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By Kouji Mimura, Tamas Kekesi, Yongfu Zhu, Masahito Uchikoshi, Minoru Isshiki

"The formation and anion exchange sorption of chloro complex ions can offer a great potential to be utilized for the separation and purification of metals in aqueous solutions. Available stability data were primarily used to estimate the predominance of chloro complex species, indicating the feasibility of such separations. Anion-exchange sorption functions, describing the equilibrium distribution of a number of important elements have been determined by the batch equilibrating method in the practical HC1 concentration range. Various oxidation states were stabilized by the addition of appropriate agents. Tendencies in oxidation, complex formation and anion exchange sorption were confirmed by spectrophotometric investigations. Based on the fundamental results, anion exchange processes have been developed for the purification of iron, cobalt, copper and zinc. The efficiency of separation was assessed and the procedure optimized by the analysis of experimental elution curves. Results have demonstrated that by properly controlling the oxidation states and HC1 concentrations, practically all the impurities can be eliminated. Computer programs have been developed to estimate complex formation and redox equilibria, to screen and correct analytical data, to determine distribution coefficients and to evaluate efficiencies of separation.IntroductionBase transition metals have long been used as the staple materials in various fields of industry. In general, there has been an increasing tendency in purity requirements but recent advances have created a rapidly increasing demand for ultra-high purity metals. To give a few examples, ultra high purity copper can be used as bonding wire and interconnection in integrated circuits, or as material for superconductor stabilizing, high-field magnets, beside its use in cryogenics and ultra high vacuum technology [1]. Iron holds promises as a constituent element in the ß-FeSi2 material to be applied in new opto-electronic devices [2] and it is currently used, together with chromium and manganese, in the production of special magneto-optical materials for digital recording. The use of ultra high purity manganese and chromium in semiconductor technology is evolving. Although not considered a transition metal, zinc is also treated here because of the major significance in compound ZnSe semiconductors [3], and the possibility to purify it by the anion exchange method."

Jan 1, 2000

By I. Gaballah

Spent hydrorefining catalysts may contain 4 to 6 % of COO and/or NiO, 8 to 16 % of Moo3 and up to 10 % V205 generally supported by alumina. Raw samples are roasted in order to eliminate carbon, sulfur and hydrocarbons contained in the spent catalysts. The roasting optimum temperature and time are 500 "C and 7 hours. Selective chlorination of roasted samples with Cl2 + air, Cl2 + N2 and Cl2 + CO is investigated in order to recover the valuable metals. Depending on the chlorination it is possible to recover more than 80 % of the Ni and Co about 95 % of the Mo and up to 80 % of vanadium compounds. Cobalt and nickel chlorides are obtained by leaching the chlorination residues' by acidified water. Molybdenum and vanadium chlorides and/or oxychlorides are obtained by selective condensation from the vapor phase. The chlorination of the catalyst support, Al2O3, can be limited to less than about 5 %. Besides the reaction temperature and time, the oxygen partial pressure of the chlorinating gas mixture appears to be the key factor for the reactions' selectivity.

Jan 1, 1993

By P. Maraboutis

Iron removal by precipitation as jarosite from Fe-Ni-Co sulfate solutions, (synthetic or real, resulting from laterites leaching) has been investigated. Precipitation was carried out at 95 C, and at an initial pH 1.6, which was either kept constant with CaCO3 or Li2CO3 additions, or left to drift with the evolution of the reaction to lower values. The precipitation of K-, NH4- and Na- jarosite was initially examined using synthetic solutions. In all cases, hydronium ions were incorporated into the precipitate as well. Residual iron in solution was lower (0.2-1 g/1) and equilibrium was achieved faster (within 4-8 h) when precipitating K¬jarosite at constant pH, using CaCO3 for neutralization. Nickel and cobalt losses were small. Na- jarosite precipitation was also studied from real solutions with high initial iron content, under constant pH=1.5, controlled with CaCO3 additions, and it was shown that low residual iron concentration in solution (0.3-0.5 g/1) can be achieved again, with relatively small nickel and cobalt losses. The thickening and filtration characteristics of the precipitates were excellent in all cases examined.

Jan 1, 1988

By H. Senoh

For the purpose of clarifying the reason caused a drastic decrease of discharge capacity for MmNi3.6Mn0.4Al0.3Co0.7 electrode at relatively low temperatures, various factors influencing the charge-discharge processes were investigated in the temperature range of 25°C to -40°C. The charge efficiency obviously decreased at low temperatures less than 0°C due to a decrease in the rate of the charge-transfer reaction on the electrode surface. Moreover, both the rate of the hydrogen diffusion from the alloy bulk to surface and the rate of the charge-transfer reaction significantly influenced the high-rate dischargeability. The addition of Mo to MmNi3.6Mn0.4Al0.3Co0.7 alloy was found to be effective for improving the electrocatalytic activity, leading to the improvements of the charge efficiency and the high-rate dischargeability at relatively low temperatures.

Jan 1, 2002

By Y. Iguchi, T. Narushima, T. Shiozawa, M. Maruyama, R. Arashi

"In situ observation system for thermal oxidation using Raman spectroscopy' was constructed, and oxide films formed on liquid pure Al and Al-Mg alloys (Mg contents = 1 and 4 mass%) were analyzed at room temperature to 1273 K in dry oxygen. In situ Raman spectra of the surface of a liquid Al-:-4mass%Mg indicated the formation of MgO • AlP3 (spinel) as oxidation products, while a -AlP3 and MgO • Alz03 (spinel) were observed on a liquid Al-1mass%Mg alloy. It was suggested that the formation of MgO film affected oxidation behavior of these alloys.IntroductionLiquid aluminum alloys are cast to ingots mainly by the continuous casting process. It is well-.known that surface cracks could be caused by oxide films formed on the surface of melt during continuous casting and defects due to the film. With regard to oxidation behavior of liquid aluminum alloys, many investigations l -s have been carried out from the view point of formation of ceramic metal composites(CMC) which are expected as cutting tools and structural materials 1.2. It is very important for reasonable continuous casting and CMC formation processes to elucidate oxidation behavior of melts.Oxidation behavior of materials generally depends on compositions and properties of oxide films formed on the surface. If in situ observations of oxide films are available during oxidation, evaluation of oxide films and interpretation of oxidation mechanism could be expected. Laser Raman spectroscopy is one of the most appropriate techniques for in situ observation of oxide films under various atmosphere at high temperatures. The authors have discussed the effects of atmospheres and sample compositions on oxide film formation mechanism on Fe-Si alloy6 and SiC-B4C composite7 on basis of an in situ observation by Raman spectroscopy. In spite of many previous studies, systematic and clear explanations have never been gotten on oxidation behavior of liquid aluminum alloys. And no in situ observation has been made except for transmission electron microscopy(TEM) and X-ray diffraction(XRD)."

Jan 1, 1996

By Jayagopal Uchil, M. Krishna, Shanta Sastcy

"Damping behaviour of aluminite particulate reinforced ZA-27 alloy metal matrix composites processed by compocasting method is studied. The weight percentage of particulate reinforcement is 0,1,2,3, and 4%. A dynamic mechanical· analyzer is used ·to measure the damping capacity and dynamic modulus at the natural frequency of the specimen over a temperature range of 30°C to 300 °C both in the heating and cooling cycle. The damping capacity of the material is found to increase with increase in temperature and weight percentage of aluminite reinforcement although this is accompanied by a decrease in dyliamic modulus.The damping capacity and dynamic young's modulus exhibit a sharp decrease in their values around 300 °C a8 ZA-27 alloy undergoes a first order phase transition in this region which is confirmed by Differential scanning calorimetric studies. Several damping mechanisms have been evaluated theoretically for the material under study. The damping capacity at low temperatures is attributed primarily to coefficient of thermal expansion mismatch induced dislocations and high intrinsic damping of the matrix. At higher temperatures the damping capacity is attributed to ZA-27/aluminite interface, phase transformations and thermoelastic damping.IntroductionMetal matrix composites. (MMCs) offer designers many added benefits, as they are particularly suited for applications requiring good strength at high temperature, good structural rigidity, dimensional stability, and lightweight [1-5]. At present, the usage of ceramic particles as reinforcement in MMCs has attracted considerable interest from scientists and engineers. The MMCs show substantially improved elastic modulus, strength, stiffiless, and tribological properties with low coefficient of thermal expansion compared with the unreinforced matrix material."

Jan 1, 2000

By Shoji Taniguchi, Lifeng Zhang, Kaike Cai

"In the present paper, based on the two-phase (Eulerian-Eulerian) model, the 3D fluid flows in gas-stirred systems, i.e., air-stirred water vessel and argon-stirred liquid steel ladle, are simulated. In the Eulerian-Eulerian two-phase model, gas and liquid are considered to be two different continuous fields. The phases are assumed to share space in proportion to their volume fractions. The exchange between the phases is represented by source terms in conversation equations. Turbulence simulated by the k- e model is assumed to be the property of the liquid phase. The following effects of mathematical treatments and operational factors on the fluid flow are discussed, such as interphase drag force, turbulent model, the size of bubble, and gas injection mode.Some interesting results are derived. Except the interphase drag force, the interphase lift force should be taken into accounted in order to exactly simulate the fluid flow in gas-stirred systems. Suitable turbulent model and drag coefficient have effect on the mathematical simulation. Injecting small bubbles can realize a well mixing flow condition. The distance between the two gas-injection nozzles has effect on the fluid flow."

Jan 1, 2000

By Guangshi Li, Xionggang Lu, Xueliang Xie, Xingli Zou, Yuyang Bian, Hongwei Cheng, Kai Zheng, Changyuan Lu

The corrosion resistance and corroded microstructure of MgO-C refractory in molten slag are investigated by immersion test in muffle furnace at 1600 °C . The microstructure and chemical compositions of the specimens after erosion experiment are characterized by scanning electron microscope (SEM) and energy dispersive X-ray (EDX). The results confirm that the oxidation of graphite is the most important degradation mode of MgO-C refractory. The structure of the refractory material is damaged due to the decrease of graphite, as a result, the periclase substrate reacts with the molten slag directly. The corrosion process is controlled by the dissolution of the refractory materials into slag, low melting point oxides are therefore generated which lead to the damage of MgO-C refractory finally.

Jan 1, 2015

By Robin M. Forbes. Jones, Suhas V. Patankar, Ramesh S. Minisandram, Jr. Carter, Kanchan M. Kelkar

"The nucleated casting process currently under development has the potential for production of Ni-base superalloy preforms that possess superior microstructure to product made by conventional casting processes, primarily for gas turbine applications. In this process, electroslag remelted (ESR) clean (i.e., free of ceramic inclusions) molten metal is conveyed via a watercooled copper Cold-walled Induction Guide (CIG) to a gas atomizer. The spray of clean metal droplets is then directly cast into a water-cooled crucible for ingot production. The microstructure of the resulting ingot preform evolves within the length scale of the individual droplets and is a function of the thermal state of the incoming metal droplets. This, in turn, depends on particle size, flight time and heat exchange with the gas phase.In the present study, computational models is developed for the analysis of the flow and heat transfer in the gas-metal spray system under axisymmetric and steady-state conditions. The gasphase flow is analyzed using an Eulerian framework and turbulent mixing within the gas phase is modeled using the two-equation k-e model. The dynamics of the metal particles is analyzed using a Lagrangian framework that involves calculation of the trajectories of the metal droplets. A two-way coupling is considered whereby the transport and heat transfer in the gas and the metal phases influence each other.The analysis is developed at two levels. The spray model performs a detailed calculation of the spray dynamics in the vicinity of the spray and is intended for predicting the temperature and mass flux distributions of the metal spray depositing into the mold. The chamber model enables prediction of gas flow and motion of metal particles in the entire spray chamber."

Jan 1, 2004

By Tao Xuea

Gold frequently occurs in nature in the form of a gold-silver alloy. Thus, investigation of the electrochemical behavior of gold-silver alloys in cyanide solution has practical significance. In this paper, the potentiodynamic method is used to determine the anodic polarization curves of gold-silver alloys (Au-10% Ag and Au-50% Ag) in cyanide solutions. To facilitate the interpretation of the results, complementary experiments conducted in NaOH solution in the absence of cyanide are also reported. The results for the Au-Ag alloys are compared with the polarization behavior of pure gold and pure silver. With the aid of potential-pH diagrams for the Au- and Ag-CN-H20 systems and electrochemical kinetics concepts, the dissolution mechanism of gold-silver alloys, the effect of the presence of silver on the cyanidation of gold, as well as the factors which control the anodic reaction rate are clarified.

Jan 1, 1998

By Florian Kongoli

New operating conditions and process parameters are often necessary in today's industrial practice of non-ferrous smelting and converting in order to accommodate various new chemical compositions of mineral charges and environmental requirements or to conceive new and more efficient industrial technologies. An important parameter in non-ferrous smelting and converting is the liquidus surface of multicomponent slags. This surface is affected by multiple factors such as temperature, gaseous potentials, the content of each component in the slag, etc., and cannot be quantified by the existing ternary liquidus diagrams. In this work a new type of representation of the liquidus surface of multi component systems has been presented by means of a thermodynamic model. This representation waives the need of the multidimensional representation of multi component systems and yields practical two-dimensional diagrams, which can be easily used in the industrial practice.

Jan 1, 2000

By Peter C. Hayes

"The high temperature reduction of solids through the use of reactive gas atmospheres has application in a wide range of industrially important processes. Whilst significant advances have been made in understanding and describing these processes, some key aspects of the chemical reactions and reaction mechanisms operating in these systems, for example, the transformation from metal oxide to metal, remain poorly understood. A number of different product morphologies have been identified in these reaction systems and the reaction rates have been shown to be critically dependent on the product structure.Theoretical examination of the elementary process steps taking place in the region of the gas/metal/metal oxide interface, combined with electron microscope studies of the resultant product microstructures, have enabled the key process and material variables responsible for the development of the various product morphologies to be identified. By considering i) established criteria for the stability of moving interfaces in a thermodynamic potential gradient, ii) the relative rates of chemical reactions on the oxide and metal surfaces, and iii) key process phenomena and physico-chemical properties of the solid phases, the mechanisms and conditions for the formation of various product morphologies are identified. Interestingly the analysis points to direct analogies between these phase transformations and, the phenomena and microstructures observed in metal solidification, and the potential to develop generic models of these fluid/solid reaction systems."

Jan 1, 2013

By Liwen Hu, Jianxun Song, Hongmin Zhu, Qiuyu Wang, Shuqiang Jiao

The subchloride titanium was prepared by sponge titanium and titanium tetrachloride in the CaCl2 at 1173 K. The species were detected are mainly titanium dichloride, and the average valent in the melt are 2.05. The accurate equilibrium constants were obtained for the reaction 3Ti2+ = 2Ti3++Ti after the accurate activities of titanium chloride were evaluated with emf method, and the observed deviations from ideal behavior are discussed.

Jan 1, 2015

By Rak-Jun Choi

Plasma-induced damage of InGaN/GaN multiple quantum well (MQW) light-emitting diodes (LEDs) has been studied in terms of forward turn-on and reverse breakdown voltages, together with etch rate and surface morphology. The physical degradation of sidewall along with rough surface morphology of n-GaN caused by increased ion scattering induced the deterioration of the forward and reverse voltages. It was found that the turn-on voltage is sensitive to the surface roughness of the etched n-GaN and the breakdown voltage is strongly affected by the sidewall contamination. Annealing under nitrogen after the mesa etching improved the electrical properties of the InGaN/GaN MQW LEOs. Efficient blue light-emitting diodes (LEOs) were fabricated using InGaN/GaN triangular MQWs. The LEOs with triangular QWs showed a lower operation voltage and 2.4 times higher light output power than those with the rectangular MQW LEOs at 20 rnA and 20 "C. The intensity of electroluminescence (EL) at 20 mA was almost independent of ambient temperature in the triangular QW LEO, but decreased substantially in the rectangular one.

Jan 1, 2003

By Oscar Perales Perez, Atsuo Kasuya, Kazuyuki Tohji, Yoshiaki Umetsu

"The removal of iron and various heavy-metal ions by their incorporation into stable ferrite-type precipitates at 25°C is a promising alternative to clean up large volumes of polluted aqueous effluents. Our research work investigated the conditions to produce magnetite and various M-bearing ferrites (where M: Zn, Cu, Co, Ni, Cd, etc.) directly from aqueous solutions at 25°C by simultaneous control of the oxidizing conditions and pH. The formation of the solids was followed by monit9ring the oxidation-reduction potential (ORP) and rate of proton release during the aerial oxidation of the suspensions at constant pH (contact stage). Only mildly oxidizing conditions, represented by ORP values between -110 mV and -150 mV and a moderate oxidation rate of Fe(II) species were conducive to well-crystallized ferrites at ambient temperature.' It was also found that increasing the Fe/M mole ratio in starting· solutions enhanced the stability ·of the M-bearing ferrites at ambient temperature. When the formation of the ferrite was incomplete, aging of the sludges in their mother liquors at 25°C promoted the crystallinity of the precipitates. The mentioned conditions ·favored the suitable progress of the ferrite-forming reaction involving the oxidation of Fe(II) entities, subsequent hydrolysis of produced Fe(III) species and dehydration of the intermediate:· Furthermore,· the ferrite formation at· low temperature permits the elimination of iron and co-existing heavy metal ions to sufficiently low concentration.In tum, the characterization of the precipitates evidenced their magnetic nature (room-temperature saturation magnetization above 60 emu/g) as well as the effective incorporation of target metal ions into the ferrite structure."

Jan 1, 2000

By M. H. Lin, S. Kou

"Czochralski pulling has been a very widely used process for growing single crystals for electronic and optical applications. Dopant segregation can significantly degrade the quality and yield of single crystals. We have used the floating-crucible technique for segregation control in Czochralski pulling, our floating crucibles being unique in that the melt passageway is very long. As such, dopant back diffusion is suppressed, even when the cross-section of the melt passageway has to be relatively large to help the melt go through or when the pulling rate is very low. Single crystals of model materials K-doped NaN03 and Pb-doped Sn have been grown with very uniform dopant concentrations. IntroductionSingle crystals of electronic and optical materials are often doped with a small amount of impurities to develop required physical properties, e.g., P and B in Si for n-type and p-type semiconductors, respectively, and Nd in YAG lasers. Dopant segregation can result in nonuniform physical properties, thus degrading the quality and yield of the resultant crystals.Figure 1 is an illustration of the conventional Czochralski process for crystal growth. Several techniques have been developed to control dopant segregation in Czochralski pulling, including the push-pull technique (1,2), the drop-pull technique (3-7) and the floating-crucible technique (8-13). The first two techniques require precise sensing devices and feedback control systems to keep the feeding rate equal to the pulling rate. The last technique is simple since the feeding rate is automatically equal to the pulling rate."

Jan 1, 1994

By lchiro Aoi, Hideo Nakae, Makoto Yoshida, Makoto Ishino

"The influence 6f gravity on the microstructure of unidirectionally solidified Cu-Pb monotectic, Ag-Si and Fe-C eutectic alloys is studied. In order to examine the influence of gravity in a lg environment, both the upward (opposite to direction of gravity) and downward (direction of gravity) unidirectional solidifications are carried out. The results are as follows: (1) For the upward solidified Ag-Si eutectic alloy, the eutectic Si continuously grows. On the other hand, in the downward solidified Ag-Si alloy, the Si grows discontinuously and disperses into the ex-Ag matrix. (2) No morphological difference in the eutectic growth is observed between the upward and downward solidified Fe-C eutectic alloys. (3) In the case of the upward solidified Cu-Pb monotectic alloy, a banded structure, which consists of Pb-rich layers and Cu-rich layers, is observed. However, such a banded structure -is not observed in the downward specimen. (4) The banded structure is not found in the upward solidified Cu-Pb-0.05 mass % Al and Cu-Pb-0.1 mass % Al alloys. In the Cu-Pb-0.05 mass% Al alloy, a fibrous -L 2 phase grows continuously parallel to the growth direction at low growth rate. Only 500 mass ppm addition of aluminum induces the morphological change of the monotectic L2 phase.IntroductionThe influence of gravity on the solidification of eutectic and monotectic alloys has been investigated in microgravity environments [l-9]. The purpose of these studies was to obtain a homogeneous microstructure of eutectic or monotectic alloys, most of which alloys tend to solidify with macro-segregation under gravity. However, in most of the previous experiments, e.g., in free fall systems, in aircraft or in space laboratories, the growth rate was too high to realize a planar solid/liquid interface. This would be due to the limited time for solidification. Thus, it was difficult to examine the influence of gravity on the planar coupled growth of the eutectic or monotectic alloy. In this study, both the downward U.D.S. (unidirectional solidification by gravity) and upward U.D.S. (opposite direction to gravity) are carried out in order to examine the influence of gravity on the coupled growth in a lg environment [l0, 11]. In the case of the downward U.D.S. using the current Bridgman method, the molten alloy must be confined between the crucible and the solid."

Jan 1, 2000

By A. Jakobsson

Studies of the rate of interdissolution in oxide systems in the solid state are of importance in materials processing through the powder-metallurgical route. As there is a need for following the rate of the such reactions continuously, a new method based on high temperature X-ray diffraction was developed. Mechanical mixtures of the oxides were placed in a high-temperature X-ray diffraction unit and the changes in the intensity and position of the peaks with highest intensity for both the components were followed as functions of time. A suitable theoretical model has been developed in order to interpret the experimental data and evaluate the diffusion coefficients. The method was applied in the case of the system MgO-NiO. The results obtained are compared with those obtained by another new method, based on solid-state galvanic cell technique with calcia stabilized zirconia electrolyte, developed in the Department of Theoretical Metallurgy. The advantage of the present techniques to monitor the progress of the reaction continuously make them suitable for computer control of such processes.

Jan 1, 1995

By B. Q. Li, Y. Shu, K Lynn

"This paper discusses the effects of magnetic field and internal radiation on the melt flow and solidification morphology during solidification processing of oxide crystals for optoelectronic and remote sensing applications. The numerical solution of the integral differential equation characterizing the internal radiation and the magnetohydrodynamic equations describing the magnetic and transport phenomena is obtained by applying the combined discontinuous and continuous finite element method. The results show that both internal radiation and an externally applied magnetic field can have important effects on the melt flow and solidification behavior during the melt processing of oxide materials.IntroductionOptical single crystals are widely used in optical and electronic devices. These crystals are often grown from high temperature oxide melts under strictly controlled conditions. As in the well-known single crystal growth processes for semiconductor wafers, thermal gradient in the melt is a major contributing fuctor to the oxide melt pool. Unlike the semiconductor single crystal growth processes, however, the oxide melt is semitransparent and internal thermal radiation plays an important role in redistributing the thermal energy in the melt pool. Our recent experience with pilot-scale plant measurements also shows that the oxide melt is electrically conducting, although its electrical conductivity is considered much lower than the liquid metal or semiconductor melt.The fact that the oxide melt is absorbing and emitting in the thermal radiation frequency range makes it difficult to study the thermal energy transport in the melt pool. This is because thermal radiation is governed by a hyperbolic differential equation, which is different from those describing the transport processes in liquids. Also, our understanding of how thermal radiation interacts with other transport mechanisms such as convection and conduction is rather limited at point in time, in particular in high temperature oxide melts for optical single crystal processing."

Jan 1, 2004

By Vincent Menard

The purpose of the present work is to demonstrate the removal of manganese from a neutral leach zinc-rich solution ([Zn] =150 g/L) at 80°C by oxidative precipitation using a gas mixture of sulphur dioxide (SO2) and oxygen (O2). In order to determine the optimum conditions for manganese removal, several bench-scale semi-batch experiments were performed, where the effects of ORP and gas mixing were investigated. These tests showed that SO2/O2 is a fast and effective oxidant for removing manganese down to ppm level as long as the appropriate ORP is attained/maintained and gas transfer kinetics are optimized.

Jan 1, 2006