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By Kazuyuki Kakegawa

"Sintered body of lead zirconate titanate (PZT) was prepared through the spark plasma sintering (SPS) technique. When the mixture of raw materials was calcined at 800°C and sintered at 900°C for 10 min. with SPS technique, the sintered body had almost theoretical density but was a mixture of lead titanate (PT) and PZT. When a calcining temperature of 1100°C was employed, sintered body had a single PZT phase but a lower density. High dielectric constant was obtained for a sample calcined at 800°C, sintered with SPS tecbriique and fired again in the air at 1100°C.IntroductionSpark plasma sintering (SPS) is a recently developed technique for sintering metals and ceramics1. The scheme of SPS is shown in Fig. 1. Sample is put in a graphite die in a vacuum chamber. It is pressed and pulse voltage is applied. The electric current heats the die. It is said that the pulse causes a spark-plasma between particles in the sample. Because of the spark- plasma, sample can be sintered at temperatures lower than that in the ordinary sintering by several hundred degrees of Celsius. The sintering period is also very short2Low sintering temperature and short sintering period in SPS technique cause low reaction rate. It is both disadvantage and advantage. In some cases, the reaction cannot be completed under the SPS conditions. If a mixture of several compositions having different properties can be sintered without a compositional change by the diffusion during the sintering, combination of properties, and therefore a design of property will be possible3. The low reaction rate of SPS may enable such combination."

Jan 1, 2000

By M. Tamura, K. Fujita, K Shinozuka, H. Daimon, H. Esaka

"In-situ observation of unidirectional solidification using transparent substance has been performed to investigate the growth direction of solid phase. Cell or dendrite of which preferred growth direction is not parallel to the heat flow direction was observed with various solidification conditions. Dimensionless growth direction (p) changes from 0 to 1 with increasing growth velocity at a constant temperature gradient. Introducing the dimensionless growth velocity, the relation between p and growth condition could be correlated.IntroductionTransition in macroscopic solidified structure from chill to columnar zone which is found in normal castings takes place via grain selection1). Cast products such as turbine blades are unidirectionally solidified, grain selection plays an important role to choose suitable crystals which have reasonable orientation in the region called ""starter"", which is a very initial part of casting2). Therefore, grain selection is a very important process in the formation of casting structure. The present authors have been studying on the process of grain selection using succinonitrile, which is a transparent organic substance and have found that the growth distance necessary for grain selection depends upon the solidification condition3-5). When the solid/liquid interface is dendritic, the grain selection occurs quickly. On the other hand, when the solid/liquid interface is cellular, it occurs slowly. We supposed that the growth direction of dendrite is different from that of cell when the substance is unidirectionally solidified. Indeed, Kurz and Fisher wrote in their text book that dendrite grows along its preferred growth direction, <100>, regardless of heat flow direction and that cell grows along heat flow direction regardless of its preferred growth direction1). However, there is no quantitative description about the growth direction when the solid/liquid interfacial morphology is cellular. Furthermore, there have been little works6) to study the growth direction of cell and dendrite."

Jan 1, 2000

By X. K. Lan

The greater demand for high-quality large-diameter crystals has led to the robust idea of a free- flying solar-powered furnace satellite, whereby the buoyancy-driven convection effects are almost nonexistent, and diffusion-controlled crystal growth with minimal radial segregation is promoted. In the proposed solar furnace, a paraboloid of revolution imaging concentrator is used to focus the sun&apos;s radiation onto an-ampoule which holds the solid charge to be processed. The charge will start melting in the vicinity of the focal point, after which it is translated in order for the melt to resolidify as a single crystal. A ray-trace method has been developed to determine the incident concentrated solar heat flux on the ampoule surface for a perfectly-aligned configuration with an incoming columnated beam. A transient 2- dimensional conduction problem with phase change is formulated, which is solved using the commercial code FIDAP. Results highlighting the feasibility of growing GaAs, Ge and Si crystals with diameters of the order of 20 cm using the solar furnace satellite concept are presented. The transient temperature fields within various charge materials are quantified.

Jan 1, 1994

By Heinz Giegerich

This paper deals with a new development in recycling second generation catalytic converters, namely metal substrate converters (MSC). It describes a patented dismantling process, whereby the MSC is segregated into it&apos;s three components outer steel shell, metal substrate carrier foil and ceramic W8shcoat with embedded precious metals.

Jan 1, 1995

By A. Siegmund, R. D. Prengaman

Lead anodes used in zinc electrowinning generally contain 0.5 - 1.0 % silver to reduce the rate of corrosion over the service life. For good quality zinc, the cathodes must contain less than 10 ppm lead. In order to reduce the lead contamination of the cathode, the lead anode must become coated with a protective layer of Pb02/Mn02. The formation of this layer may take as long as 30 - 60 days, during which time zinc production is substantially reduced and the cathodes are contaminated with lead. To improve the mechanical properties of Pb-Ag-anodes alloying elements such as calcium, strontium, barium and others are added. The production of cast lead-silver or lead-silver-calcium anodes often results in the formation of numerous holes, voids or laps in the anode surface that can initiate localized internal corrosion. Based on the experience as the major supplier of rolled anodes for copper electrowinning, RSR Technologies has developed an improved anode for zinc electrowinning. The anode consists of a rolled Pb- Ag-Ca-alloy with a controlled surface grain structure. It forms an adherent protective oxide coating within 2 - 3 days when placed in an electrowinning cell. The preferred calcium and silver contents of the alloy are 0.03 - 0.08 % and 0.3 - 0.4%, respectively. Rolling sheets significantly reduces the presence of internal porosity or laps. The lack of defects results in long anode life. The rolling also produces a uniform grain structure to which the corrosion product readily adheres, thus significantly reducing the conditioning period.

Jan 1, 2000

By Cleusa Cristina Bueno Martha de Souza

Hydrometallurgical techniques for processing metals are becoming an efficient method for recovering metals. Although batteries&apos; manufacturers have got rid of mercury content, some efforts have been made for recovering other metals enclosed in the battery formula. This paper discusses the bench scale experiments in the purification process of leached solutions from alkaline spent batteries. After leaching process using sulfuric acid as leachant, the solutions containing Fe, Cd, Pb, MIl, Zn and K were neutralized to precipitate iron hydroxide. In a second step, the purification experiments were carried out with excess of zinc dust to try to remove Cd while Mn and Zn still remain in the solution to be recovered in an electrolysis stage. The purification experiments procedures were conducted at different temperatures and times to find out properly conditions from the viewpoint of metals removal After filtration the solutions were submitted to chemical analysis to certify the metals content extracted.

Jan 1, 2001

By Chikabumi Yamauchi, Masami Tashiro, Toshiharu Fujisawa, Hiroyuki Snano

"Rare earth metals usually contain large amount of oxygen because of their reactiveness, and therefore oxygen removal is one of the major problems on the purification of rare earth metals. In the present research work, halide flux treatment at high temperature under inert gas atmosphere was applied to the oxygen removal from neodymium. NdF3 was used as a halide flux. Deoxidation reaction and its mechanism were discussed based on the experimental results. Halide flux treatment is very effective for oxygen removal from rare earth metals.IntroductionSolid Sate Electrotransport (SSE) process has been successfully applied for the elimination of interstitial gaseous impurities from chemically active metals[l]-[5]. However, to achieve a higher effectiveness of the SSE process, it is required a very low initial impurity content in the metal. In case of rare earth metals, it is known that they usually contain large amount of oxygen that should be lowered as much as possible before applying the SSE process. In addition, if effective oxygen removal is achieved by simple process, it is significant also from the industrial viewpoint. In the present work, the application of a halide flux treatment is investigated to remove oxygen from neodymium by using NdF3 as a flux. At first, deoxidation reaction and its mechanism were discussed based on the phase diagram of the Nd-NdF3-Ndp3 quasi-ternary system. Based on the results, oxygen content in deoxidized neodymium was calculated theoretically and it was verified by deoxidation experiments."

Jan 1, 1998

By J. M. Figueiredo, A. R. Silva, M. C. Coelho, R. M. Guedes

"With the continuous depletion of conventional sources of non ferrous metals, low grade complex sulphide deposits have been regarded as an alternative source of supply of zinc, copper, lead and also silver and gold. In spite of very important efforts in research in this domain it is still a long way to go in order to achieve reliable technological solutions both in ore dressing and metallurgical treatments which enable these complex materials to be regarded as commodities. The RLE process to treat bulk concentrates such as those obtained from portuguese ores, under development at LNETI and QUIMIGAL premises, combines experienced unit operations and innovative configurations and is an effective contribution for the future use of these materials. The results of three years of experimental work and main conclusions on the overall feasibility of the process are presented.IntroductionIn spite of the very well-known problems associated to the development of complex sulphide deposits, the economical importance of the enormous reserves of these materials, widespread all over the world, is so evident that its future use as source of supply of basic and precious metals and other minor elements is almost unavoidable.Critical steps in that direction are mainly concerned with favourable economical conditions and sound metallurgical practice for the treatment of nonferrous metals concentrates, which are nowadays still considered as non-conventional raw materials.Since Portugal is one of the countries where these orebodies occur more extensively, Portuguese authorities have dedicated since the beginning of the seventies, a big effort on finding economical and reliable processes for the recovery of copper, lead, zinc and also gold and silver, and for this purpose, several alternatives on ore dressing and metallurgical processing were studied, however without full sucess.Five years ago LNETI, a research laboratory, and QUIMIGAL, a chemical company, both state owned, decided to launch a research programme for the development of a metallurgical process for the treatment of NFM concentrates, which received financial support from NATO under its programme ""Science for Stability""."

Jan 1, 1988

By Francis Vanbellen

Umicore Precious Metals Refining operates an integrated precious metals smelting and refining plant in Hoboken, Belgium. Once a smelter and refiner of complex concentrates, the plant today?s feed consists exclusively of industrial and consumer recycled products, making it the world?s largest recycling facility for precious metals. Unlike the fairy tale of the Frog Prince, it took much more than a princess? kiss to successfully realize this makeover. A completely renewed plant has been built over the past decade. The most visible technological innovation was the commissioning of the Pb-Cu smelter. Its flexibility towards very different types of feed makes it perfectly suited as main entry to the Hoboken flow sheet. A new Cu-leaching & electro winning plant and precious metals refinery make up the Precious Metals Operations (PMO) whose targets are fast throughput and maximized yields for gold, silver and the platinum group metals. The Base Metals Operations (BMO), flexibly process the by-products from the PMO, valorizing ?impurities? like indium, tellurium, selenium and others. Off gas and waste water treatments ensure compliance with strict environmental standards. Precious metals recycling is an art that goes beyond mastering a unique flow sheet. Umicore Precious Metals Refining offers a complete recycling service, taking care of sampling and assaying, metals management and logistics. The quality of this integral service is recognized through the attribution of ISO certifications for our operational activities, sampling and the environmental care. And it?s an art that follows Michelangelo?s experience: ?Art is 5% of inspiration and 95% of transpiration.?

Jan 1, 2006

By Peter K. Liaw, Charlie R. Brooks, David C. Joy, Wei Zhao

In this paper, effects of oxidation, porosity and fiber-fabric stacking sequence on flexural strength of a continuous silicon carbide fiber (SiCr) fabric-reinforced SiC ceramic-matrix composite (CFCC) were studied. The failure mechanisms were correlated with flexural strengths of CFCC samples, both before and after oxidation. Microstructures and fractography were investigated using scanning electron microscopy (SEM). The chemical change after oxidation, such as Si, C, and 0, and their distributions, were detected by the SEM energy-dispersive X-ray spectroscopy (EDXS) line-scan chemical analysis technique. These effects on the strength of the CFCC can be attributed to following reasons: (i) The decrease in the flexural strength after oxidation is mainly due to degradation of the strength of Nicalon fibers and the damage of fiber/matrix interface both caused by high-temperature chemical reactions, (ii) Porosity is not too important in affecting the strength of the CFCC, when the bonding of the forced flow chemical vapor infiltration (FCVI)-SiC matrix is stronger than that of the fiber/matrix interface. However, a higher porosity content will be harmful, because higher porosity will both decrease the effective elastic modulus of the FCVI-SiC and make pore-linkage easier to occur, which is more likely to cause premature failure, (iii) The variation in the lamina stacking sequence of the CFCC changes the elastic stress distributions along the thickness direction of specimens, the magnitude of ceramic matrix-cracking stress, the effective elastic moduli of the laminate, and different crack initiation sites as well as different failure modes, and thus, leading to the scatter in the flexural strength of the CFCC.

Jan 1, 1998

By Kazuki Morita

Dissolution mechanism and solubility of chlorine in the oxide melts, such as CaO-SiO2-Al2O3 (-Na2O), Na2O-SiO2-Al2O3 and CaO-SiO2-FeO systems, have been equilibrium technique was employed with controlled Po2 and PCl2, (Po2 = 10-6 -10 19 atm, PCl2 10-6 -10-13 atm at 1673-1748 K). The solubility of chlorine in the 40mass%CaO-40mass%SiO2- 20mass%Al2O3, slag was found to vary in proportion to Pb2/ w and pc/z/p&apos; which proved that chlorine dissolved in the melts as C1 anion. Hence, the chloride capacity (CCI-), indicating the ability of molten oxide to absorb chlorine, has been defined as; The Ccl value was observed to increase with increasing slag basicity and temperature, and showed a reasonable relationship with that Of CS2-. Based on the result obtained in the present study, chlorine distribution during incineration with slags was predicted quantitatively.

Jan 1, 2003

By H. J. Thevik, A. K. Dahle

"A mathematical model that calculates the stress development in a coherent and stationary dendritic network due to interdendritic flow is proposed. The fluid flow is assumed to be related to the solidification shrinkage, and under the assumption of no porosity formation and unidirectional solidification, the shrinkage-induced flow within the mushy zone is calculated analytically. The interdendritic melt flow exerts a force on the solid network and an analytical expression for the stress build-up in the network is developed. Parameter studies illustrating the influence of cooling conditions, mushy zone length, dendrite coherency, fraction solid, volume fraction of eutectic, and solidification shrinkage upon the stress development within the solid network are presented. Comparing the magnitude of the calculated stresses to measurements of the strength in equiaxed mushy zones shows that it is possible for the stresses to exceed the strength, thereby resulting in reorientation or collapse of the dendritic network.IntroductionInterdendritic fluid flow is at present regarded as a very important mechanism for feeding of shrinkage during solidification of metal alloys. Solidification of many alloys is often characterised by heterogeneous nucleation of the primary phase on substrates in the melt with subsequent evolution of equiaxed dendrites. These equiaxed dendrites can initially grow freely, but impinge on each other and form a continuous dendritic network, ie. dendrite coherency, quite early in the solidification process. Measurements of the dendrite coherency point have shown that the dendritic network is established at solid fractions ranging between 0.1 and 0.5, and most often around about 0.2 [l]. Depending on the alloy composition this means that as much as 70 to 80% of the volumetric shrinkage has to be compensated by flow of liquid through the interdendritic network. Interdendritic flow occurs with a much larger resistance compared to free flow of the liquid and flow of a liquid with dispersed crystals. The pressure drop associated with the interdendritic flow increases rapidly with decreasing fraction ofliquid."

Jan 1, 1999

By Reza Rahimi, M. Nili Ahmadabadi

"Because of high cost and shortage of primary resources of Ni-base superalloys, revert alloys can be used as a part of charging materials for production of superalloys ingots. The current study is based on recycling of IN738LC, a Ni-base superalloy, using 30% and 50% reverted alloy and balanced amount of virgin raw materials. Therefore, it has been attempted to cast an alloy with references to standard chemical composition and mechanical properties. After charging and casting in vacuum melting furnaces, chemical composition verification and non-destructive tests (i.e. Penetration and Radiography Tests), quality of samples were evaluated at elevated temperature by stress-rupture test. Results acquired from chemical composition and mechanical test indicate that cast ingots using 30% and 50% reverted alloy is reliable and consistent with the quality control requirements.IntroductionIn recent years, there have been many fluctuations in cost and availability of raw materials which are extremely determining in Ni-base superalloys production. Accessibility to the high purity metals such as Cobalt, Molybdenum, Tantalum, Niobium and etc. have been problematical during the past decades. Therefore, shortages of critical raw materials beside the economical considerations motivated the alloy suppliers and investigators to study and find alternate sources such as reclamation and recycling of scraps [1].There are a lot of reasons for the necessity of recycling; perhaps the most justifiable one is that consumers themselves produce scraps. For example, the weight of a finished superalloy product could be less than one-third of the cast alloy weight and in the case of complicated machined parts; this portion may reach to one-tenth [2]. High values of constituents, reduction of energy consumption and environmental concerns have all strengthened the obligation of recycling in Ni-base superalloys.Because of the high degree of risk in usage of improper materials for production of turbine blades, a delicately controlled program for recycling is needed. Depending on the type of scraps, this program can define the recycling procedure, required instruments, allowable percentage of scrap for usage and finally confidence level of the process."

Jan 1, 2012

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction. The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory- scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the detennination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the detennined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors detennining the time of reduction.

Jan 1, 2003

By Stanko Nikolic

Ferrous calcium silicate slags are potentially important for future practice in copper converting operations and processes and can be described by the ?Cu2O?-FeO-Fe2O3-CaO-SiO2 system. Despite its industrial importance the phase equilibria in this system have not been fully investigated. Characterization of this slag system is necessary to improve the design and optimization parameters of new processes, including fluxing and operating temperatures. Experimental methods have been developed to investigate the phase equilibria of these slags at copper saturation and without copper. This technique involved equilibration of samples at a fixed oxygen partial pressure, rapid quenching, and analysis of the compositions of phases using electron probe x-ray microanalysis (EPMA). Liquidus and solidus data are reported for the primary phase fields of spinel, wollastonite and tridymite at 1250oC and an oxygen partial pressure of 10-6atm. The resulting data has been used to construct liquidus isotherms in the ?FeO?-CaO-SiO2 system both in equilibrium with and without molten copper. The experimental results were compared with the predictions of a thermodynamic computer package utilizing a self consistent thermodynamic database. The predictions of the model were in good agreement with the experimental isotherms when projected onto the FeO-CaO-SiO2 section, however the copper concentrations in the liquid phase at copper saturation were lower than predicted using the current database of the model.

Jan 1, 2006

By Tangstadm Merete, Eli Ringdalen

"This paper presents an overview of results from The Norwegian Research Institution SINTEF and the Norwegian University of Science and Technology, NTNU regarding new and ongoing research in silicon production. The main studies are related to condensation of SiO gas and cavity formation. If SiO gas condensation is increased at the top of the furnace resulting in SiO content in the off-gas closer to equilibrium, the Si yield will be increased significantly. Experimental work, simulating a cavity under industrial conditions, has shown that the cavity grows downwards from one layer. Physical appearance of zones in industrial furnaces, and selected reactions in these, are discussed based on results from excavation of industrial furnaces and results from laboratory experiments. Experimental studies of reaction rates for the formation of SiO are presented. Quartz properties are demonstrated to vary between differing quartz types and the effect of this is discussed.Introduction Both the theoretical and industrial issues associated with the production of silicon are described in detail in the textbook written by Schei et al [1]. This book covers the knowledge of silicon production process up to 1998. Together with the work by Myrhaug [1] and by Aasly[2], this is the main basis for this paper. Recent and ongoing research at SINTEF and NTNU focusing on production of Si and SiO in the high temperature zone, dissociation of SiO and condensate and cavity formation will be discussed."

Jan 1, 2012

By Guo Xueyi

The electrochemical couple behavior of manganese dioxide with ferrous/ferric ions in acidic chloride medium was investigated, It was proven that the dissolution of Mn01 is due to the electrochemical couple reaction between MnO2/Mn2+ and Fe2+/lFe3+ in the solution, The driving force for the process originates from the rest potential difference of the two couples. The reduction of Mn02 is controlled by clectrochemical kinetics, whereas the conversion of F e2+ to Fe3+ is limited by diffusion, The factors such as the Mn2+, Fe2+, Fe3+, Cl concentration, pH of the solution and the temperature, have much influence on the kinetics of the couple process, This study will be useful to elucidate the mechanism for the leaching of manganese nodule from the deep ocean as well as manganese dioxide ores in land,

Jan 1, 2003

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen temary system, which is of fundamental importance for discussing the recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, Sb015 and Sb203 in the PbO-SbOu and PbO-Sb203 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult&apos;s law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Laura Garcia H, Juan Carlos Gonzalez Islas, Luis Garcia Lechuga, Pedro Alberto Ramirez Ortega

"Electrochemical studies were performed to silver recovery from industrial wastes (radiographic films) on litanium flat electrode using a filter press-type electrochemical reactor with vertical orientation (known as REOV-01), as counter electrode was used a mesh-type DSA. Voltammetric studies were employed to fmd the current range under which silver reduction occurs. Using chronopotentiometric studies with controlled current, homogeneous deposits were obtained on the surface of the Ti electrode, to a current of -210 mA during 120 minutes to a constant linear flow velocity of 15 Lmin-1 was achieved 97% of silver recovery from industrial wastes. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy studies corroborated the presence of silver on Ti flat electrode. In addition, the silver concentration in the solution after the experiments was 1 ppm below environmental requirements. This indicates the viability of a filter press-type electrochemical reactor with vertical orientation (REOV-01) for silver recovery from radiographic filmsIntroductionIn recent years, the industrial sector has shown an increase in the use of silver due to new applications in different areas. In sectors such as photography, the consumption of silver has declined as a result of the boom in digital photography. However, the use of silver in radiographic applications has not shown greater variation (47.16 Moz), as the image quality is essential for diagnosis in various fields, such as medicine. All the silver used in photographic applications is discarded completely (solid or in effluent). At the present, several countries have been involved in silver recovering from industrial wastes due to the economic value and environmental impact they represent. The main source of silver recovery is the wastes generated by the photographic sector. Various technologies have attempted to recover silver contained in these wastes. However, they have not fully satisfied the requirements of maximum recovery, nor environmental level (less than 5 ppm) of silver in effluents [1,2]."

Jan 1, 2014

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction, The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory-scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the determination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the determined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors determining the time of reduction.

Jan 1, 2003