988

By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995