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By Masatsugu Morimitsu, Tian Zhang

"This paper presents a novel anode for oxygen evolution in acidic aqueous solutions to produce non-ferrous metals by electrowinning. The method to prepare the anode was thermal decomposition of a precursor solution, and the obtained anode consisted of Ru02-based oxide catalytic layers formed on a titanium substrate, in which the catalytic layer contains nano-oxide particles as the active component. The oxygen evolution potential was lower than amorphous lr02-Ta20s coated titanium anodes so that the cell voltage of electrowinning was further reduced with the amorphous Ru02-based electrode.IntroductionElectrowinning (EW) is used to produce high purity of non-ferrous metals, and the primary metal production of copper, zinc, nickel, and cobalt by EW consumes huge electric energy worldwide, which tends to increase with increasing demand of such metals. The reduction of electric energy consumption is a significant issue for electrowinning industry, which means that the cell voltage reduction is needed to realize more energy-efficient EW processes. Another issue is also indicated from environmental perspectives; i.e., an improvement in EW plant environment by eliminating hazardous byproducts and wastes. Such byproducts and wastes include lead oxide, manganese oxide, and acid mist.We have been developing the anodes for energy-efficient and environmentally friendly electrowinning processes [ 1-11]. The development has been successfully done with the invention of the smart anode, MSA TM (Morimitsu Smart Anode) [ 1-5], which has low polarization for the main reaction and high polarization for the side reaction, in which the main reaction is oxygen or chlorine evolution, while the side reaction is the anodic deposition of each or both of lead oxide, manganese oxide, and cobalt oxide. The anode consists of a valve metal substrate coated with amorphous or less crystalline oxide catalytic layers. One of the typical examples of such oxides is amorphous lr02-Ta20s, and the substrate is normally titanium plate or mesh. The most important point of the oxide is that the amorphization or less crystallinity induce the increase in the active surface area only to the main reaction, not to the side reaction, thereby the polarization of the main reaction being reduced.In this paper, we present the smart anode consisting of RuO2-based catalyst formed on titanium substrates for oxygen evolution in electrowinning. The preparation, characterization, and polarization behaviors of the anodes are shown, and the cell voltage data for zinc or copper electrowinning using the anodes are also presented."

Jan 1, 2012

By Jeffrey Shepherd, Scott R. Smith, Eduard Guerra

"Electrochemical and spectroscopic evidence for the dissolution of a Au electrode by meso-2,3- dimercaptosuccinic acid (DMSA) from an acidic LiCl04 electrolyte is presented. Near the potential of zero charge, DMSA was determined to form a stable layer on the metal surface but at more anodic polarizations, DMSA was displaced from the metal through an oxidative process. The anodic displacement of the layer from the electrode resulted in a small amount of Au that was detected in the electrolyte using atomic absorption analysis. The extent of Au dissolution, was monitored while holding the potential of the electrode for 24 hours at the thermodynamic Eo/H,O in LiCl04 electrolytes containing 10 mM DMSA. This routine resulted in detectable quantities of a soluble Au-DMSA complex in the electrolyte and the greatest leaching was observed at a pH = 2.0. At room temperature, the leaching rate was stable at 10.9 µg cm·2 hr·' however, upon increasing the temperature to 50.0°C, the rate of Au dissolution increased yielding an average rate of extraction of 40.1 µg cm·2 hr- 1. Interestingly, after the first 12 hours of leaching at 50.0°C, the leaching current decreased dramatically suggesting surface passivation which prevented further Au extraction. The implications of this process in the industrial leaching of Au will be discussed.IntroductionThe use of cyanide in the industrial process of leaching Au from ores has raised concerns regarding both operational safety and environmental issues surrounding the disposal of spent leaching eftluents in tailings ponds. Depending on the chemical nature of the processed ore, the spent solutions that are released into the tailings ponds can contain toxic cyanide, either dissolved or complexed with different metals and may pose serious risk to wildlife as well as freshwater contamination to nearby water systems. Because of these issues, some recent studies have focused on the exploration of more environmentally-friendly molecules to selectively leach Au with appropriate kinetics. However, to effectively leach Au into an aqueous solution, a suitable ligand that reacts to form a stable chemical bond with Au is needed to form soluble Au complexes that can be later recovered [I]. Recently several sulfur bearing alternatives have been shown to leach significant quantities of Au in aqueous solutions. These include thiourea [2], thiocyanate [3], and thiosulphate [4]. However, alkylthiols are also known to quickly form a stable covalent Au-S bond [5], but have been relatively understudied in term of their ability to leach Au in solution, even though some short chain thiols are water soluble and relatively nontoxic."

Jan 1, 2012

By Jie Li, Liangxing Jiang, Yexiang Liu, Junfeng Gui, Bo Hong, Xiaocong Zhong, Yanqing Lai, Xiaoying Yu

"Pb-based alloys with Pr and Ag were prepared in vacuum electromagnetic induction furnace. The tensile strength, corrosion rate and anodic potential in sulfate solution were measured, and the experimental data were analyzed according to the metallographic phases of alloys, the micromorphology and composition of their oxide films. The results show that, with the addition of Pr, the ultimate tensile strength and corrosion rate of pure lead were increased, and the anodic potential decreased. The extra addition of Ag can improve the properties of alloy further. Comparing with Pb-Ag0.8 alloy which is widely used in zinc electrowinning industry, the ultimate tensile strength of Pb-Ag0.6-Pr2.0 alloy was increased by 31.75%, the anodic potential under 50mA/cm2 was decreased by 30m V.IntroductionIn zinc electrowinning industry, the Pb-Ag (0.5-1.0 wt.%, 0.8wt.% normally) anode is widely used as an insoluble anode['l. It can meet the basic requirements, but still has several problems such as high oxygen evolution over-potential (about 860mV), unsatisfactory corrosion resistance, lead contamination of the cathode product and high consumption of Ag etc.In order to reduce the energy consumption, enhance the corrosion resistance, improve the product quality and reduce the consumption of Ag (or even dispense with it), much research has been done, mainly focusing on Pb-based alloy anodes and Ti-based coated anodes. Detailed investigations have already been carried out on binary alloys (Pb-Ca and Pb-Co), ternary alloys (Pb-Ag-Ca, Pb-Ag-Ti, Pb-Ag-Sn, Pb-Sr-Sn, and Pb-Ca-Sn) and quaternary alloys (Pb-Ca-Sr-Ag, Pb-Ca-Ce-Ag, and Pb-Ag-Sn-Co)[Z-4l, Although these anodes can effectively reduce the consumption of Ag, only the Pb-Co and Pb-Ag-Sn-Co anodes perform well with regard to reducing the anodic potential. However, their complicated manufacturing conditions restrict further commercial use.Besides its application in nonferrous metal electro-winning industry, Pb-based alloy is also used as grid alloy for lead-acid battery, serving as active materials supporter and current collector. In order to enhance the corrosion resistance and deep-cycling performance, reduce the impedance of the corrosion film, the addition of appropriate rare earth elements into anodic grid alloys has become a research focus. Studies proved that RE can enhance the mechanical strength of grids, inhibit the formation of anodic Pb(II) film on the surface of grids and then reduce the impedance of the film[ 10-12l."

Jan 1, 2013

By Gaifeng Xue, Lei Zhang, Xia Liu, Lina Wang, Pu Liu, Benquan Fu

"Experiments were conducted to investigate the behavior of the integrated process with a three-dimensional electrode reactor combined with Fenton process for coking wastewater treatment. Effects of initial pH value, reaction time, H20 2 dosage, Fe2+ dosage on Total organic carbon (f OC) removal rate were investigated. The kinetics of degradation of TOC from coking wastewater by three-dimensional fluid bed electrode reactor combined with Fenton process was also studied. Experimental results shows that three-dimensional fluid bed electrode reactor combined with Fenton process had better synergic effect, average 17.4% TOC removal rate was improved within an hour. It was found that TOC degradation in coking wastewater followed a pseudo-first-order reaction kinetic model. The optimum degradation efficiencies of TOC were up to 60% as pH3.4, 3.5 mM ofFe2+ andl.2-1.8ml/L H20 2 in 90min reaction period. Furthermore, the integrated process showed a rapid reaction performance at a low temperature within a short reaction time and remained high efficiencies for TOC removal. Overall, the integrated process was proved feasible for coking wastewater treatment in practical applications.IntroductionCoking wastewater is generated from coal coking, coal gas purification, and by-product recovery processes of coking, which is composed of phenolic compounds, heterocyclic compounds, polycyclic aromatic hydrocarbons, ammonia, cyanide, polycyclic nitrogen-containing aromatics, acyclic compounds, etc. Most of these constituents are refractory, poor biodegradability, toxic and carcinogenic['-31. Currently, coking wastewater is usually treated by different forms of A/O biological nitrogen removal process as the primary treatment process, but the aforementioned processes are not efficient enough to meet the requirements from the National Discharge Standard in China (GB13456-1992). According to the continuous requirement on improving environmental protection for coking industry (revised 2008), increasing wastewater utilization ratio and reducing discharge of effluent in the coke industry has to be implemented for cleaner production and sustainable development. Therefore, advanced technologies need to be developed to treat coking wastewater and reutilize the product as industrial cooling water, which would be one of the best choices to achieve zero discharge of wastewater and reduce water consumption per ton of steel [4-51 . In this study, three-dimensional fluidized bed electrode reactor combined with Fenton process was adopted to advanced treatment of coking wastewater, and the effects of operating conditions, including H2O 2 dosage, Fe2+ dosage, initial pH, and reaction time on TOC removal rate, were investigated. Meantime, study of kinetics of reaction was estimated."

Jan 1, 2013

By E. A. Chavarriaga, L. J. Jaramillo, O. J. Restrepo

"This paper presents the results of the manufacturing ceramic pigments with spinel structure, using methods of synthesis of low temperature. In this work we obtained spinel structures type by the methods of Self-combustion, Coprecipitation, Microemulsion, Gel citrate and Pechini. These methods become an attractive alternative to traditional method (ceramic method), since we can work at a lower temperature, reducing manufacturing costs, lower fuel consumption, less wear on equipment and other environmental and economic implications. Also it is possible to have control over features such as stoichiometry, morphology of the products, reaction times and structures. The products obtained by these routes will be used in the manufacture of ceramic pigments and characterized using different techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-VIS spectrophotometry.IntroductionSpinels are ternary oxides AB204, where A and B are cations occupying tetrahedral and octahedral positions respectively. These oxides exhibit interesting electrical, magnetic and catalytic properties [1-4], depending on its nature, charging and intrinsic distribution of ions [5].The most widely used method to prepare spinels has been through solid state reaction, which consists of mixed oxides at high temperatures [6, 7]. In the last years, there have been a strong tendency to use chemical routes for the synthesis of crystalline ceramic particles at low temperatures [8,9]. Unconventional methods currently employed for the synthesis of complex oxides are Gel citrate method, Pechini, Spontaneous combustion, Microemulsion and Coprecipitation. Pechini method [10, 11], based on polymeric precursors, does not require high temperatures and allows stoichiometric control for greater reproducibility. This method involves the formation of a polymeric resin between a metal quelate and polyhydroxy acid of alcohol by polyestirification.Coprecipitation is important for many environmental problems related to water resources, including acid mine drainage, migration of radionuclides in waste repositories dirty, transport of contaminant metals in the industry, metal concentrations in aqueous systems and the technology of wastewater treatment. The coprecipitation process can vary in each case; the partition in the solid phase can be carried out by surface adsorption, ion exchange, surface precipitation, occlusion and formation of solid solution. The formation of solid solution is the result of structural incorporation of the marker in structural support sites resulting in a minor component in the solid solution with the host phase that has a very low solubility of pure solid [12]. Synthesis by gel citrate method allows the use of a route to obtain ceramic pigments from a very simple experimental system in which the stoichiometric control, the size and shape of the particles and the purity of the phases obtained can be controlled more accurately [13]."

Jan 1, 2012

By Xuewei Lv, Maojun Zhou, Xiaobo Huang, Rende Zhang

"The characterization of the surface roughness of the mineral particles is of vital importance for the studies of the mineral processing. In this study, an evaluation of the roughness of the iron ore particles, with the measurements of size distribution and the measurements of specific surface area with the liquid nitrogen absorption, was developed. The main theory of this method is the fact that the roughness of the particle influences the specific surface area apparently. The specific surface area of the particles can be measured with the laser diffraction method and the liquid nitrogen absorption method. The influence of the surface roughness of the particle can be measured with the nitrogen absorption and cannot be measured with the laser diffraction. Therefore, the roughness can be got by comparing the specific surface area with two measurement methods.IntroductionThe characterization of the surface roughness of the mineral particles is of vital importance for the studies of the mineral processing. There are three main methods for measuring the size distribution of mineral particles: sieving, laser diffraction, and sedimentationl). Many techniques involve sedimentation such as the Horiba2, 3) and the Cyclo-sizer1). In the mineral industry, size distribution is usually determined by sieving because it can be carried out accurately for all particle sizes larger than 45 . The preferred method to obtain the size distribution of finer particles is laser diffractometry. The technique has several advantages: it produces measurements in a few minutes with considerably less labor compared with the cyclo-sizer and for a range of sizes considerably wider in comparison with the sedigraph4). The equivalent-sphere size distribution reported by laser diffractometry is valid for metallurgical calculations and can be routinely used in mineral processing plants. The surface area of the particles can be measured by the BET method of nitrogen adsorption, or it can be calculated from the size distribution. However, the latter calculation requires the size distribution to be accurately known across the whole size range, and assumptions have to be made about the shapes and surface roughness of the particles and presence or absence of pores (see below). The BET method is based on the physical adsorption of gas over the whole exposed surface area and measures the surface area stemming from the roughness and open pores on the surface of the particle5). The calculation of the surface area from the size distribution is usually based on the assumption that all the particles are smooth spheres, without considering the shape and/or roughness of the particles. Determining the surface roughness of the particle with these methods, is the objective of this study."

Jan 1, 2012

By M. Okido, R. Ichino, K. Kuroda

"Compound semiconductor, ZnTe, was electrodeposited in an acidic solution with K2TeO3, ZnSO4 and Na2SO4 solution. Since the reduction potential Te(IV)/Te(O) is remarkably noble from the solution comparing to Zn(II)/Zn(O), code position of Te and Zn was thought to be difficult from this solution. Resulting from EQCM analysis, furthermore, Te(IV) reduced to Te(O) and Te(-II) in this order so that Te catholically dissolved from the electrode surface at more negative potential. But ZnTe alloy were formed by the UPD of Zn at -0.7V at 298K on Te surface in lmM K2TeO3, 100mM ZnSO4 and 100mM Na2SO4 solution adjusted at pH 4. Content of Te in the deposits is, however, more than 80%.Electrolytic temperature is well known to affect on the deposits characteristics. The higher bath temperature was, the better ZnTe crystal was detected in this study. Thermal electrode method is a. process of heating only substrate by flowing ac current in substrate. This process makes the surface temperature of substrate higher than boiling point of the solution, 373K. From EDX analysis, deposits without thermal current were Te-rich, Te content in the deposits with thermal current decreased with increasing of thermal current. Te content was 62% for 5A ac current, 51 % for I OA and 45% for 20A, respectively. The deposits that produced with ac current of IOA were closed to the stoichiometric ratio, i.e. ZnTe.Consequently, thermal electrode method is more effective to obtain a good crystallized ZnTe without heat treatment after deposition.IntroductionThe current subject of solar cell materials is silicon. Compound semiconductors including GaAs and II-VI group are generally used in the developing field of digital information such as the rapid cellular phone and car telephone. Compound semiconductors consist of more than 2 kinds of element. There are many materials for these compound semiconductors such a SiC, InSb, CdS for binary system and CuinSe2 for ternary system. It becomes generally difficult, to produce high quality crystal with increasing of kinds of element due to a complicated structure and a compound ratio of element. Semiconductor materials as a device are usually simple binary compounds and/or these mixed crystals. Properties of compound semiconductors have variety of the forbidden band and lattice constant and that can be change easily by addition of another element for the usage of the solar cell. Since most compound semiconductors are direct interband transition type, which has steep optics absorption edge and large light absorption coefficient."

Jan 1, 2000

By William Brinkman, Mark Jolly, Nasim Soleimanian, Karl Dearn, Oliver Brinkman

"Glass manufacturing is a heat intensive process. There is a direct correlation between the batch distribution techniques and the furnace energy consumption, productivity, and quality of the glass manufactured. All four major segments (float, container, fibre, and specialty glasses) would benefit from using an optimised batch distribution technique where possible. Oscillating batch chargers (OBC) have been in use since the early 70s, despite their superior batch shape, coverage, and in turn positive effects on the energy consumption and productivity of the furnace they are almost exclusively used in container glass manufacturing. The OBC’s main difference compared with other charging methods is its ability to directly influence the batch initial velocity. This paper reports on results achieved in CFD models (GFM) used to study effect of the machine on the overall energy consumption in the doghouse and the melt space.IntroductionGlass manufacturing can be divided to four major segments float glass, container glass, fiberglass, and specialty glasses. The financial cost of manufacture, its impact on the environment, lack of standardisation and mounting pressure imposed by the authorities for reduction in emissions means that the industry and its suppliers are utilising CFD modelling in order to tackle these challenges. The need for high temperature to create and maintain the viscous flow, homogenisation of the glass melt, and maintenance of the process to allow continuous output of glass of the right quality are the contributors to the energy intensive activities that are involved in continuous glass manufacturing. This in turn has resulted in design of large container glass furnaces which have high energy consumption, low specific performance, and high CO2 emissions where the most efficient furnaces in the container glass sector have a specific primary energy consumption of 3.8 GJ /tonne of glass at a level of 50% cullet in the batch making even very small improvements in efficiency by operation optimisation a value adding activity [1-14].The theoretical calculated energy required to melt glass is 2 to 3 times less than the energy actually used to melt glass as a result of glass melt passing a zone 5 to 8 times before leaving the tank.[8]. This causes contamination as the result of mixing between the completely molten glass free from bubbles returning to the batch area where there is freshly molten non-homogeneous glass, still containing very large numbers of bubbles and un-molten batch. At high temperature some components are dissolved rather than melted. Given that an un-molten batch is a good thermal insulator, it can be transported a long way into the furnace, increasing the need for homogenization which also increases the glass residence time of glass melt. This is why large unbroken strings of batch should be avoided, as should an overall blanket without gaps."

Jan 1, 2014

By Xiaohui Li, Lianyun Liu, Hongmin Zhu, Chunfang Zi, Kai Huang, Hongjie Li

"The dissolution kinetics of steelmaking slag in pure water was studied, and the relative influential factors were investigated. The dissolution behavior of slag particles in water was well described by Noyes–Whitney equation, and for this kind of sparingly soluble rigid mineral this simple model was extensively applicable to describe their dissolution process. Experimental data were also obtained to confirm the significant promotion effect on the growth of some algae.1 . IntroductionIt has been found that the population of phytoplankton distributed in the ocean was significantly related to the concentration of some elements [1]. For example, silicon and iron were very low in the high-nitrate low-chlorophyll (HNLC) areas, which was the main factor limiting phytoplankton and other biomass growth in these open ocean surface water [7]. The silicon and iron-rich test also confirmed that the supply of these elements had the direct effect on the growth of phytoplankton processes at HNLC areas [2-8]. So in order to promote the growth of phytoplankton in these ocean areas, providing some of these elements into these ocean areas is a natural idea for choice. Steelmaking slag is a good resource for consideration because it usually contains silicon, iron, phosphorus and other elements that are necessary for the growth of phytoplankton [8-10].Haraguchi has proposed the following idea that [5-6], if steelmaking slag can be spread to the open ocean, the trace components like silicate, iron and phosphate as the indispensable nutrients for the growth of phytoplankton, will be leached into the sea water, not only promoting the growth of phytoplankton, but also making good use of these huge amount of steelmaking slag produced every year. Based on this idea, they have carried out studies in recent years and they found that silicon and iron in the slag could be extracted into seawater effectively and play a positive role in the growth process of many algae. About the dissolution of the steelmaking slag, the Japanese scholars' research work mainly focused on the thermodynamic analysis of its dissolution possibility, and in the process of dissolution they tried to adjust the pH value of the seawater by continuously adding hydrochloric acid, which was deviated from the natural conditions of dissolution, and so the laws drawn under these special conditions can not give the identical guide to the practical application. Therefore, it is quite necessary to investigate the dissolution behavior of the steelmaking slag in the seawater at the normal pH range without adjustment to simulate the dissolution possibility under the natural conditions. In the present study, the silicon extraction behavior from the steelmaking slag was investigated and the dissolution kinetics in this process was also discussed in detail. Further studies were also performed here to evaluate the promotion of steelmaking slag on the growth of algae."

Jan 1, 2011

By Y. Moriya, Y. Sadayoshi, Y. Nonogaki, Y. Takeda

"Preparation and growth processes of CaF2 on Si(111) and of . InxGa1-x,As islands on CaF2 by molecular beam epitaxy (MBE) are described. It was found that first of all the Si(111) surface treatment process to obtain the 7x7 reconstructed structure was necessary to ensure the cleanness of the surface and to grow a flat and high quality CaF2 on it. Growth of InxGa11-x,As islands on CaF2 was tried by droplet heteroepitaxy using the same MBE reactor. In,GaxGa1-xAs islands were successfully grown epitaxially, and the size and density of the islands dependent on the In composition were investigated.IntroductionThough semiconductor/semiconductor heterostructures are widely used for many device applications, small band off-sets of the conduction bands and the valence bands restrict the utilization of the intra-subband transitions to far-infrared regions. With InAs as the quantum well and fluorides as the barrier layers, we can design three-electronic-level systems in the infrared region, which is the low loss transmission window of the silica optical fibers. To realize those structures, we have grown InxGa1-xAs islands on CaF2 thin films that were epitaxially formed on Si(111) substrates by molecular beam epitaxy. By the droplet heteroepitaxy that we invented, the InxGa1-xAs islands with height of -10 nm have been obtained successfully. Optimum processing to obtain atomically smooth surfaces of Si and CaF2 and high quality InxGa1-xAs islands is reported.ExperimentsMBEMachineCaF2 was grown on Si(111) and InxGa1-xAs islands were grown on CaF2 successively by MBE. The MBE machine consisted of a growth (or reactor) chamber and a loading chamber. The reactor chamber was equipped with Ga, In, As and Er metal source cells and CaF2 and BaF2 source cells. Cell materials were P-BN for Ga, In and As metals, and were graphite for CaF 2, BaF 2 and Er to avoid reaction with BN cells. The electron gun and screen were attached to the reactor to observe the RHEED pattern during the substrate surface treatment and the growth of CaF2 and InxGa1-xAs islands. The substrate manipulator was designed to heat up the Si substrate up to 1,200°C for the surface cleaning. The QMS was also equipped to analyze the residual gas species in the reactor chamber. The base pressure of the reactor chamber was 2-5x10-11 Torr, being pumped by ion pump and the liquid nitrogen shroud"

Jan 1, 2000

By Nagahiro Saito, Takashi Nishimura, Takamichi Ichikawa, Akio Fuwa

"Yttria-stabilized zircohia (YSZ) has high potential to be used as solid-oxide fuel cell (SOFC) electrolyte. However, the high efficiency of SOFC has not been yet achieved due to the high internal resistance of bulk electrolyte. The resistance becomes lower with the decrease in the electrolyte thickness. Thus, the decrease in electrolyte thickness leads to lower internal resistance. . The aim of this study is as follows: (a) to prepare the thin films of YSZ by inductively-coupled RF plasma-enhanced metal organic chemical vapor deposition (PEMOCVD) process using Zr(t-OC4H9)4,Y(DPMh and oxygeil, and (b) to reveal the relationship between the structural characterizations and the process parameters.1. IntroductionYttia-stabilized zirconia (YSZ) has, been widely used as not only heat-resistant materials but also the components in automotive oxygen sensors, electrolytes of solid-oxide fuel cell (SOFC)(1)(2) and the buffer layers for the high-temperature superconductor because of its low thermal conductivity, good mechanical properties and high ionic conductivity. However, it is said that the internal resistance of the bulk electrolyte is too high to be appropriate as a solid electrolyte for high-efficient SOFC. The authors believe that the thin YSZ electrolyte can give a high performance to characteristics SOFC, since the internal resistance becomes lower with the decrease of electrolyte thickness. Thus the process technology to prepare YSZ thin films is desirable and must be established.In recent years, the YSZ thin films have been reported by chemical vapor deposition (CVD), thermal CVD using metal chlorides (MC) of ZrCl4 and YC(3)(4), thermal CVD using metal organic compounds (MO)(5)(10) Zr(t-OC4H9)4 and Y(C11H19O2)(11) and plasma-enhanced (PE) CVD using MO. Here, these methods are called MCCVD, MOCVD and PEMOCVD. MCCVD has two disadvantages; a large quantity of chlorinated impurities in deposited films and high processing temperature (> 1273K). This high processing temperature leads to damage of substrates in particular, so the application of this technology is limited. On the other hands, the processing temperature by MOCVD becomes and is lower. Unfortunately, the accurate vapor pressures of these metal organic compounds have not been, known so: that it is difficult to control the composition and the film thickness by MOCVD method well. Moreover, the large amount of carbonic compounds in the films prepared by MOCVD method is produced. However, plasma-effect has been reported to decrease large amount of the carbonic impurities by PEMOCVD. However, PEMOCVD has many reaction parameters in plasma processing; the geometry of experimental apparatus, radio frequency, electronic power input and so on. Thus, the general understanding about the relationship among reaction parameters, the composition and crystal structure of thin deposit film by this method has not yet been established."

Jan 1, 2000

By P. K. Jimack, C. E. Goodyer, A. M. Mullis, P. C. Bollada

"We review the application of advanced numerical techniques such as adaptive mesh refmement, implicit time-stepping, multigrid solvers and massively parallel implementations as a route to obtaining solutions to the 3-dimensional phase-field problem with a domain size and interface resolution previously possible only in 2-dimensions. Using such techniques it is shown that such models are tractable even as the interface width approaches the solute capillary length.IntroductionMulti-scale modelling impinges upon many areas of science, engineering and technology where the interplay between processes occurring on disparate length and/or timescales can affect the properties of systems in a complex, and sometimes unforeseen, manner. One such is the processing of materials where interactions at the atomic scale, through the nano- and microstructural scale can have a profound affect on the macro-scale response of engineering components. Here we focus on one such problem, the crystallisation of alloy melts, to illustrate how a range of advanced numerical techniques make the modelling of such systems tractable.The modelling of solidification structures, in particular the growth of dendritic crystals, is a subject of intense and enduring interest within the scientific community, both because dendrites are a prime example of spontaneous pattern formation and they have a pervasive influence on the engineering properties of metals. For alloy systems, which form the vast majority of engineering materials, solidification involves the rejection of both solute and latent heat from the growing solid, forming a coupled diffusion problem in which both the chemical and thermal diffusion equations should be solved. The multi-scale nature of this problem arises from the disparity between the thermal and solutal diffusivities for most liquid metals, which are typically 10-5 m2 s-1 and 10-9 m2 s-1 respectively. The ratio of these two, referred to as the Lewis number (Le =Dia), is therefore typically of the order 10,000 and gives a measure of the multi-scale nature of the problem. In fact, in many cases the thermal diffusivity is so much larger than its solutal counterpart that thermal diffusion is considered instantaneous, wherein the system can be approximated as isothermal such that the multi-scale calculation does not need to be performed. This is certainly a reasonable approach in most conventional castings. However, there is a class of solidification problem in which this approach is far from satisfactory, namely Rapid Solidification (RS). The application of isothermal phase-field models in such situations are highly likely to produce spurious results or to fail totally, particularly for temperatures below To (the temperature at which the free energies of the solid and liquid phases are equal at the concentration of the bulk alloy), wherein partitionless solidification may occur."

Jan 1, 2013

By Shulan Wang, Xuan Liu, Li Li

"Electrochemistry of Fe(III) in 69CaCl2-12CaF2-19KF and 81CaCl2-19KF (mole percentage, %) was investigated at 827 oC on molybdenum electrode by cyclic voltammetry, chronoamperometry and galvanostatic electrolysis using Fe2O3 as the Fe(III) source. The reduction of Fe(III) to Fe was conducted in one step and controlled by diffusion process. Fe(III) shown greater reduction rate and diffusion coefficient in molten 81CaCl2-19KF than in 69CaCl2- 12CaF2-19KF. Galvanostic electrolysis of Fe was performed in both molten salts with a cylindrical cathode rotating at 200 r/min and dendritic iron deposit was obtained.Keywords: iron; electrolysis; electrochemistry; molten saltIntroductionThe production of iron and steel causes huge emissions of CO2. Iron electrowinning in molten salts with dissolved Fe2O3 using an inert oxygen evolving anode is an alternative process to reduce or eliminate the formation of CO2. Research on novel process of producing metal has been reported recently [1-2] by using CaCl2 as the main electrolyte and dissolving CaO in CaCl2 due to the high solubility of CaO in the melt. This process has been used in preparing many active metals and alloys [3-14]. In the present work, the electrochemical behavior of iron in CaCl2-KF was studied and transport property of iron ion in the melt was discussed.ExperimentalCaCl2,CaF2 and KF (in analytical purity) were dried in air for 48 h. Mixed salts used in experiments were placed in a graphite crucible (??58 mm inner diameter). The graphite crucible together with the salts was heated at 473 K for 12 h in a furnace with flowing Ar (99.99%) before further heating. Temperature inside the furnace was measured by an S type thermocouple. Electrochemical measurements, such as cyclic voltammetry and chronocoulometry, were performed in a three electrode cell by EG&G PAR273A potentiostat/galvanostatand. Galvanostatic electrodepositon of iron was conducted in a two electrode cell. Molybdenum (??2 mm) and iron (??5 mm) were used as the working electrode (WE) and the reference electrode, respectively. A graphite crucible and a magnetite rod (??25 mm ) consisted of 100% magnetite and sintered at 950 oC in argon atmosphere for 2 h with electrical conductivity of 366 O-1m-1 at room temperature were used as the counter electrodes in the galvanostatic electrolysis experiment. Carbon (??10 mm) was used as the counter electrode in electrochemical measurement. The deposits were washed in distilled water bubbled with argon and dried in air before being characterized by X-ray diffraction (PW3040/60 diffractometer) and scanning electron microscope (SEM, SSX-550)."

Jan 1, 2014

By Gerald Onyedika, Tochi Onwumere, Martin Ogwuegbu

"The kinetic study for the leaching of iron from cassiterite ore in KOH solution was studied. The effects of KOH concentration, particle size and reaction temperature on the leaching rate of iron were also examined. The results of leaching studies showed that the leaching of iron from cassiterite ore in KOH solution is significantly influenced by the reaction temperature, KOH concentration, and decrease in particle size. The study showed that 90.62% of iron ore was leached in 8M KOH solution at 80°C within 120 minutes. The experimental data were well evaluated using the shrinking model for surface chemical reaction and diffusion control through the product layer. The activation energies for the iron ore dissolution using the two models were calculated to be 32.06KJmor1 and 97.97 KJmor' respectively.IntroductionIn recent times, there has been increasing attention on the kinetic study of mineral dissolution. In most of these studies, the experimental results were analyzed with a suitable shrinking core model under the assumption that the ore is a homogeneous spherical solid phase [1-4]. A study of the dissolution kinetics of a Nigerian cassiterite ore by hydrochloric acid showed that increase in the hydrochloric acid concentration is accompanied with increase in the amount of cassiterite ore dissolved at various times [4]. The optimal concentration was found to be 4.0M HCl, after which there was a decline in the amount of the ore dissolved, which showed that the concentration of the reagent has a significant effect on the leaching rate of the ore. Also in studying the effect of stirring speed on the rate of cassiterite ore dissolution while keeping other conditions constant for 120 minutes, the result showed that the rate of cassiterite ore dissolution was dependent on the stirring speed over a range of 0 to 630 rpm. Above 360 rpm, the stirring speed no longer had any effect on the solid dissolution. The dissolution rates of cassiterite were analyzed using a suitable shrinking model. The results showed that the reaction was controlled by the diffusion of tin through the porous product layer, a reaction order with respect to hydrogen ion concentration of 0.92 M and activation energy of 50.05KJmor'. In another kinetic study on the leaching of a low grade niobium-tantalum ore with concentrated KOH solution the effect ofreaction temperature, KOH concentration, agitation speed, particle size and alkali-to-ore mass ratio on the dissolution rate of niobium were examined [5]. The result of niobium leaching from low grade niobium-tantalum ore with concentrated KOH, solution at different agitation speeds showed that the dissolution rate increased with increase in agitation rate. In the case of particle size effect, the results show that small particles require much shorter time for complete dissolution than the large ones."

Jan 1, 2013

By Chikabumi Yamauchi, Mitsuru Tanahashi, Tsuyoshi Taniguchi, Nobuo Furuta, Toshiharu Fujisawa

"It is essential to clarify the equilibrium relations among nonmetallic inclusions of the Mn0-SiO2-CrOx system and molten stainless steel in order to control non-metallic inclusions formed by the deoxidation of stainless steel with silicon. In the present study, the phase equilibria of the MnO-SiO2-CrOx system were measured by conducting the following experiments under controlled oxygen partial pressure, Po2, at 1873 K:1) Phase equilibria of the MnO-Cr20 3 binary system were measured for Po2 = 2 x 10-6 ~2 x 102 Pa.2) Phase equilibria of the MnO-SiO2-CrOx ternary system were measured for Po2 = 2 X 10-6 Pa.Based on the results, the phase diagram of this ternary system was established under the condition of the Si-deoxidation process of stainless steel (Po2 = 2 x 10-6 Pa and T = 1873 K).IntroductionAt the deoxidation stage in steelmaking process, generally multiple deoxidizers participate in deoxidation reactions, and the composition of deoxidation products ""non-metallic inclusions"" greatly varies depending on deoxidizing efoments and their contents. In order to control non-metallic inclusions formed by the refining process of steel, it is essential to clarify the equilibrium relations among non-metallic inclusions and molten steel.Especially, during the refining process of stainless steel, nonmetallic inclusions in molten steel seem to- change as follows. After the oxidation refining, Mn-chromite is formed in molten steel as non-metallic inclusion. By the deoxidation with silicon addition (mainly less than 1 mass%), Mn-chromite inclusions are changed their compositions to Mn-silicate. Segawa et al.[l] have reported the effect of amount of silicon addition on composition and mass ratio· of non-metallic inclusions during the Sideoxidation process of 18Cr-8Ni stainless steel at 1873 K, as shown in Figuri; L At higher silicon content than 0.5 mass%, only Mn-silicate was identified as non-metallic inclusion. On the other hand, at lower silicon content, both of Mn-chromite (MnO Cr2O 3) and Mn-silicate were identified. However, the thermodynamic and the kinetic analyses of the above-mentioned Sicdeoxidation process have not been made due to lack in the thermodynamic data for the non-metallic inclusions· of the MnO-SiO2-CrOx system, such as the phase diagrams, the activities of the components, and the free energy of intermediate compounds. In relation to the phase diagram of this system, those of the MnO-SiO2 [2] and the SiO2-Cr2O 3 [3] binary systems have been only reported"

Jan 1, 2000

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 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