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By N. Ono, H. Fujiwara, S. Otsuka-Yao-Matsuo, T. Omata

"The electrical conductivity and the oxygen release and uptake of sintered indium tin oxide (ITO) upon heating and cooling under the condition that P(O2)/P*=4.9X10-4 (P* = atmospheric pressure), :when P(O2) was approximately 50Pa, were simultaneously measured by using a closed-system oxygen-gas analyzer. A large increasing in -the electrical conductivity - upon the· oxygen release detected in 1130<T<1273K was observed. Quantitative relationship between the number of oxygen atom released from ITO and the conduction electron density in ITO was studied. The release of one oxygen atom agreed with the generation of two conduction electrons, i.e., the efficiency-carrier-generation for the oxygen release from the ITO was almost one. The oxygen atom released must be originally at the quasi-anion site in the C-type rare-earth lattice, i.e., the 16c site in the space group of Ia3, as an interstitial excess oxygen, Oi"". It was concluded that the mechanism of conduction carrier generation and compensation upon SnO2 doping into In2O3 can be expressed by the defect equation, 2SnO2-2Sn1n +2(1-z)e'+zOi""+3O0 x+(l-z)/2O2, and that the oxygen release bringing the increase in the electrical · conductivity can be expressed by the equation, Oi""-1/2O2+2e'.IntroductionThin films of SnO2-doped In2O 3 (generally designated as ITO, for indium tin oxide), which have high optical transparency for visible light and high electrical conductivity, have been used as transparent electrodes for liquid crystal and electrochromic displays. It is well known that the electrical conductivity of ITO depends on the content of SnOi-dopant and oxygen. However, a reliable relationship between electrical conductivity and the absolute oxygen content in ITO has yet to be reported. The elucidation of such a relationship is one of the important clues for realizing extremely highly conductive ITO electrodes."

Jan 1, 2000

By Corby G. Anderson

Today, with a stringent economic and environmental climate prevailing in the copper business, there is increased interest in evaluating new processing alternatives for production. Hydrometallurgical pressure oxidation of copper concentrates is one of the more viable approaches and several technological candidates have emerged. Of these, an overlooked but, ironically the first industrially proven methodology, utilized nitrogen species catalyzation in the oxidizing pressure leach system to produce copper via SX!EW. Given its many inherent process advantages, this may prove to be a feasible process alternative for the future. In this paper, the history of the system and its application to chalcopyrite concentrates will be outlined. In particular, a novel methodology for effective recovery of precious metals from chalcopyrite concentrates will be discussed. Finally, the perceived economics of this unique industrially proven process will be delineated.

Jan 1, 2000

By T. Shimizu

In Japan, the emission standard of selenium in effluent was set at a maximum of20 mgll in Feb. &apos;94 for the first time, and it is scheduled to be further decreased to a maximum of 0.1 mg/I from Feb. &apos;97 due to tightening of the Water Pollution Prevention Act. Selenium (IV) and (VI) are generally found in effluent from precious metals refineries. Although selenium (IV) can be easily eliminated by some reducing agents, selenium (VI) is more difficult to be reduced. Therefore, many smelters are having difficulty in complying with the new emission standard. At Mitsubishi Materials&apos; Naoshima smelter, the behavior and the elimination of selenium in effluent have been extensively investigated. As a result, it was found that two strategies were particularly effective. One of them is improving the overall operation of precious metals refinery, that is, feeding uniformly the effluent to the waste-water treatment plant, reducing the effluent volume by recycling and recovering more selenium (IV) in the effluent. The other is eliminating selenium (VI) in the effluent from the precious metals refinery. It was found that selenium (VI) can be effectively reduced by using hydrazine under high? sulphuric acid concentration and high temperature conditions. By using these measures, it is considered that Naoshima Smelter will be able to comply with the new emission standard.

Jan 1, 1996

By Robert S. Gärtner

The selective aluminum extraction by 3 different calixarenes (p-tert-butyl-calix[4]arene-tetra¬2-acetic-acid-ethyl-ester, p-tert-butyl-calix[4]arene-tetra-2-acetic-acid and p-tert-butyl-calix-[4]arene-di-2-acetic-acid-ethyl-ester) from an industrial pickling bath solution was studied. The pickling bath solution contained hydrofluoric and phosphoric acid as its main components. The aluminum removal was not successful and also no significant extraction of trace metals present was observed.

Jan 1, 1999

By Gus Van Weert

This paper describes the results of autoclave testwork where ferric nitrate was hydrolysed in the presence of certain cations and anions and the resulting hematite analyzed for foreign constituents. For the cations Zn++, Ni++, Cu++, and AI+++, selectivity factors of over 107 were found. Magnesium gave 3.106. These factors are calculated as Me/Fe in solution over Me/Fe in the hematite; Me representing the metal in ion added. As-a result of the testwork at Delft University of Technology, BUDELCO (the Netherlands electrolytic zinc producer) ran a series of ferric nitrate hydrolysis tests in the presence of 10 additional trace elements. Impurity levels were prejudiced on Me2 EPHA extraction of iron from their zinc circuit, followed by HNO3 stripping. Good selectivity against base metals was confirmed, but trace elements forming anions (As. Sb) and sulphate were incorporated in the hematite. These BUDELCO results are also presented.

Jan 1, 1995

By Christine Wenzl, Andreas Filzwieser, Stefan Konetschnik

"The METTOP-BRX-Technology is a novel manifold electrolyte inlet, which allows improved productivity and production in new and existing tankhouses by achieving higher current efficiency and cathode quality, as well as using current densities higher than 400 A/m2. Two installation examples are shown: Montanwerke Brixlegg AG, Brixlegg, Austria (upgrade of existing tankhouse) and Xiangguang Copper, Yanggu, China (new tank house). Montanwerke Brixlegg AG has been using the METTOP-BRX-Technology since 2005, and converted half of the whole tankhouse to METTOP-BRX in 2011 in order to use a current density of more than 400 A/m2. Xiangguang Copper started up their second tankhouse in May 2011. This tankhouse was constructed in the same way as the existing tankhouse, but was designed for 292,000 t/a cathode copper (existing tankhouse: 200,000 t/a) by using the METTOP-BRX-Technology. This production increase is a consequence of a much higher current density, namely 410 A/m2, compared to 280 A/m2 in the old tankhouse.IntroductionCopper electrorefining has been practised for more than hundred years, the last big change being the implementation of stainless steel cathodes in the 1980s [1], In 2005, the METTOP-BRXTechnology was first introduced. This technology was developed jointly by METTOP and Montanwerke Brixlegg, Austria, and allows improvements in productivity and production in new and existing tankhouses in an economic way. The METTOP-BRX-Technology is a novel manifold inlet that allows improved tankhouse productivity by increasing current density and/or current efficiency while maintaining or improving cathode quality [2]."

Jan 1, 2012

By R. C. Hubli

Copper (II) chloride has proven to be an efficient lixiviant for copper sulphide ores and secondary sources of copper such as scrap. Nickel sulphides are generally associated with copper ores and copper-nickel matte is an intermediate product of processing mixed sulphides. While the copper species in aqueous chloride media are present as chlorocomplexes, the presence of nickel as Ni++ offers effective separation between the two by solvent extraction techniques. Oxidation of millerite by cupric chloride in sodium chloride solutions has been studied as a function of rate of agitation, leaching time, temperature, acid concentration and total initial cupric concentration. The reaction has a 1/2 order of dependence on initial cupric concentration in the range of 0.0 to 0.5M. The activation energy for the temperature range 333 -363 K has been found to be 59.2 kJ/mol with chemical reaction at the unreacted mineral surface as the rate controlling step. The rate expression, according to the shrinking-core model, for initial cupric concentrations between 0.0 to O.5M, is evaluated as

Jan 1, 1996

By Jun Iwai, Osamu Takai, Yasushi Inoue, Hiroyuki Sugimura

"Infrared reflection absorption measurement was performed during plasma-enhanced chemical vapor deposition of silicon dioxide films at room temperature. Hydrocarbon contaminants adsorbed onto growing film surface are oxidized by oxygen radicals in plasma resulting functional groups which include C=O and C-O bondings. These groups exist only near the surface and are hydrolyzed rapidly after exposure to air.IntroductionRecently low-temperature silicon dioxide (SiO2) deposition has been in a growing industrial demand in pa1ticular, polymelic substrates such as polycarbonate and polyethylene telephthalate, which have poor heat resistance, need low process temperature (near room temperature) in coating of SiO2 which is a suitable material to improve optical and mechanical properties of polymenc products. Plasma enhanced chemical vapor deposition (PECVD) using organosilicon reactants is one of the most promising technique for lowering process temperature, so that it has been extensively studied1-12. In the present; however, hydrocarbon contaminants and a plenty of Si-OH termination in Si-O-Si networks tend to exist in the films, which degrade mechanical, optical and electrical properties of the films. It is necessary to understand the deposition mechanism at, low temperature in order to solve the problems. We have studied the low-temperature PECVD of Si02 by spectroscopic diagnosing techniques such as optical emission and mass analysis6-7, 11- 12Infrared reflection absorption spectroscopy (IR-RAS) has been a well-established technique for characterization of thin films on metals as· well as on semiconductors and insulators13-17. In this paper, we report on' the surface reaction of room-temperature PECVD of Si02by using in situ IR-RAS."

Jan 1, 2000

By M. K. Yelloji Roa

Effect of conditioning with Thiobacillus ferrooxidans on the floatability of sphaierite and galena has been determined in this work. The flotation behavior of the conditioned minerals clearly shows that such bacterial conditioning does produce marked modification of their surfaces. The variables affecting the surface modification and thereby the flotation response of the minerals were found to be cell concentration used for bacterial conditioning, the period of biotreatment and the pulp density. Importantly, while the enhancement in flotation obtained due to sulphuric acid treatment was retarded by biotreatment in the case of galena at all cell concentrations due to electrochemical effects, such decrease occurred in the case of sphalerite only at cell concentration sufficiently high for their attachment to the mineral surface. The effect of bacterial conditioning has significant implications to the differential flotation of sphalerite and galena. Mechanisms responsible for the modification of the surface properties of these sulphides due, to bacterial conditioning are discussed.

Jan 1, 1991

By Yongxiang Yang

High temperature processing of raw materials in metals production and recycling often involves complex multi-phase fluid flow and heterogeneous chemical reactions at various scales. Good understanding of the process physics and chemistry is crucial for process operation and process development. The traditional scale-up process through laboratory scale ? pilot scale ? commercial scale route has been more and more complemented and partially replaced by full-scale process simulation. Computational fluid dynamics (CFD) has become a very useful simulation tool in process research and development. At the same time industrial applications challenge the CFD development with its complex transport phenomena, often in large-scale reactors with small-scale physics and chemistry. The current paper discusses the applications of CFD to a number of high temperature metallurgical and materials processing applications. The research was carried out by using commercial CFD codes as the framework, and the emphasis was given to the special efforts for the development and implementations of sub-models with process-dependent physical and chemical characteristics. To illustrate the application of CFD simulation to high temperature metallurgical processes and coupling of sub-models to the general-purpose CFD codes, five examples are given: (1) melting of aluminium scrap in a rotary furnace for recycling, (2) molten hot metal flow in a heterogeneous coke-bed of a blast furnace hearth, (3) gas flow heat and mass transfer in a submerge electric arc furnace for phosphorus production, (4) high temperature incineration of hazardous waste in a rotary kiln, and (5) transient heating of metals in heat treatment furnaces.

Jan 1, 2006

By Tao Li

The development of DP(Dual Phase) steels and TRIP(Transformation Induced Plasticity) steels has received much attention in recent years due to their high strength and simultaneous good ductility, which provides the potential for weight reduce and resource savings on certain components in automobile or other industries. So a controlled rolling process was simulated in the present study by thermomechanical simulator (Gleeble 1500) for producing DP steels on a kind of low carbon steel containing a small amount of Si and Cr. F+M dual phase microstructures have been obtained during continuous cooling processes of a wide cooling rate range from 10°C /s to 60°C /s. The grain size of the dual phase steel developed can be refined to less than 5 m through the mechanism of deformation induced ferrite (DIF) transformation. The ultrafine ferritic grains are equiaxed with high-angle boundary, and the martensite islands of an average size less than 5m disperse uniformly in the ferrite matrix. The ultrafine martensite islands not only inhibit the growth of ultrafine ferritic grains and improve the bonding of F/M interface, but also increase remarkably the strain hardening rate in the processing of the present Dual-Phase steel. As a result, the tensile strength of ultrafine grained Dual-Phase steel reaches higher than 1000 MPa. The result shows that an ultrafine grained Dual-Phase steel of low carbon and low alloy is promised to exhibit desired F+M microstructure by means of this new TMCP process.

Jan 1, 2006

By André L. de Vegt

Soil and groundwater beneath a zinc production plant in The Netherlands are contaminated with metals and sulfate. To avoid contamination of nearby drinking water aquifers, a hydro-geological containment system and a biological treatment plant for the extracted ground water have been installed. Currently about 5000 m3/day of groundwater is extracted from a combination of 12 shallow and deep wells. Heavy metals and sulfate have to be removed from the extracted water before it can be discharged into a river. Several water treatment methods have been studied and pilot tested at the site. The preferred and selected process is based on the activity of sulfate reducing bacteria (SRB) and combines sulfate removal and heavy metal removal in one single installation. Anaerobic bacteria reduce sulfate to sulfide resulting in the precipitation of metal sulfides. Excess sulfide Is biologically converted to elemental sulfur. A full scale biological treatment system was started up in May 1992. Design, start-up, commissioning and operational experiences are reported in this paper. Concentrations of metals and sulfate in the SRB water treatment plant effluent are well within the limits set by the Dutch Authorities for discharge to surface water.

Jan 1, 1995

By B. J. Scheiner

The presence of organic materials in gold ores interferes with gold extraction by cyanidation. The carbon contained in the ore has been shown to adsorb gold cyanide complex from solution. Removal of the carbon content by roasting or chemical oxidation prior to cyanidation results in gold extractions of 85 to 95%. This paper discusses how the mineralogy of the carbonaceous gold ores affects gold recovery by cyanidation. It also discusses the advantages and disadvantages of roasting and chemical treatment to render the ore amenable to cyanidation.

Jan 1, 1987

By Zhang Hengzhong

Ni-P-Fe slag is the by-product in the production of phosphate fertilizer in blast furnace with nickel contained serpentine ore as the raw material. It contains nearly 5-7% Ni, 65-7( Fe, and 10-12% P. The slag is very hard to process, it neither dissolves in aqueous ammonia, nor in sulphate acid. In the stiff the technique to treat the slag in order to extract valuable nickel was developed, it essentially consisted of the processes of roasting, leaching, separation and purification. Nickel sulphate was prepared with this method.

Jan 1, 1993

By Xiao Y. Yan

A fused salt electrochemical process was investigated for the synthesis of non-oxide ceramic powders directly from metal oxides, boric oxide, and carbon powders by electro-deoxidation. Sintered pellets of the mixed powders were designed to act as a composite cathode in the electrolytic cell. Electrolysis was carried out in molten CaCl2-NaCl eutectic at 3.1 V and at 600-900 ºC under argon. The favoured cathodic reaction was the removal of the oxygen from the oxides to produce metal atoms that reacted with either the reduced boron atoms, forming a metal boride, or the carbon initially present in the sintered pellets to produce a metal carbide. The technical viability of the process was demonstrated by the electro-deoxidation of sintered pellets of TiO2/B2O3 and TiO2/C to produce TiB2 and TiC, respectively. Compared to existing carbothermic reduction process, this new electrochemical process may be less energy intensive and may lead to lower production costs. I

Jan 1, 2008

By K. H. Bech, S. T. Johansen

"The mass transfer at fluid-fluid interfaces due to turbulent agitation is investigated theoretically. In particular a theory is derived for interface stresses due to interface energy and surface renewal. This theory indicates that surface renewal may take place if the geometry is sufficiently large and if surface tension is sufficiently low.By using a model for a typical turbulent structure we compute the interface mass transfer for a stressless interface and a fully interface. Results for the general situation is not presently available. The computed results are used to derive analytical expressions for the mass transfer based on turbulent kinetic energy and free stream turbulent length scales.One important application of the theory is the mass transfer at the electrolyte side of the bath-metal interface in the Hall-Heroult process. For this process we show that mass transfer should be expected to be of the rigid surface type."

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&apos;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 Takeshita. Takuo

"In this work, the progress of the HDDR process is discussed mainly on the Nd-Fe-B magnet system. There are three technologies being used for the Nd-Fe-B permanent magnet production; the sintering technique, the rapid quenching annealing and the HDDR process. The HDDR process utilizes· the HDDR phenomenon, in which hydrogen absorbing intermetallic compounds go through as they are heated in hydrogen atmosphere, Hydrogenation - Decomposition Desorption - Recombination. In the HDDR process, these four steps in the HDDR phenomenon are processed by choosing suitable reaction conditions regarding to hydrogen gas pressure, temperature, rate ·of desorption and etc., and we can produce permanent magnet powders of good magnetic properties with microstructures consisting with sub-micron size crystalline grains. In the anisotropic magnet powders, the sub-micron size crystals are being mostly aligned in the crystallographic c-axis direction. Possible applications of the HDDR process to other systems are also discussed.Microstructures of the Nd-Fe-B Permanent MagnetsIt is well known that magnet properties of magnetic materials are very sensitive to their microstructures [l]. This is seen in almost all magnet materials from soft magnetic materials and hard magnetic materials to magnetic memory materials. In this regard, the production technology is very important for the control of microstructures of permanent magnets The Nd-Fe-B magnet is the most powerful permanent magnet as a practical permanent magnet, and its coercivity force is much dependant on the microstructure as is the case for other permanent magnets."

Jan 1, 2000

By Mikiya Tanaka

Keywords: Solvent extraction, nickel, electroless plating, accelerating effect With the increasing importance of electroless nickel plating technology in many fields such as the electronic and automobile industries, the treatment of spent baths is becoming a serious problem. Although the spent baths are currently treated by a conventional precipitation method, a method with no sludge generation is desired. Previously, we proposed the solvent extraction recovery of nickel from the spent baths by means of solvent extraction using LIX84I as the extractant. However, a problem of this method was that the extraction and stripping of nickel were not fast enough to achieve high efficiencies when the continuous extractor was used. We have overcome this difficulty by finding that the addition of an acidic organophosphorous reagent in small amount into the organic phase markedly promotes the extraction and stripping rates of the nickel. Shaking-out tests using a separatory funnel at 240 spm revealed that the time to reach the equilibria is more than 60 min with only 20 vol% LIX84I, but is reduced to 10 min and 2.5 min by adding 2 vol% DP8R, respectively, during the extraction and the stripping with sulfuric acid.

Jan 1, 2004

By Reinhard F. Dobner

After a short introduction about the HK&apos;s secondary smelter process and explanations concerning the anodes produced the regulation and buffering of bleed will be described and the principles of technology for processing of bleed will be presented. Modernization aspects, especially installation equipment, and the different types of evaporators used will be described in detail. Besides, experience made with acid-resistant materials - stainless steel, enamel, plastics - will be reported. Environmental aspects such as water and air pollution will be outlined briefly and in conclusion the quality of products obtained as well as quality control will be presented.

Jan 1, 1997