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By Toshiyuki Hashida, Victor M. Lopez-Hirata

"Small-punch tests and determination of fracture toughness JIC were conducted at 4 and 77 K on new cryogenic JN1, JJ1 and JK2 austenitic stainless steels, after isothermal aging. Equivalent fracture strain ?qf determined by measuring the reduction of thickness in the small-punch test specimen. A linear dependence of JIC on ?qf was found in these new materials. Regression analysis of experimental data produced the following linear relation JIC = 1304.1 ?qf + 8.09 [kJm-2]. An analysis of present work relation was pursued on the basis of material properties and evaluation method of he. Results showed that the slope value has a strong dependence on material yield strength and JIC evaluation method. This linear relation is useful for the evaluation of fracture toughness JIC, measuring the equivalent fracture strain ?qf by means of small-punch test. Thus it can be useful for assessing the degradation of fracture toughness in small areas such as, the heat-affected zone in welded components.IntroductionCryogenic structural materials for superconducting magnets of fusion nuclear reactor are required to possess a good combination of strength and toughness. The mechanical properties are required beyond the capability of conventional austenitic stainless steels [1]. New cryogenic JN1, JJ1 and JK2 austenitic stainless steels were developed by the Japan Atomic Energy Research Institute (JAERI) [1]. The structure of superconducting magnets is constructed by welding of 200 = thick plates of these steels, which are solution treated at high temperatures and then water-quenched to avoid intergranular precipitation. However, the welding process involves heating and cooling [2], which cause microstructural changes in both base metal and weld. In this heterogeneous microstructure, it is important to estimate the fracture toughness of these materials at cryogenic temperatures. Therefore, it is necessary to evaluate the effect of aging process on the fracture toughness behavior of these new steels. To determine the cryogenic fracture toughness, the elastic-plastic JIC value has been co=only used [2]; however, the specimen size is much larger than heat-affected zones in welded components. Small-punch (SP) testing method, employing miniature specimens, has permitted to evaluate the fracture toughness behavior at different temperatures in different nuclear reactor materials [3,4]. Mao et al. [5,6] and Misawa et al. [7] found a linear relation between JIC value and equivalent fracture strain ?qf, determined by SP method in non-ferrous alloys and ferritic steels at room temperature and austenitic stainless steels at 4 and 77 K, respectively. So that, this kind of correlation would be very useful to assess the fracture toughness JICe values by means of SP test in small zones of welded components."

Jan 1, 2012

By Guanghua Wen, Jian Li, Mingmei Zhu, Fei Xiong, Shengjian Cao

"Small inclusions removal from molten steel in a continuous casting tundish by gas bubbles, which were generated in the turbulent flow region by introducing inert gas, was analyzed theoretically and the inclusion-bubble adhesion and flotation process was also observed by high-speed photo-graph in water model. Results showed that small inclusions in the range of 20-50µm removal from molten steel by bubbles flotation involves three stages: contact, adhesion and flotation. The inclusion-bubble adhesion processes include two ways: inclusions adhering to the upper part of the bubble and inclusions adhering to the lower part of the bubble. As the bubble floats up, the number of inclusions adhering to the bubble are increased. The proper size of bubbles, which could enhance small inclusions removal efficiency, should be controlled in the range of 1-2mm.IntroductionReducing inclusions content in molten steel is a very important way to improve quality of steel, and one of the main tasks in steel making process.A variety of methods have been used for inclusions removal in molten steel. At present, the main approaches to remove inclusions are gas stirring, slag cleaning, filtering, centrifugal separating, and by means of ultrasonic or electromagnetic field. Among these techniques, gas stirring is the most widely and effectively method for inclusions removal. Inclusions in molten steel will be aggregated and generated to form larger size inclusions, and subsequently floated to the surface of molten steel by buoyancy; meanwhile, some inclusions will be adhered to bubbles and floated together to metal-slag interface where inclusions are absorbed by the covering slag layer. Some research work showed that flow behaviors of small bubbles are different from that of big ones [1-2], and smaller bubbles are more efficiency for fine inclusions removal in molten steel.There are many methods to generate bubbles. During steelmaking process, highly turbulent flow in the ladle shroud can split introduced inert gas into small bubbles, which enhances the removal of fine inclusions from molten steel. Turbulent flow of molten steel injected into tundish from ladle shroud has a high speed and it is a strong turbulent area in continuous casting. The gas can be introduced into the shroud below the slide gate. The high turbulence flow would break up the gas into small gas bubbles. Fine inclusions will be easily adhered to small bubbles and subsequently floated to the surface of molten steel. Generation of small bubbles in ladle shroud have been studied in some literatures [3-4]. Some research have analyzed the fine inclusions removal with injecting gas from the ladle shroud by mathematical simulation, and the results show that the refining method can obviously improve the removal efficiency of fine inclusions in tundish [5-8]."

Jan 1, 2013

By Yotamu Stephen Rainford Hara

"The study focuses on the reduction mechanisms of copper, cobalt and iron during carbothermic reduction of copper-cobalt mineral sulphide concentrates in the presence of lime, in the temperature range of 1073K and 1273K. We have used three types of mineral concentrates which were derived from froth flotation from the Copperbelt region in Zambia. The reduction mechanisms were studied using thermogravimetric analysis in which selected reactions were stopped at different times for characterising the reaction mechanism using optical microscopy, XRD and SEM-EDX analyses. Using SEM-EDX analysis, we have analysed in details the stages of metallic phase formation during reduction process. Metallic cobalt and iron were embedded into copper, thereby permitting magnetic separation of the reduced metals even though copper is diamagnetic. Methods of preferential reduction of metal values were investigated by analysing the metallic phase formation.IntroductionIn conventional smelting or converting of copper sulphide minerals, metallic copper forms by giving off S02 gas on. Although in terms of overall energy balance the selective oxidation for metal production has major advantages, the process suffers from drawbacks in smelting complex concentrates containing copper, cobalt and iron sulphides minerals and these are: (i) cobalt and iron are oxidised, and consequently cobalt is lost into the slag phase. (ii) The volume of S02 gas produced is in low concentrations, which is insufficient for extracting sulphur or manufacturing sulphuric acid. The release of dilute S02 causes serious environmental pollution. The major cause for the loss of cobalt and iron into the slag, is due to that fact that the oxides of these metals are more stable than their sulphides. Since cobalt and copper are more valuable than iron, reducing conditions are required in a separate slag treatment reactor using electric arc melting for recovering the lost metal oxides from slag. This energy-intensive step makes metal making expensive.During chemical beneficiation of mineral sulphides (Cu2S, CoS, FeS) in the presence oflime (CaO), two types of equilibrium conditions may be set up either by forming CaS under reducing conditions, or by stabilizing CaS04 under oxidising conditions [l]. By comparison in the presence of carbon, CaS and metallic phases form, enabling the recovery of metals from sulphide minerals, which have been investigated by a number of authors [2-9]. During reduction of metal sulphide in the presence of lime and with carbon, it has been proven that the overall reaction le proceeds via two main steps: [5, 8, 9] (i) the anion exchange reaction between metal sulphides (MS) and CaO as shown in equation la, followed by (ii) the reduction of metal oxide (MO) via reaction lb."

Jan 1, 2013

By Che Xin, Liu Tianlong, Bi Hongyun, Chen Lijia

"High-cycle fatigue experiments were conducted at 800°C in laboratory air for three ferrite stainless steels including 15CrNbTi, 15CrMoNbTi and 18CrNbTi, where the stress ratio of 0.l was adopted. The experimental results show that at 800°C, the fatigue limit of the 15CrMoNbTi steel is the highest, the fatigue limit of the 15CrNbTi steel is slightly lower than that of the 15CrMoNbTi steel, and the fatigue limit of the 18CrNbTi steel is the lowest. At the same maximum stress, the 15CrMoNbTi steel has longer fatigue lives than the 15CrNbTi steel in the low stress area, while the 18CrNbTi steel has the shortest fatigue life. In addition, the observations on the fracture surfaces of fatigue specimens reveal that the fatigue cracks initiate transgranularly at the free surface of the specimens and propagate in a transgranular mode.IntroductionIn modem automotive industry, the manufacturers have paid great efforts to clean exhaust gas and to improve fuel economy. It is thought an effective way to increase the temperature of combustion chamber in automotive engine. And thus, the manifold closed to the engine in automotive exhaust system can suffer high temperature up to approximately 1000°C. Because of their relatively low thermal expansion coefficient, high yield strength at elevated temperature and good fatigue resistance, ferrite stainless steels, especially added with alloying elements such as Mo, Nb and Ti, are increasingly used for automotive exhaust systems [1-3]. In fact, exhaust manifold operated under high frequency vibration and exposed to high temperature exhausting gas also requires good fatigue resistance at elevated temperature. Some studies on the high temperature fatigue characteristics of stainless steel have been documented. It has beeen found that the fatigue limit of four ferrite stainless steels including 409L, 436L, 429EM and 444 (18Cr- 2Mo) reduces significantly with increasing temperature [4, 5]. In the research concerning the effect of a-phase embrittlement on fatigue behavior in a high-chromium ferrite stainless steel, it is noted that the precipitation of brittle a-phase will reduce the crack initiation and growth resistances and result in a decrease in fatigue limit [6]. In this investigation, the high-cycle fatigue behavior of three ferrite stainless steels including 18CrNbTi, 15CrNbTi and 15CrMoNbTi at 800°C have been studied to address the mechanical aspect of high-cycle fatigue behavior for ferrite stainless steels and to provide the theoretical reference for the safe design of automotive exhaust system."

Jan 1, 2013

By Björn Hinzel, Joachim Rösler

"The most important characteristic of open-pored metals is porosity, since it enables all of their functional applications as filters or sound absorbers. Due to the notch effect of the pores, mechanical properties of porous metals are better than the ones of comparable structures made of polymers or ceramics. Consequently, only open-pored metals can be used in aircrafts to reduce flow noise or noise resulting from the core engine by acoustic absorption. Absorption properties depend highly on pore size and porosity of the material, which must be characterized as precisely as possible in order to analyze the correlation between morphology and noise reduction performance. Here, a line segmenting method is explained in order to characterize pore size and porosity of absorber materials using image processing based on two dimensional microscopy images, including sample preparation and specification of the set-up. Then, the influence of the pore structure on the measured absorption behavior is discussed. Finally, the correlation of acoustic behavior, pore morphology, and porosity is outlined.IntroductionSignificant noise loads affect everyone causing anxiety, depression, insomnia and other effects which impair health and productivity [1],[2]. Due to the rising number of flights and aircrafts, air traffic noise increases dramatically. To counter this development, various approaches have been developed to reduce the different noise sources resulting from airframe, jet or engine [3],[4],[5],[6]. One approach to reduce this noise is the application of noise reducing liners in the hot gas path [7]. This is especially important, since the engine is becoming the dominant noise source of modern airplanes during take-off [8]. Due to the elevated temperatures and high fatigue loading in this part of the aero-engine, conventional passive absorber materials cannot be used. Polymers would not be able to bear the heat and ceramic fibers would crack under the mechanical loading due to the notch effect. Consequently, this study focuses on metals with open pores, which can resist elevated temperatures and fatigue loading and additionally resemble geometrically conventional passive absorbers. Based on the production processes, e.g. sintering of metal fibers [7], powder processing using a foaming agent [9], coating of polymer foams [10], or using melt infiltration techniques [11], the characteristic dimension of the porosity is usually in the range of 0.01-10mm. In this work, sintered metals and metal sponges are analyzed after the theory of sound absorption is briefly outlined. Then, measurements of the acoustic absorption of metal sponges and sintered metals in an impedance tube are performed. To understand and predict the acoustic properties of metals with open porosity, it is necessary to characterize the materials as precisely as possible. This is explained in detail using a line segmenting technique, followed by a discussion of the connection of pore characteristics and acoustic absorption. Finally, a conclusion is given."

Jan 1, 2012

By S. -H. Jeon, Y. -S. Choi

"The three dimensional current distribution on the rectangular cathode is predicted using a boundary element method with a linear element of trigonal type. The effect of cell geometry and anode shape on current distribution is simulated. Calculated results compare well with experimental results. The proper combination of anode size and distance between electrodes increase the current uniformity.The importance of electrodeposition as a fabrication technology in the electronics industry is large and growing. The main advantages of this wet processing method, in comparison to other dry processing methods, lie in its high yield, rapid processing and low cost. In nearly every application of electrodeposition the pursuit of deposit uniformity, especially thickness uniformity, has been technically imperative. The thickness uniformity of the deposit depends largely on the current distribution over the cathode. The current distribution is primarily determined by the geometrical characteristics of the electrodes and the cell. Also the polarization at the electrode surface and the mass transfer affect the current distribution.The current distribution is an important consideration for those involved in designing electrochemical systems and electroplating systems in particular. Although it is important, the common practice in industry is to use trial and error method to design the cell that optimize the uniformity of current distributions in electroplating. The purpose of this paper is to illustrate the useof boundary element method to predict three-dimensional current distribution in rectangular cell.The calculation of the current distribution is possible by various numerical techniques, which include the finite difference method (FDM)1, the finite element method (FEM)2, and the boundary element method (BEM)3,4. These methods of the numerical calculation have various problems, respectively, but the BEM is considered to be the most efficient. This is due to the fact that the BEM has the advantage of solving field equations only on the surface of a calculation domain. A good comparison between the BEM and the FEM for the secondary current distribution in a Hull cell was made by Matlosz et al.5The fundamentals on the theory of current distribution in electroplating are well-established in the literature by a number of authors.6, 7, 8 However, a small fraction of these works have been specially addressed to three-dimensional analysis, and, mostly thel·10 have focused on the problem qualitatively rather than quantitatively.Extending the previous work to three-dimension, we developed the program for the quantitative calculation of 3-dimensional current distribution using a boundary element method with a linear element of trigonal type. Integrals with singularity from the fundamental solution have been analytically computed and it is shown in detail in the Iiterature11. This paper deals with the three dimensional current distribution for the electrode position of copper in a cubic type cell and the effect of anode shape, size and the distance between electrodes on current distribution is studied."

Jan 1, 1997

By Sridhar Komarneni

"Microwave-hydrothermal processing is a novel technique which combines the conventional hydrothermal processing with microwave field and we previously showed for the first time, that ceramic powders can be rapidly produced by this technique. This review paper deals with the synthesis of unary oxides such as Fe203, Ti02, Zr02, etc., binary oxides such as BaTiO3, SrTiO 3, PbTiO 3, SrZrO 3, KNbO3, etc., and ternary oxides such as NaTi2 (PO4)3 and pyrochlore phases of Pb(Mg1/3Nb2/3)O3, Pb(Zn1/3Nb2/3)O3 etc. and metal powders such as Cu, Ni, etc. below 195°C. This method can be adopted to the synthesis of a large variety of powders by the appropriate control of pH, Eh, temperature/pressure and concentration of chemical species. The main advantages of this method compared to conventional hydrothermal processing are (a) it increases the kinetics of reaction by one to two orders of magnitude, and (b) it can lead to novel phases especially those with layered structures.IntroductionConventional hydrothermal processing is a well-established synthesis technique which has been extensively used in the preparation of fine ceramic powders [1-5], large single crystals [6-8] and massive cement blocks [9]. Technologically important ceramic powders such as BaTiO 3, Al203 etc. made by the hydrothermal process are now commercially available. Although there are numerous methods for materials synthesis, hydrothermal method is truly a low temperature and environmentally benign process. For example, ZrSi04 (Zircon) which is extensively used in ceramic industry can be prepared hydrothermally at 150·C [10] compared to sol-gel or solid-state method [11,12] which require a temperature of about 1000·C. The hydrothermal method is environmentally benign because hydrothermal reactions are carried out in closed systems at low temperatures and the contents can be recovered and recycled after cooling to the ambient conditions. One of the disadvantages with any low temperature processing method is slow kinetics. For this reason we have combined the hydrothermal method with microwaves to enhance kinetics and we named this method as ""Microwave-hydrothermal"" processing [13- 16]. Although the combination of microwave and hydrothermal techniques has been used in the past few years to dissolve all kinds of inorganic (e.g. alumino silicate rocks) and organic materials rapidly for chemical analysis, we were the first to show its potential value for the synthesis of various ceramic powders [13-16]. In this paper, I show that this novel method is applicable to the synthesis of all unary, binary and multinary oxides by the appropriate control of pH, Eh, temperature, pressure and concentration of chemical species. In addition, this method is also found to be useful for the preparation of metal powders."

Jan 1, 1994

By A. M. Alfantazi, M. Boissoneault, D. B. Dreisinger, J. Synnott

"The effects of five commercially available foaming reagents (range of 0 to 25 ppm) namely Dowfroth 250, Saponin, Yucca, Licorice and Meta-Para Cresol on acid mist control, current efficiency, polarization behavior, and deposit morphology and orientation were investigated. The deposition was carried out using a bench scale electrolysis apparatus (cell volume 3L) at 500 Nm-2 and 38°C for 3 hours from Kidd Creek zinc electrolyte. The acid mist control capability of the various reagents was studied and compared by characterizing the foam layer generated during actual electrowinning conditions and by direct quantitative measurements of acid mist levels on top of the electrowinning cells. Within the range considered, the addition of these reagents reduced the current efficiency, refined the grain size of the deposit, and changed to preferred orientation of most of the deposits. Among the reagents tested, acid mist measurements indicated that Licorice and Dowfroth 250 were the best acid mist suppressant at emissions of 0.30 mglm3 and 031 mg/m3 respectively while Yucca and MPC produced the most mist at 3.0 mg/m3 and 33 mg/m3 emission rates, respectively.IntroductionMost of the world's primary zinc is produced via a combined roast-Ieach-purificationelectrowinning process. Depending on the electrolysis conditions, several additives may be added to the electrolyte. Some (e.g. glue, antimony, sodium carbonate) are added to mainly counteract the detrimental effects caused by impurities while others (e.g. licorice, Saponin) are used as foaming reagents to prevent excessive acid mist formation. Acid mist emission is a problem in many electrolysis operations because it corrodes the equipment and is a health hazard to the workers in the tankhouse as well as it pollutes the environment. Due to recent trends towards more environmental protection and more stringent in-plant hygiene, there is an increasing need to minimize these aerosols. In order to eliminate or minimize these aerosols foaming agents are usually added to the electrolyte to produce a foam layer on top of the electrolyte, thus trapping most of the mist. The ideal foaming agent would trap all of the mist and would not interfere with the electrowinning process. It is also evident that the reagent toxicology, cost and availability are important factors that need to be considered.Review of the available literature clearly indicated that very little work has been done in the past on the subject of acid mist control in electrowinning operations particularly in the area of foaming and anti-misting properties of surfactants. Two papers [1,2] have reviewed briefly the existing technologies for acid mist control. Recently, most of the work in this area has focused on the development of special mechanical devices that could be attached to the electrodes and control the mist generation at the source before it is emitted to the cellhouse [2-5]. On the other hand, extensive body of literature exists that deals with the effects of anti-misting reagents on the electrowinning aspects [6-7]."

Jan 1, 1997

By John E. Dutrizac, Tzong T. Chen

"Laboratory experiments were undertaken to ascertain the behaviour of various ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C and in the presence of 40 or 50 g/L of hematite seed. Copper, nickel and zinc are not significantly incorporated in hematite precipitates. Although the nickel contents increase to 0.22% as the Ni concentration increases to 60 g/L, the solid solution Ni contents are low relative to the bulk Ni contents. Thus, part of the Ni may be present as tiny particles of poorly soluble NiS04.H20. Increasing germanium concentrations to 2,000 mg/L result in products containing up to 0.59% Ge. The Ge occurs either in solid solution in the hematite or is adsorbed on the nanometer-size hematite crystallites. Increasing As(V) concentrations to 10 g/L increase the AsO4 contents of the products up to 16%. However, the products consist of hematite together with As04-containing Fe(SO4)(OH) and an unknown Fe-AsO4 species. All the hematite products contain - 1% SO4 which appears to be adsorbed on the nanometer-size hematite crystallites.IntroductionDissolved iron is a common impurity in most hydrometallurgical processing circuits and, generally, the iron must be eliminated prior to the subsequent recovery of the sought after metals. Simple neutralization of iron-rich solutions yields slurries which are difficult to thicken and filter. To address these concerns, the jarosite, goethite and hematite processes have been developed, and these technologies are able to reject the dissolved iron in a readily filterable form [1]. Despite its higher cost, the hematite process offers several potential advantages. Because hematite is an iron-rich, high-density compound, its formation would reduce the mass of residue and the size of a residue storage pond. Hematite is the thermodynamically stable form of iron under ambient conditions, and this stability would facilitate the impoundment of hematite precipitates. Furthermore, hematite has some market potential for cement manufacture and even for iron making [2]. In all the commercial hematite processes, the dissolved ferric ions are first reduced to the ferrous state. Subsequently, the pH of the solution is adjusted and the solution is then oxidized. The ferric ions gradually generated during solution oxidation hydrolyze and precipitate mostly as hematite, although commercial hematite products also contain trace or minor amounts of jarosite-type compounds. However, there are potential advantages in precipitating hematite directly from ferric ion solutions, as the reduction and subsequent oxidation of the iron are not required. Although the precipitation of hematite directly from relatively concentrated ferric sulphate solutions (up to 0.5 M Fe(SO4)is) was recently demonstrated [3], the behaviour of impurity species during hematite precipitation is largely unknown. To address this issue, systematic laboratory experiments were undertaken to ascertain the behaviour of a number of ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C, and the results are presented in this paper."

Jan 1, 2012

By Toshitaka Ota, Hisao Suzuki, Minoru Takahashi

"Perovskite-type lead zinc niobate (PZN) exhibits excellent electrical properties such as high dielectric constant, high electrostrictive coefficient and superior piezoelectricity. Therefore, PZN ceramics are very promising for high performance electronic devices. However, perovskite phase PZN is not stable under the ambient atmosphere. Accordingly, it is very difficult to prepare single-phase perovskite PZN ceramics. In this study, A-site cation of lead was partially substituted for barium to stabilize the perovskite phase of the PZN (Ba-doped PZN) powder. In addition, molecular design of an alkoxide precursor was controlled for a low-temperature processing. As a result, molecular design to suppress the lead-volatilization during calcination was preferred for a low-temperature processing. Processing temperature for a single-phase perovskite was depended on the amount of barium dopant. Doping of20 mole% of barium resulted in the single phase perovskite at 900 °C. The temperature for the single phase perovskite of Ba-doped PZN powder, which depended upon the amount of Ba-doping, was lower than that of the powder prepared by the atmosphere controlled conventional powder processing at least by 150 °C.IntroductionFerroelectric thin films and powders with perovskite structure are of renewed interest for micro-electronic applications, including ferroelectric random access memory (FRAM), dynamic random access memory (DRAM), and thin-layer capacitors integrated onto a silicon wafer [1-3]. In addition, recent advancement in micro-machine requires a high performance micro-actuator [4]. A perovskite type relaxor of Pb(Zn113 Nb213)03 is one of the promising materials for a high performance capacitor and microactuator because of their high permittivity and electrostrictive coefficient [5]. Therefore, this paper focuses on the low temperature processing of Ba-doped PZN powders.Chemical solution deposition (CSD) from molecular-designed alkoxide precursor solution is one of the most promising techniques for processing high-performance powders and thin films because it offers precise control of compositions on a molecular scale as well as a low processing temperature [6]. However, chemical solution deposition of perovskite type PZN powders and ceramics are very difficult because of the formation of stable pyrochlore phases. Therefore in the past, PZN powders and single crystal have been prepared by the hydrothermal method or flux method as well as the partial substitution method of a A-site cation [7-10]. In this study, a suitable molecular design for a preparation of perovskite type Ba-doped PZN powders with a chemical solution deposition process is investigated as well as the effect of A-site cation substitution. Chemical solution deposition from molecular-designed alkoxide precursor solution is expected to decrease the amount of a A-site substitution and/or a crystallization temperature for a single phase perovskite. This paper describes ""the relation between molecular-design and processing temperatures for a single-phase perovskite of Ba-doped PZN powders in comparison with the conventional oxides mixing method."

Jan 1, 2000

By Henrik Gudbrandsen, Geir Martin Haarberg, Ana Maria Martinez, Karen S. Osen, Sverre Rolseth

"The Several approaches were tried for developing an electrochemical route for producing high purity silicon from molten salts. K2SiF6 and metallurgical grade silicon were used as the source of silicon. Molten LiF-KF and pure KF with additions of K2SiF6 were used as electrolytes at temperatures from 550 - 900 oC. Silicon was cathodically deposited and anodically dissolved in the fluoride electrolytes. High electrorefining efficiency was obtained for many elements after electrolysis experiments at constant potential or constant current. The main challenge was to reduce the contents of boron and phosphorus. Another difficulty was to remove inclusions of solidified electrolyte. The lowest energy consumption was estimated to be ~ 3 kWh/kg Si, while the best current efficiency for Si deposition was found to be ~ 95 %.IntroductionSilicon is the most important material for photovoltaic power generation devices because of high feasible efficiency, low ecological impact and slow degradation. Development of a new and less expensive route for producing silicon of the desired quality is necessary in order to make solar cells competitive. Electrochemical routes may be an alternative possibility, and many laboratory studies have been reported over the past few decades. Most of the studies have been performed in molten salts, chloride or fluoride, at moderate temperatures so that solid silicon was deposited at the cathode. The production of high purity silicon has shown an annual increase of about 25 %, due to the increasing demand of solar grade silicon (SoG-Si). For future increased use of solar energy it is important to develop alternative, more energy efficient and cheaper processes for SoG-Si production compared to the Siemens process.Common silicon sources have been SiO2 and K2SiF6 for electrowinning and MG-Si in the case of electrorefining. A serious challenge is to find an oxygen evolving anode for electrolytes containing dissolved oxides. Especially at moderate to high temperatures and in molten fluoride electrolytes this is a difficult task.Many experimental results have been reported in molten chloride electrolytes. Nohira et al. [1-3] and Chen et al. [4] cathodically deposited silicon by electrodeoxidation of solid SiO2 in molten CaCl2 by potentiostatic electrolysis. An alternatice approach is to use electrorefining of low-cost metallurgical grade silicon (MGSi) to produce SOG-Si. In previous studies [5], an MG-Si anode was used, and silicon was successfully electrodeposited on a molybdenum wire in a CaCl2 based melt. It was found that the anode was strongly passivated due to the precipitation of silicon. Also, some deposits detached from the molybdenum wire because of the poor adherence to the cathode.Considering the Cu-Si alloy which has a good segregation effect for some impurities, and should not passivate, could be a good candidate anode for electrorefining. [6]."

Jan 1, 2014

By Himaki Nakano, Kenji Hara, Toshiaki Tsuru, Shunsuke Kawano, Takeshi Ohgai, Hisaaki Fukushima, Shigeo Kobayashi, Tetsuya Akiyama

"Electrodeposition of Fe-Ni and Zn-Ni alloys from aqueous solutions is one of the well-known examples of anomalous codeposition in which less noble metal deposits preferentially. In this paper, the electrodeposition behavior of these alloy systems was compared between the methanol and aqueous baths. In Fe-Ni system, the significant suppression of the deposition rate of more noble Ni was observed over a wide range of electrolysis conditions in both methanol and aqueous baths. However, the electrodeposition of Zn-Ni alloys showed the typical feature of normal type codeposition in the methanol baths, which was completely different from that in aqueous sulfate baths. The difference in the electrodeposition mechanism between Fe-Ni and Zn-Ni alloys was discussed on the basis of the alloy deposition behavior in the baths in which the activity of water was varied:INTRODUCTION'It has been well known that Fe-Ni alloys show an excellent soft magnetic property. Therefore, thin films of this alloy have been used to fabricate the'-various magnetic devices. For the production of Fe-Ni thin films, dry processes such as sputtering, PVD and CVD are 'employed frequently and the resulting films showed a preferable property as a magnetic material. Electrolyses as a production technique of thin films, on the other hand, has the advantage over other processes in its cheaper production cost due to the simplicity of the production unit The Zn-iron-group metal alloys such as Zn-Ni and Zn-Fe electrodeposited on a steel sheet ale known to exhibit excellent corrosion resistance and therefore the electrodeposition of these, alloys has been applied to the production of surface treated steel sheets mainly for automotive body panels.According to Brenner (1), the electrodeposition behavior of Fe-Ni and Zn-Ni alloys was' classified into the' 'anomalous type. In this type of codeposition, less noble metal, i.e. Fe for Fe-Ni and Zn for Zn-Ni system, deposits preferentially and the change in -the alloy composition- with the variation of electrolysis conditions was unpredictable because of their obscure deposition mechanism. Since most properties of the alloys mainly depend on their composition, the composition of the deposited' alloys must be controlled strictly. Therefore, it is neces5al)' to clarify the mechanism of anomalous codepasition in Fe-Ni and Zn-Ni systems: Several mechanisms have been proposed so fur, and among them the hydroxide .suppression mechanism (2), (3) has been regarded most plauslble depend on their composition, the composition of the deposited' alloys must be controlled strictly. Therefore, it is necessary to clarify the mechanism of anomalous codeposition in Fe-Ni and Zn-Ni systems: Several mechanisms have been proposed so far, and among them the hydroxide suppression mechanism (2), (3) has been regarded most plausible. According to this mechanism, it can be predicted that the codeposition behavior depends greatly on the characteristic of water solvent in this study, using methanol as a solvent, the electrodeposition behavior of the anomalous codeposition was investigated to discuss the validity of the hydroxide suppression mechanism."

Jan 1, 2000

By Z. Zhang, Cuihuan Huang, Zongshu Zou, Nan Wang, Xueqian Xin

"Vitrification is considered as an attractive procedure for municipal solid waste incineration ash, which can realize the volume reduction and innocent treatment of incineration ash, as well as reuse of bottom ash. The main oxide components of molten ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the total mass. The phase relations and thermodynamic properties of the CaO-Al2O3-SiO2-FeOx-MgO-Na2O oxide system is highly required, and is of great scientific significance for optimization of vitrification processing and sustainable resource utilization of melting slag. A study on the equilibria phase relations of CaO-SiO2-MgO-FeOx system was done by using CALPHAD method based on FactSage in this paper. The modeling parameters for the thermodynamic properties of liquid phase in CaO-SiO2-MgO-FeOx system were established and the equilibrium phase relations of MgO-SiO2-FeOx and CaO-SiO2-FeOx-MgO systems were calculated for different temperatures and oxygen partial pressures.IntroductionThe main oxide components of vitrified bottom ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the bottom ash by weight [1]. During slag processing and modification, the knowledge of thermodynamic properties and liquidus temperature in the related slag system is highly required [2-5], which is not yet available. Through literature survey [6-9], it is clear that the systematic information on the concerned complex slag system is scarce. Most binary subsystems except FeOx-Na2O have been investigated well. Among ternary subsystems, few phase relations of the Na2O-MgO-SiO2 ternary system are available. For the phase relations of the system Na2O-MgO-Al2O3, all the studies are focused on the Al2O3-rich region. Investigation on the CaO-Al2O3-FeOx system is limited to Fe2O3-containing system with relatively higher oxygen potential. Most quaternary systems are not studied well except the CaO-MgO-Al2O3-SiO2 system, mainly due to their metallurgical importance. Figure 1 demonstrates the research status of the vitrified bottom ash slag with almost zero effort [10]. The effort here is defined based on the published literature by considering the number of publications, the investigated composition ranges, and the research details. So far the engineers in the field have to make assumptions of the thermodynamic properties of the simplified oxide system, without taking into consideration the interactions of the different oxide components, which hinders the development of the slag valorization and utilization. In order to provide thermodynamic properties for the application of the vitrified bottom ash, the six-component oxide system (CaO-MgO-Al2O3-SiO2-FeOx-Na2O) will be investigated through both experimental approach and computer modeling."

Jan 1, 2011

By S. Goto, S. Yamashita, K. Hata

"The average consumption of zinc dust for purification of zinc leaching solution is more than 25 kg per tonne of electrolytic zinc. Authors proposed to remove impurities in zinc leaching solution by electrolysis instead of cementation by zinc dust. The effects of copper and arsenic on electrodeposition of cobalt in zinc sulfate solution were examined fundamentally using a potentiostat. It is observed that cobalt is easily deposited on a cathode at potentials under -480mV with arsenic. Mesh cathodes of stainless steel and lead anodes were used in a small electrolytic cell and the electrolyte was circulated through 'the electrodes during the electrolysis. The effect of electrolyte circulating rate , pH, cell temperature, current density, and concentration of copper and arsenious ions on removal of cobalt were studied. Removal of Cd and Ni are also examined.IntroductionCobalt is difficult to remove from a zinc leaching solution by a simple cementation reaction using zinc dust. However, it is easily precipitated by zinc dust with co-addition of arsenious or stibinous oxide and copper ion in practical operations(I), (2), (3). The consumption of zinc dust for purification is 16-152 kg per tonne of electrolytic zinc and 65% of this zinc dust consumption is used for cobalt purification. The average retention time for purification of cobalt is 4.5 hours (1). A more economical process for purification is desired instead of zinc dust. The mechanism of this acceleration effect of copper and arsenious oxide on removal of cobalt are explained by the authorsas follows; a galvanic cell is formed between zinc dust and copper which is precipitated firstly, and cobalt is reduced on copper as Co-As alloy by this galvanic current(2). This assumption was confirmed in experiments using a galvanic cell with a membrane( 4). The following galvanic reactions occur between zinc dust and copper precipitate; on copper cathode,2H+ + 2e -= Hz(g)2Coz+ + 2HAs02 + 6H ++ 10e -= 2CoAs + 4HzOand on zinc anode,Zn = Zn = 2+ 2e –This galvanic current becomes almost zero in a zinc sulfate solution which includes only cobalt and no arsenious oxide, and cobalt is weakly deposited on a copper cathode. Cobalt deposition requiers a high degree of cathodic polarization. However, the galvanic current flows almost constantly in an electrolyte, which includes arsenious oxide, and the cathode potential is kept at about -500mV. Cobalt is precipitated as Co-As on the cathode.The authors assumed that cobalt may be removed by electrolysis at a very low current density instead of zinc dust and the following experiments were carried out. In the first part of this paper, the fundamental experiments using a potentiostat on the behaviour of cobalt in zinc sulfate solution are described. In the second part, the results of the electrolysis are reported. Cobalt is removed by a new type of an electrolytic cell, which was desigoed to <Iccelerate the rate of deposition of cobalt. The removal of cadmium and nickel in a solution which includes cobalt and arsenic are also examined."

Jan 1, 1997

By K. S. Han, M. Yoshimuura, H. Fujita, Y. Sato, S. W. Song

"Film of LlCoO2 as cathode material for rechargeable lithium microbatteries has been fabricated on the platinum metal substrate by electrochemical-hydrothermal method in concentrated LiOH solution at 200 °C as Soft Solution-Processing. The film fabrication has been understood in terms of dissolution of cobalt metal powders and subsequent oxidative deposition on the substrate. The film structure was characterized using scanning electron microscope, X-ray diffraction analysis; X-ray photoelectron spectroscopy and micro-Raman spectroscopy.IntroductionRapid growth of wireless communications and emerging integrated optoelectronic circuits caused the miniaturization· cif electronic devices, thus the demand for high energy density microbatteries as a power source for the microelectronics increases. In this regard, all solid-state lithium microbatteries including LiCoO2 and LlMn2O 4 [l-4], the most promising intercalation cathode material, have been developed. However, major difficulty of .fabrication of a lithium microbattery arose from the preparation of cathode film, according to a· recent report on Rare Metal News [5]. Although many attempts have been made to deposit the cathode films, all those methods are mostly chemical vapor deposiiton (CVD), various evaporation, sputtering techniques and spray pyrolysis. These methods require preparation of bulk cathode materials cir its precursor, then deposition with complicated instruments including high· vacuum system, and even postsynthesis annealing to obtain desire electrochemical 'properties. It is clear that all of these techniques are neither economic nor environmentally friendly. Compared to those methods, film form.ation from an aqueous solution is thought to be simpler and more economical, and requires much· less energy consumption. Our .group has demonstrated the utility of Soft SolutionProcessing [6,7], which is defined as environmentally friendly processing using (aqueous) solutions, to produce films of a variety of functional solid materials. According to the Pourvaix's diagram [8], some metal can be dissolved in an alkaline solution and consequently combined with hydroxyl group or oxygen anion forming metalate or metalite. Cobalt also seemed to form cobaltite, HCoOi in strong alkaline solution in the Pourvaix's pH-potential diagram. Based on this information, it was expected that LiCoO2 could be prepared using the cobalt metal in Li OH solution by Soft Solution-Processing. Recently, we reported the successful single step fabrication of electrochemically active LlCoO2 films on the cobalt metal substrate by hydrothermal methods without any post-synthesis annealing as Soft SolutionProcessing [9,10]. Film formation mechanism could be elucidated by the following evidences. . As expected from Pourvaix's diagram, cobalt metal was dissolved in concentrated LiOH solution forming dissolved cobalt species which was detected by an observation of absorption band in UV-VIS absorption spectrum [10]. Thus the reaction was assumed to be started from dissolution. Time dependent potential of Co electrode exhibited only one-step evolution with 0.6 eV from Co metal to LiCoO2 [10]. Another strong evidence was the finding of LiCoO2 powder precipitates at the bottom of tetlon beaker after the reaction [11]. Based on those experimental findings, it was understood that film is formed by dissolution-precipitation mechanism [9-11]."

Jan 1, 2000

By Payal Bakshi, Sangeeta Tiwari, Mohini Saxena, Anusha Sharma

"Recycling and reuse is perhaps the most favorable and beneficial way to solve the problem of industrial waste disposal. However, the use of industrial wastes like fly ash, tailings etc is in practice for brick manufacturing, land filling, embankments filling etc. These existing practices do not add enough value to the wastes. Moreover, some wastes may have very good potential to be incorporated in valuable products like paints. This study reveals about the value addition of industrial wastes like fly ash, copper tailing and blue dust as an extender in paints. Comparative properties and characteristics of these three wastes for application in paints are discussed. Fly ash, copper tailing and blue dust were characterized for physical, chemical and mineralogical properties and used in different paint formulation based on their potential to the particular application. Fly ash has been found very useful in enamel, primers and flat paints while copper tailing was found suitable in oil based paint formulations. The performance of fly ash and copper tailing paints were evaluated by comparing with those of conventional whiting extender. Blue dust was compared with conventional iron oxide for use in priming coats. The extender properties of these new material and paints prepared out of blue dust, fly ash, copper tailing, were found better than the existing related materials.IntroductionIndustrial development and environmental reforms should run parallel to benefit each other. This is the best policy, which must be adopted by industries for the sustainability of the current modern life. The high degree of industrialization and urbanization adds scads of waste resulting problem of pollution and challenges of their safe disposal. The nature of waste depends on the process that produces waste as its by-product. Therefore, policies/plans are prepared by keeping the view of possible potential hazards. Among the different wastes some are generated in the industries, which have great importance in the country’s economy, like fly ash waste from thermal power industry and mining waste. In India the total contribution of thermal power in the total electricity generation is more than 70% and it produces about 123 million ton of the fly ash annually [1]. On the other hand mining plus extraction of ferrous and nonferrous metals also produce waste in million tonnes of categories [2]. Since the generation of this waste is very high they cover large land area for their disposal and dumping [3]. The storage of this waste in the dumping sites for long time duration may cause problem of land, surface water, ground water and fertile soil contamination [4]. As far as Indian fly ash is concerned it does not contain toxic element over the limits of hazardous waste [5]. However, in general most of the metals deposits are found in the form of pyrite based ores. Mining wastes contain toxic elements e.g. heavy metals in varying amount, which get mobilized when pyrite get oxidized to sulphate producing sulphuric acid [6,7]. These ores contain very less amount of targeted metals in themselves thus they require extensive preprocesses for concentration of the metals [8]."

Jan 1, 2008

By M. F. Hochella

Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis have been used to study the mode of occurrence and mineral associations of gold in partially oxidized high grade gold ore from the Carlin sediment-hosted deposit. Rounded.gold particles have been observed that range in size from 0.03 to 0.1 p.m (300 to 1000 A) in diameter. The gold is associated with maghemite h-Fep3l and a K-Al-Si-bearing phase that is suspected to be illite. Detailed descriptions of gold and its mineral associations in &apos;Carlin-type&apos; gold deposits are critical not only to understanding the mechanism of fluid transport and precipitation of gold, but also to developing improved metallurgical techniques for the recovery of gold from refractory ore. Direct observation of gold in unoxidized ore is rare due to its relatively high degree of dissemination and low average bulk concentration which averages 9 ppm according to Radtke (1). Hausen and Kerr (2) observed 1 to 5 p.m grains of gold directly in oxidized ore but these microscopically visible particles account for only a small percentage of gold present in the ore. The samples used in this study were selected from individual beds of high grade, partially oxidized ore (4.55 oz/ton or 156 ppm gold) that were collected in the Main pit of the Carlin mine. The samples were collected from several thinly laminated carbonate micrite beds within the top 50 meters of the Roberts Mountains Formation. The carbonate micrite has been altered by hydrothermal fluids to a calcite-absent, moderately silicified rock referred to as alteration zone #3 by Bakken and Einaudi (3). Based on petrographic and SEM studies, the samples contain carbonaceous matter, and both pyrite and iron oxide pseudomorphs after pyrite. The oxidation of pyrite may be a pro-duct of deep weathering, in which case limited remobilization of gold may have occurred. TEM sections of the rock were prepared by first embedding small chips in low viscosity epoxy. The epoxy blocks were cut with a Reichert Ultracut E ultramicrotome, producing thin sections less than 0.1 p.m thick. The sections were examined with a Phil-lips 400ST TEM at 120 keV in both imaging and selected area diffraction modes. Native golci*was easily detected in TEM bright field images due to the large electron density contrast between gold and all other phases that are present (Figs. 1 and 2), Gold was positively identified with high spatial resolution EDX analysis in the transmission electron microscope, although selected area diffraction of individual grains was not successful EDX analyses of the platy and massive minerals immediately surrounding the gold particles typically indicate the presence of Si, AI, K, and Fe, However, the d-spacings derived from selected area diffraction of these polycrystalline masses (as, for example, in Fig. 2) give an exact match for maghemite. As a result, there is no diffraction information to identify the K-AI-Si-bearing phase(s). The lack of a diffraction pattern could be due to either electron beam damage or to a poorly crystalline phase(s).

Jan 1, 1987

By Elli Nurminen

Sulphate decomposition was studied in the conditions of a typical copper flash smelting heat recovery boiler. The aim was to determine the kinetics of the copper sulphate decomposition reactions and to find out if they are likely to take place in the process conditions prevailing in an industrial HRB. The information is essential in CFD-modelling of the reactions taking place in the boiler and for optimising the process. Thermal decomposition of sulphates was studied by thermogravimetry. The experiments were conducted with a commercial copper sulphate, a partially sulphated copper oxide and an actual process flue dust. The main variables studied were temperature and gas composition of a N2-O2-SO2-mixture. The samples were characterized with SEM, optical microscope and XRD. Temperature affected the decomposition rate strongly but the gas composition had a minor effect on the kinetics. The decomposition was fastest in the partly sulphated oxide and slowest in commercial copper sulphate. Keywords: Sulphate decomposition, flash smelting, heat recovery boiler, flue dust

Jan 1, 2004

By H. K. Lin

Thermodynamics of Cu-C1-H2O system and the kinetics of copper dissolution in cupric chloride solution were studied with emphasis on possible difficulties which may occur during copper electrowinning. E,-pC1 diagram of this system wasestablished. Equilibriumdistributionof various copper chloride complexes of different valent states at the presence of metallic copper was computed through the relations of the simultaneous equilibria. The mechanism-of copper dissolution in the cupric chloride solutions was proposed and the mechanism of copper electroposition was discussed. The researched results were used for guiding the investigation of copper electrowinning from cupric chloride solution.

Jan 1, 1991

By John Nauman

Liquid ferrous silicates that are related to cop- per slags have been studied as media for the transfer of heat in pyrometallurgical processes. The effective thermal diffusivities have been measured from 1025Oto 1400°C, and values in the range of 0.004 to 0.007 cm2/ sec have been obtained. The heat-transfer characteristics of these slags have been determined by measuring the rise of temperature of a cold nickel sphere immersed in the liquid slag. The sphere is spun about its vertical axis to obtain a well characterized flow of liquid about the sphere. The principal barrier to the transfer of heat from the bulk slag to the metal sphere is a solid shell of slag that forms around the sphere and subsequently melts. It appears that the detailed nature of this shell is important to theheat- transfer process. A mathematical model is used to predict the rate of heating of the sphere, and to evaluate various aspects of the system that can influence the transfer of heat.

Jan 1, 1976