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By Vladimir Lobanov, Vladimir Skorohodov, Andrew Evdokimov, Ural State Technical University 19, Boris Radionov

"The bulk of raw materials in metallurgy of secondary platinum metals are the wastes such as multilayered ceramic-metal systems, e.g. the spent catalysts of the chemical and petrochemical industry, automobile catalysts, etc. Due high chemical resistance of a ceramic basis the extraction of platinum metals by leaching even at very fine crushing is poor. The study of sorption leaching of platinum and a palladium from the spent automobile catalysts are carried out. The average content of PGM is 0.5%. A few methods of raw materials sampling were compared: 1) direct hydrometallurgical leaching of platinum metals from the fine-grained catalyst and atomic absorption analysis of the obtained solutions; 2) fusion to a metal or sulphidic collector of precious metals with the alloy analysis by direct spectrometry; 3) fusion with dissolution of a precious metals collector and atomic absorption analysis of PGM in solutions. Leaching allows detecting out no more than 90% of a palladium and 80% of platinum. Fusion to a collector gives the best results at the chemical ending. Researches on sorption leaching are executed. Under optimum conditions the extraction of platinum metals to concentrates is comparable with similar indicators of collector fusion.The large part of raw materials in metallurgy of secondary platinum metals are the multilayered or tridimensional ceramic-metal systems, in particular the spent catalysts of the chemical and petrochemical industry, automobile catalysts, ceramic-metal condensers, etc. The content of the sum of PGMs can be from hundreds grams per ton to several percent. For processing of such materials the hydrometallurgical methods of platinum metals leaching by various reagents are used commonly. High chemical resistance of the ceramic basis covering the metal particles causes low recovery even at very fine grinding. Other fundamentally different method of catalysts opening includes dissolution of the ceramic basis in the solutions of hydrofluoric acid and the subsequent recovery of platinum metals from insoluble residue. Application of this method is associated to use of corrosive medias and appropriate equipment. Fusion of the specified materials with collecting of PGM by copper, nickel or lead at the specialized enterprises provides higher extraction in semiproduct. At the same time, complexity and duration of the subsequent extraction of platinum metals concentrates causes high total cost per unit. Thereby this method is economically acceptable only for rather poor raw materials (no more than 0,1%). Undoubtedly, that the raw materials with the high content of PGM are reasonable to process by individual technology. In the present work the processing of some kinds of ceramic-metal raw materials, particularly automobile catalysts (neutralizers) with various collectors at the conditions of a target fusion are investigated."

Jan 1, 2008

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 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 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 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 Hongmin Zhu, Kai Huang, Shuqiang Jiao

"Garlic peel was used as the raw material to synthesize the biosorbent for the selective recovery of precious metals from the acid chloride solution. Garlic peel is rich in carboxyl-, amino- and thiol-groups, has the potential of exhibiting high affinity to Au(III) when appropriate chemical modification process was employed. Here in the present study, the biosorbent was prepared by cross-linking garlic peel particles with concentrated sulfuric acid. Adsorption tests for mixing different metal ions such as Au(III), Fe(III), Cu(II), Ni(II) and Zn(II) from various concentrations of hydrochloric acid media indicated that Au(III) was selectively adsorbed on the cross-linked garlic peel gel over the other coexisting base metal ions investigated. The crosslinking mechanism and selective adsorption of Au(III) were also investigated briefly.IntroductionPrecious metals are quite popularly applied in the modern industries such as jewelry, electronics and electrical devices, catalysts in chemical industry, etc. While their high values, limited deposit and quite large demand in industry makes its recovery from the industrial wastes, typically e-wastes, quite necessary. Actually, many techniques have been developed to recycle and recover the precious metals from various industrial wastes effectively in last decades, but the cleaning and ecofriendly processes are still seriously scarce [1]. Taking into account of the typical recovery processes using cyanide lixiviant in the alkaline media, or aqua regia, followed by the further recovery process using activated carbon adsorption or cementation with zinc, iron or aluminum plate or powder, though they both are quite effective recovery processes, if considering the special requirements on safety and ecofriendliness for the modern hydrometallurgical processes, various improved or novel extraction processes are greatly demanded [2]. Recently, the biosorption technology applied to the recover precious metals in the hydrometallurgical process has become a concern [3,4]. Inoue’s research group made great progress in the recovery of precious metals such as gold, palladium and platinum from the e-wastes such as spent mobile phone by using biosorption from the hydrochloric acid media [5,6]. This new hydrometallurgical process exhibits the prominent advantages of being cost-effective for its short process, easy operation and near-zero emission. In the above recycling process for e-wastes treatment, the preparation of biosorbents is the key and backbone of the whole recovery process. For this purpose, they developed a series of suitable sorbents for precious metals recovery by using the tanning-based or cellulose-based biomass such as persimmon peel, grape peel, orange juicing residue, waste cotton, waste paper through the crosslinking process with concentrated sulfuric acid and relative chemical modification processes [7-10]. In the present study, we also applied this technique to prepare the biosorbent of precious metal uptaking by using garlic peels as the raw materials, and investigated the adsorption properties of such-obtained gel in the hydrochloric acid media."

Jan 1, 2012

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 H. Kung, T. R. Jervis, M. Nastasi, T. E. Mitchell

"A systematic study of the structure-mechanical properties relationship is reported for nanolayered composites of MoSh-SiC, Mo-MoSh, Mo-MoShNx, MoSi2-MoSi2Nx, and Mo-MoShMoSi2Nx (x=3-4) synthesised by sputtering techniques. These composites have been studied by nano-indentation and cross-sectional TEM as a function of annealing temperature. As-deposited layers are amorphous except for Mo. With increasing annealing temperature, first MoSh and then SiC crystallize, while the hardness progressively increases until the layers start to spheroidize and grain growth sets in at 900ºC. For the case of Mo-MoSi2, the layers react and the composite deteriorates rapidly. However, MoSi2Nx remains amorphous up to 1000ºC, suggesting that it could act as a diffusion barrier between Mo and MoSi2. In fact the Mo. MoSi2Nx, MoSi2-MoSi2Nx and Mo-MoSi2-MoSi2Nx nanolayers are found to remain stable up to such temperatures. IntroductionMolybdenum dislicide, MoSh, is a potential matrix material for high temperature structural composites due to its high melting point and good oxidation resistance at elevated temperature [1]. The two major drawbacks for structural applications are inadequate high temperature strength and poor low temperature ductility. Silicon Carbide (SiC) being hard and thermally compatible with most ceramics and intermetallic compounds, has been found to be suitable for second phase reinforcement in various structural applications and, in particular, the addition of SiC whiskers improves the high temperature yield strength of MoSi2 [2]. While most of the research in MoSb-SiC composites has been on the particulate form of SiC, laminated composites may offer unique properties. It has been shown that synthetic multilayers with alternating layers of metal and/or compounds may exhibit interesting mechanical properties [3]. Enhancement in mechanical properties by decreasing the wavelength of multilayer spacing has been studied extensively. In general, two types of strengthening have been proposed: (1) Hall-Petch strengthening [4,5], where the strength increase is inversely proportional to the square root of the layer thickness; (2) Koehler modulus strengthening [6], which increases with modulus difference and decreasing layer thickness. In the present study, we have performed a systematic study of the relationship between strength and structure in a number of different nanolayered systems based on MoSh. Layer thicknesses have been varied and their nanostructures have been varied by heat treatment. Previous work on MoSi2-SiC is summarized [7]. In an attempt to improve fracture toughness, MoSh-Mo nanolayered materials have been prepared but are found to react and deteriorate. Previous work has shown that nitrided MoSi2 (MoSi2Nx with x=3-4) is highly stable [8] and so nanolayered composites of MoSi2-MoSi2Nx and Mo-MoSi2-MoSi2Nx have been prepared to assess the' stability and mechanical properties of these composites. Preliminary results are presented."

Jan 1, 1994

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 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 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 Damien Wagner

To reduce the emission of greenhouse gases by the steel industry, particularly for ironmaking, the production of DRI (Direct Reduced Iron) using hydrogen as the reducing gas instead of carbon monoxide is being considered. In this context, the reduction of pure hematite by hydrogen was studied at the laboratory scale, varying the experimental conditions and observing the rate and the course of the reaction. All the reduction experiments were performed in a thermobalance and supplementary characterization methods were used like scanning and transmission electron microscopy, X-ray diffraction, and Mössbauer spectrometry. The influence of rising temperature in the range 550-900°C is to accelerate the reaction; no slowing down was observed, contrary to some literature conclusions. A series of experiments consisted in interrupting the runs before complete conversion, thus enabling the characterization of partially reduced samples. Interpretation confirms the occurrence of three successive and rather separate reduction steps, through magnetite and wustite to iron, and illustrates a clear structural evolution of the samples. Finally, the influence of the sample type was revealed comparing a regular powder, a nanopowder and a sintered sample. The regular powder proved to be the most reactive despite its larger grain size, due to a more porous final structure.

Jan 1, 2006

By V. Baltazar

The behaviour of arsenic and antimony during copper electrorefining was studied in order to identify the conditions under which good quality copper cathodes could be produced from anodes with high levels of these impurities. Examination of the effect of current density over the range 21 to 37 mA/cm2 indicated that the relative amounts of As and Sb entering the electrolyte affected the onset of passivation. When the ratio of As/Sb entering the electrolyte was greater than 2, the anodes showed no sign of passivation even at the highest current density; when the ratio was less than 2, the anodes passivated at 37 mA/cm2. Cathode analyses showed that anodes with an As/Sb dissolution ratio less than 2.0 tend to produce cathodes of inferior quality even at normal current densities (25.7 mA/cm2). The criterion of a minimum As/Sb dissolution ratio of 2.0, and mathematical correlations for the distribution of As and Sb between the electrolyte and slime developed in a previous study, allow the calculation of the maximum allowable Sb level in en anode for a given As concentration. Analyses of plant data at the CCR Division of Noranda Inc. for the last four years of operation have demonstrated that the use of this as a quality control tool has allowed the quality of copper cathodes to be maintained despite a significant increase in the average Sb levels in anode receipts.

Jan 1, 1987

By Serdar Aksu, Fiona M. Doyle

"CMP will be an essential process in the production of integrated circuits containing copper interconnects. This study aims to improve our mechanistic understanding of the role that organic chelating agents might play in the reactive slurries used in copper CMP. Copper dissolution behavior in EDTA arid glycine was first examined by producing potential-pH diagrams for the copper-water-EDTA and copper-water-glycine 'systems. The results of potentiodynamic polarization experiments were then considered in light of these diagrams. . In-situ polarization experiments were conducted to gain insight into the electrochemistry of copper during dynamic polishing in slurries prepared from EDT A and glycine.IntroductionCopper has recently started to replace aluminum as the interconnect metal in integrated circuits. Copper interconnection offers faster and more reliable integrated circuits due to its higher electrical conductivity and superior electromigration resistance (1). The damascene method is used to form multilevel interconnects in the manufacture of integrated circuit devices with copper metallization (2, 3). Copper is deposited by CVD or electroplating into vias and trenches etched in the interlayer dielectric (IDL), over a diffusion barrier usually made from titanium, tantalum or their nitrides. Chemical mechanical planarization (CMP) then prepares the wafer for the next deposition step, by removing excess copper and planarizing the surface. During CMP, the wafer is rotated and pressed against a rotating platen covered with a polishing pad. Chemically active slurries containing submicron size abrasive particles (Si02, Al20 3, ceria, diamond, etc.) are applied. Both the mechanical action of the abrasive particles and the chemical action of slurry constituents remove material from the wafer surface. Planarization results because material is removed faster from protruding regions on the surface than from recessed regions. Since CMP can globally planarize .the entire wafer, it has become one of the key technologies for producing integrated circuits with copper metallization."

Jan 1, 2000

By Keiji Okumura, Hong Lan, Masamichi Sano

"Magnesium has been well known as one of the excellent agent of desulfurization, deoxidation, etc. in iron- and steelmaking because of its high reactivity. Since its production is energy nitensive, the price is very high. Thus magnesium has not widely been used as an agent in metal refining ·processes. In the present work, reduction of magnesia by carbon and aluminum is examined. Because the reaction is very sensitive to temperature, non-isothermal technique is applied to investigate the reaction kinetics. The effects of heating rate .and reaction interface area on the reaction kinetics .are studied. .A kinetic model is proposed based on the experimental results.IntroductionFor the metal refining processes, the production of high purity metal has been one of the most important research subject. In order to produce the high purity metal, the amount of the refining agent and the consumed energy is increasing. Therefore, if the future earth environment is taken into consideration, the further efficient and energy saving processes are required. Generally, Cao slag has mainly been used for desulfurization of molten iron as a desulfurization agent. However, environmental problems, such as recycling of disposal slags, are still unsolved. On the other hand, the deoxidation of molten steel is mainly performed by addition of aluminum. Therefore, the alumina inclusions· remain in. molten steel and the great efforts have been made to the removal of the inclusions. The affinity of magnesium with sulfur and oxygen is strong, and magnesium is well known as a powerful desulfurization and deoxidation agent. However, magnesium has been seldom used for the steel' refining process. The following reasons are considered. Generally, magnesium is expensive. And at iron- and steelmaking temperatures, the refining efficiency becomes low due to its abruptly .evaporation."

Jan 1, 2000

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 John J. Jonas, Sang-Hyun Cho, Ki-Bong Kang

"The recrystallization behavior of Nb micro alloyed steels containing Cr, Mo, Ni and Ti. was studied using hot torsion testing with the aim of modeling the recrystallization processes and the mean flow stress taking into account the microstructural behavior during hot rolling. The kinetics of static and metadynamic recrystallization were characterized and appropriate expressions were formulated for the recrystallization kinetics. These are shown that the recrystallization kinetics depend on steel composition and the processing conditions. The stress-strain curves were determined in order to derive new equations for the peak stress, peak strain, mean flow stress and softening kinetics. The peak strain is influenced by the presence of alloying elements; their addition, which has a solute drag effect, retards the rate of grain boundary motion, shifting the peak to the right. The addition of Nb to the steel results in a significant increment in the activation energy for hot deformation, and Mo has smaller effect than Nb, but Cr has the opposite effect. It was also found that the deformation activation energy in these steels was not altered by the addition of Ni. The rate of metadynamic recrystallization increases with strain rate and temperature and is observed to be independent of strain, in contrast to the observations for static recrystallization.The mean flow stress (MFS) calculations, based on the Sims analysis, are then compared with the predictions of a model based on an improved Misaka mean flow stress equation in which solute effects, strain accumulation, as well as the kinetics of static and metadynamic recrystallization are accounted for. Good agreement between the measured mean flow stresses, which is obtained from the mill logs of POSCO Kwangyang #3 HSM (hot strip mill), and 'predicted ones is obtained over the whole range of rolling temperatures. The results demonstrate that dynamic recrystallization followed by metadynamic recrystallization, supported by the unexpected load drops, sometimes occurs for the rolling schedules studied in the present analysis."

Jan 1, 2001

By U. Meyer, A. Alonso, P. Banios

The sampling of cathodes has changed with the introduction of the ISA-process in copper refineries. A Jernkontoret joint working group of refineries and rod plants from both primary and recycled copper plants has been investigating whether the actual sampling of cathodes is representative for this type of cathodes. As a first stage, samples were sent to the members of the working group with the objective to find an easy basis for a comparison of the results of the next stages. All samples show the same tendency for nearly all elements. In some cases, there may exist differences in calibration and for some elements the detection limits are too high, especially when Optical Spectrometry is used. In the second stage, discs were compared with melted samples to answer the question whether the punching of discs is sufficient for the quality control of the cathode. The analyses of the discs represent fairly well the cathode quality. There are differences between cathodes from different crops. Three punches are sufficient to determine the cathode quality. Finally, samples from various lots of cathodes were compared with samples from the rod produced from these cathodes. The impurity content of the rod corresponds to the impurity content of the cathode.

Jan 1, 2000