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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 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 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 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 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 Thomas Schuman, Jaan Kers, Lucas N. W. Damoah, Xiangjun Zuo, Lifeng Zhang

"Rapid technological innovation has propelled the use of electronic equipment leading to the generation of more and more waste electrical and electronic equipments (WEEE). Printed wiring board (PWB) is a component made of one or more layers of insulating material with electrical conductors. To investigate an environmentally friendly process to recycle PWBs, PWB samples with and without additives were pyrolyzed. Liquid, gas and solid products were achieved with different conversion fraction. Analysis of the exhaust gases from the experiments using GC-MS and MS showed that without CaCO3 additives poisonous gases such as C6H6 and HBr were produced which were adequately controlled if CaCO3 was added.IntroductionPyrolysis is one of the best methods for treating complex mixtures of waste polymers and to recover the material and energy content. The process consists of thermal decomposition at moderate temperatures in total absence or small amount of oxygen in which the structures of polymers break down into smaller intermediate products "". The decomposition temperature of a substance is the temperature at which the substance breaks up into smaller substances or into its constituent atoms 2). Thermal treatment of PWBs were reported using DC Arc Plasma furnace 3), and fixed bed reactor 4). One drawback in dealing with thermal treatment of PWB scraps is the likely production of super-toxic halogenated dibenzodioxins and dibenzofurans from the bromine containing structures. Pyrolysis of organic materials contained in waste PWBs leads to the formation of gases, oils, and chars which can be used as chemical feedstock or fuels ""'. Dehalogenation of the pyrolysis product of electronic scraps is essential to make it commercially acceptable. It would be obviously the most advantageous solution as pyrolysis and dehalogenation are carried out simultaneously. Reported pyrolysis investigations are at experimental stage and have been carried out in vacuum, molten salt, fluidized bed, rotary kiln, entrained, stationary, and moving bed reactors 7). Comparing to the incineration and combustion of PWBs, the pyrolysis process has several characteristics: 8'"">) 1). Converting the organic solid substance into fuel gas, fuel oil and carbon-black as storage energy; 2) Emitting toxic substances such as sulfur, bromine and heavy metals in wastes; and 3) Keeping metals from being oxidized. Although many researches into the pyrolysis of PWB wastes have been reported, most of the works have been carried out using analytical pyrolysis techniques or very small batch reactors ""~'5). Also, most of the works for the pyrolysis of PWBs haves concentrated on the composition of the organic products, particularly the brominated organics. The current study is to investigate the pyrolysis of PWB powders in a small TG-DTA scale and a 50-gram tube furnace scale."

Jan 1, 2011

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 Shilai Yuan, Huimin Lu, Zhijiang Gao, Panpan Wang

"Solvent refining of silicon through using Si-Al melts is a valid method to remove the impurities from metallurgical grade silicon (MG-Si) melt. The thermodynamic behavior of impurities Fe, Al, Ca, Ti, Cu, C, B and P in MG-Si during the solidification of MG-Si was studied based on the available thermodynamic parameters and experimental data. The morphology of inclusions was investigated by Scanning Electron Microscope (SEM). The chemical composition of inclusions in MG-Si and Al-Si melt was analyzed by EPMA. It is found that the amount of white inclusion reduces and most impurities are solved into the Al-Si melts. After solidification of Si–Al alloy using induction heating and acid leaching, impurities can be effectively removed. The solidification of silicon from the Si–Al melt is found to be more effective for purification than general silicon solidification.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. Multicrystalline silicon has now become the main material in the photovoltaic market because of its low production cost and because of the relative high conversion efficiency of solar cells made from this material, which has been studied for a long time [1-3].Electronic grade (EG) silicon (99.9999999% Si) is commonly used as the raw material to produce SOG-Si (99.9999% Si). Silicon produced from the chemical routes restricts the development of solar cells due to environment threaten, high energy consumption and low productivity. Purification of metallurgical grade silicon (MG-Si) is a low cost, environment friendly method. Although several metallurgical processes such as directional solidification, vacuum refining and electron beam melting [4], have been developed, the cost reduction and refining efficiencies for manufacturing silicon is still have to be further optimized.In the purification process, it is difficult to remove boron and phosphorus by the conventional metal refining method. The refining efficiency depends on the segregation behavior of different elements in solid silicon and the liquid phase. The segregation ratios of all investigated impurities were found to be much smaller than the segregation coefficients between solid and liquid Al-Si melts [5]. For instance, the segregation coefficient of B in Si is 0.8 at the silicon melting point (1687K), whereas it is around 0.2 when silicon is solidified from Si-Al melt at 1273K. For phosphorus the segregation coefficient is 0.06 when silicon is solidified from Si-Al melt at 973K°C, which is much less than 0.35 for recrystallization from liquid silicon. Since the segregation coefficient of boron in silicon is 0.8, it cannot be removed by directional solidification."

Jan 1, 2014

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 Björn Hinzel, Joachim Rösler

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

Jan 1, 2012

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

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

Jan 1, 1997

By 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 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 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 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