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By Peng Jianping, Feng Naixiang, Di Yuezhong, Wang Yaowu, Pan Xijuan

A vacuum silicon thermal reduction lithium process is developed in present work which used lithium hydroxide, alumina and calcium oxide as raw materials. The process contains two steps, which are that Li5AlO4 clinker is prepared in ambient environment, and that metal lithium is extracted from Li5AlO4 clinker with ferro-silicon alloy as reductant in vacuum. On the basis of thermodynamic analysis and investigative experiments, feasibility of this process is proved. The results show that Li5AlO4 can be generated by calcination lithium hydroxide and alumina, the burning loss is above 31% under the conditions of calicination temperature above 750℃ and time more than 90min. The main phases of calcination product are Li5AlO4 and CaO. When the calcination product is reduced by ferro-silicon alloy in vacuum, the lithium reduction ratio can be over 80% under the conditions of reduction temperature 1200℃ and reduction time 60min.

Jan 1, 2014

By Kouji Mimura, Manabu Kishida, Minoru Isshiki

"Purification of metallurgical grade silicon (MG-Si) by the plasma-arc zone melting method (PZM) has been examined. The process consisted in the horizontal displacement of a molten zone heated by Ar- and 10%H2+Ar- plasma-arc under atmospheric pressure. This technique, especially using hydrogen plasma-arc, promoted the segregation of impurities from the head to the tail of the bar and the vaporization of impurities of higher vapor pressures. Metallic impurities such as Fe, Ti, Cr, Mn,. Cu, Al and Ca were reduced to less than 1 mass ppm at the head side of the Si bar. Non-metallic impurities such as boron, phosphorous, carbon and oxygen were also reduced by the zoning effect and, furthermore, by activated hydrogen atoms dissociated in the high temperature plasma-arc according to the following reaction: Q (in liq.Si) + 2H = H20. Plasma-arc zone melting with hydrogen plasma has been recognized to become an effective purification technique of MG-Si for the production of a low cost solar grade Si (SOG-Si).IntroductionDemand of high-purity Si for solar grade silicon (SOG-Si) is supposed to be further growing in the near future. The purity of SOG-Si required for the photovoltaic cell is more than six nines. An expensive semiconductor grade silicon (SEG-Si) with the purity of around eleven nines has been used to satisfy the demand. Development of techniques and processes for the production of a low cost SOG-Si is therefore necessary [l]. Although many purification techniques, such as directional solidification, plasmaarc melting and electron beam melting [1-6], and processes, such as carbothermic reduction of high purity silica [7], have been examined and proposed for this purpose, a more efficient and practical purification technique is still required.In the present work, the purification of MG-Si has been investigated using a plasma-arc zone melting (PZM) technique developed by the authors. Plasma-arc melting, which is well· known as a useful melting method for various metals and alloys, has been recognized to be efficient for refining and degassing several metals if hydrogen is added to the plasma generating gas, resulting in the so-called hydrogen plasma-arc. For example, deoxidation of Fe, Co and Ta [8,9], decarburization of Fe [9] and removal of metallic impurities from Zr, Ta and Fe [10-12] have been reported. This excellent refining effect is considered to be caused by dissociated and activated hydrogen atoms formed in the high temperature plasma-arc."

Jan 1, 2000

By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995

By Hideya Sato

Refractory wear caused by melts is one of the major determining factors for the interval of shut-down repair of the metallurgical furnaces in general. Calcium ferrite slag employed by M it subishi Continuous Copper Converter, shows hi& fluidity and corrosive characteristics against most of the refractories. In order to improve the corrosion resistance of the refractories, the mechanism of MgO-based refractory wear by the calcium ferrite slag was intensively studied. The dissolution behavior of the refractory into the molten slag and the penetration of the molten slag into the refractory were observed by crucible tests and newly developed oscillating furnace tests. It was found that the wear of MgO-based refractories by the calcium ferrite slag is mainly dominated by the internal structural failure caused by the penetration of CaO-Cu20 rich slag which is formed as a result of the preferential absorption of FeO, from original slag by the spinel of the refractory.

Jan 1, 1999

By E. Dendy Sloan

An overview of hydrate properties is given, with emphasis on unusual deviations from ice, the most common solid water form. Reliable sample preparation and reproduction of in situ hydrates provide the foundation for all hydrate science and engineering. Relations are given to connect the three domains in the title: (1) micro-scopic properties measured with Raman, NMR, and diffraction spectroscopy, (2) meso-scopic properties measured with single crystals, and (3) macro-scopic properties measured with pressures, temperatures, volumes, etc. A principal illustration relates micro-scopic and macro-scopic domains. Experiments provides the basis for improving statistical thermodynamics model for these compounds. To date, this model is one of the most commonly used industrial statistical thermodynamics applications, based upon the classical model of van der Waals and Platteeuw (1959). Microscopic measurements and simulations indicate model assumption improvements, resulting in the next generation of the statistical thermodynamics for improved macroscopic property prediction.

Jan 1, 2002

By Jay. M. Khodadadi, Josef Štetina, František Kavicka

"With the aid of the proper original numerical model of solidification the instruction for preparation of input parameters for numerical simulation of technological processes, with change of the phase or structure, will be presented. A method of calculation analysis of influence of therrpophysical properties of materials entering the system of casting-mould-cores environment, and also of boundary conditions on the required simulation accuracy will be suggested. For the cast material, the influence of heat .conductivity, specific heat capacity, density and latent heat of phase transformation also has been analysed. For metallic or non-metallic moulding material"" the influence of the see main parameters has been analysed and, furthermore, their combination, influence of thermal conductivity, and of heat storage. The order of influence of all quoted parameters of a casting and moulding material was established. For example heat conductivity in the liquid state is on the last place. From the boundary conditions the -most important influence on the total solidification time and · on the mechanism of forming of temperature field has the ·boundary condition on the casting mould boundary, then follows the boundary condition on the level of a molten metal. The negligible influence has the boundary condition on the mould frame and on the bottom.IntroductionThe original and universal mathematical model of solidification, cooling and heating has been set up and checked, in order to be capable of analysing a one- to three-dimensional steady or unsteady temperature field of the casting-mould-environment system and, namely, of the system as a whole or its arbitrary parts, during any industrial technological process whose individual processes could be solidification, cooling, heating, refrigeration and others, in any sequence or singly. The model enables the simulation of traditional and also non-traditional technologies of casting in foundries, metallurgical plants, forging operations, heat treatment processes, etc. If solidification is not the matter, the metal part of the system need not be called the casting but a component, a block, a forging and the like."

Jan 1, 2000

By Pertti Koukkari, Nagendra Tripathi, Karri Penttilä, Justin Salminen

A computational fluid dynamic model for a novel flash ironmaking process based on the direct gaseous reduction of iron oxide concentrates is presented. The model solves the threedimensional governing equations including both gas-phase and gas-solid reaction kinetics. The turbulence-chemistry interaction in the gas-phase is modeled by the eddy dissipation concept incorporating chemical kinetics. The particle cloud model is used to track the particle phase in a Lagrangian framework. A nucleation and growth kinetics rate expression is adopted to calculate the reduction rate of magnetite concentrate particles. Benchmark experiments reported in the literature for a nonreacting swirling gas jet and a nonpremixed hydrogen jet flame were simulated for validation. The model predictions showed good agreement with measurements in terms of gas velocity, gas temperature and species concentrations. The relevance of the computational model for the analysis of a bench reactor operation and the design of an industrialpilot plant is discussed.

Jan 1, 2014

By Masami Taguchi

"It is found that lead monoxide, PbO, has an ionic conductivity, and the all solid-state electrochemical cell using this oxide as an electrolyte has attracted the attention of battery researchers. In this study, thin film PbO2/PbO/Pb solid cells were produced on glass substrates and their discharge properties were investigated. The acti.ve material for the positive electrode, PbO2, was obtained by reactive sputtering of a Pb target in oxygen plasma. The PbO electrolyte and the active material for the negative electrode, Pb, were vacuum evaporated from /3 -PbO powder and a Pb block, respectively. The open-circuit voltage of the cell agreed with the theoretical value based on the thermodynamic data, and the close-circuit voltage was improved by the addition of a univalent impurity such as sodium or potassium to the PbO electrolyte. The connection of the cells in series and in parallel produced a higher electromotive force and a larger capacity. Also, the charge-discharge cycling test revealed that the cell could be charged and function as a storage battery.IntroductionGenerally, the ionic conductivity of a solid-state electrolyte is lower than that of a liquid electrolyte near room temperature. This has been a serious obstacle to using such electrolytes in an electrochemical cell. However, some solid-state electrolytes, which can preferentially pass a specified ion and have high ionic conductivity, have been found. Lead monoxide, PbO, which is an oxygen ion conductor, is such an example (1)(2). If a solid-state electrolyte is adopted for use in an electrochemical cell the problem associated with a liquid electrolyte such as leakage can be alleviated. The cell structure also can be simplified, because the electrolyte plays the role of separator to prevent the active materials from mixing. Thus, physical vapor deposition technology may make it possible to develop a very thin film cell, which consists of only solid phases (3)(4). In this study, the thin film PbO2/PbO/Pb solid cell with a thickness· of only a few micrometers, in which all the constituents were systematically deposited on a glass substrate by reactive sputtering and vacuum evaporation, has been produced and the charge-discharge properties were investigated. An attempt was made to improve the discharge properties by doping impurities such as Na2CO3 and Sb2O3 into the PbO electrolyte. Moreover, the connection of the cells in series and in parallel to get a higher electromotive force and a larger capacity, and the charge-discharge cycling test to determine its use as a storage battery were carried out."

Jan 1, 2000

By N. J. Themelis

The basic chemical, thermal and transport principles that underlie sulfide smelting of. copper, nickel and lead are reviewed. Two basic types of modern smelting processes are distinguished?: flash-smelting, where the predominant reactions occur between oxygen-bearing gas and concentrate particles dispersed therein; and bath-smelting where the concentrate is enveloped and reacted in a turbulent bath of matte, slag and gas. The controlling heat and mass transfer phenomena are discussed, and appropriate correlations are proposed.

Jan 1, 1983

By M. Yoshida, S. Hanada, T. Takasugi

"A study has been conducted to examine the effect of ternary alloying elements on high temperature deformation of the C15 NbCr2 based intermetallics in Nb-Cr-X (X=V, Mo and W) alloy systems, which have attractive properties as high temperature structural materials. The high temperature deformation of the C15 NbCr2 intermetallics can be improved by two alloying methods. One method is based on geometrical consideration for site occupation and atomic size factor of component elements and additive elements in the single phase C15 lattice; addition of Mo and V can promote dislocation movement without introducing significant hardening. The other method is based on microstructural modification through ternary alloying; moderate addition of these elements results in a variety of duplex microstructure consisting of the C15 phase and bee solid solution without forming any intermediate phases, and can enhance the high temperature deformability. Particularly, alloys with duplex microstructure equilibrating with Cr-rich bee solid solution is shown to exhibit superior deform ability. Also, lattice property of the additive atoms in the C15 structure and phase relation between the C15 structure and the bee solid solution are investigated by OM, XRD, TEM and ALCHEMI observations and then discussed in association with observed mechanical behavior.IntroductionLaves intermetallics with AB2 stoichiometry belong to the largest group in a large number of intermetallics with various kind of crystal structures, and have a variation of the cubic CIS, the hexagonal C14 and the dihexagonal C36 structures, depending on stacking sequence of XYZ type, each of which consists of four interpenetrating atomic layers (1-3). Some of the Laves intermetallics have good functional properties and therefore are considered to be used as, for instance, magnetic materials, magneto-optical materials, hydrogen storage materials and superconducting materials (2). Also, the Laves intermetallics are considered to be good candidate as high temperature structural materials operating at high temperatures and in severe environment because they have high melting point, low density, and potential resistance to corrosion and oxidation. However, the Laves intermetallics are very brittle at low temperatures because they consist of complex crystal structures similar to many other intermetallics."

Jan 1, 1996

By Regina Krachler, Herbert Ipser

"The principles of the derivation of statistical-thermodynamic models to interpret the compositional variation of thermodynamic properties in non-stoichiometric intermetallic compounds are discussed. Two types of models are distinguished: the Bragg-Williams type, where the total energy of the crystal is taken as the sum of the interaction energies of all nearest-neighbor pairs of atoms, and the Wagner-Schottky type, where the internal energy, the volume, and the vibrational entropy of the crystal are assumed to be linear functions of the numbers of atoms or vacancies on the different sublattices.A Wagner-Schottky type model is used for the description of two examples with different crystal structures:For B'-FeAl (with B2-structure) defect concentrations and their variation with composition are derived from the results of measurements of the aluminum vapor pressure; the resulting values are compared with results of other independent experimental methods.For Rh3~ (with an NiAs-derivative structure) the defect mechanism responsible for nonstoichiometry is worked out by application of a theoretical model to the results of tellurium vapor pressure measurements. In addition it is shown that the shape of the activity curve indicates a certain sequence of superstructures.In principle, there are no limitations to the application of statistical thermodynamics to experimental thermodynamic data as long as these are available with sufficient accuracy, and as long as it is ensured that the distribution of the point defects is truly random, i.e. that there are no aggregates of defects."

Jan 1, 1996

By Chen Song

Cobalt basic carbonate particles were precipitated from 1.0mol cobalt nitrate or cobalt sulfate solution with ammonia carbonate. By controlling the zeta-potential of the particles and the ionic strength of the solution, the uniform particles with ellipsoid or rod shapes were obtained. During the precipitation process, the interface tension was diminished to the minimum and therefore the Ostwald ripening and secondary nucleation were both inhibited. The morphology and the size control by zeta-potential seem to be the result of thermodynamics rather than classical crystalline kinetics. The particle sizes were in the range of 0.4-0.6, 0.3-0.4 micrometer. After thermolysis, the spinel-type C0304 particles were produced. The morphologies of C0304 particles were similar to that of their precursors.

Jan 1, 2003

By C. Beckermann

"A diffuse interface model is derived for the direct simulation of two-phase flows with surface tension, density differences between the phases, and phase change. The derivation starts from the balance equations for a sharp interface and uses a formal averaging procedure on an atomic scale to obtain diffuse interface versions of the equations. Two approaches are considered: (i) the two phases have different velocities inside the interface and separate conservation equations are solved for each phase, and (ii) the two phases have the same velocity inside the diffuse interfuce and mixture conservation equations are solved. Based on a superposition of microscopic (atomic-scale) and macroscopic interface morphologies, an expression for the interfacial momentum source term is introduced that models surface tension effects and accounts for immiscibility between the phases.IntroductionDiffuse interface methods have been a popular tool in the direct simulation of two-phase flows [I]. In diffuse interface approaches, the interface between the two phases is characterized by a rapid but smooth transition in the properties, such as density and viscosity. Usually, a phase function ? is introduced to represent this transition, and the evolution of ? in the domain is computed from a separate equation or recipe. A unique set of conservation equations (e.g., mass and momentum) is solved on the entire domain, irrespective of the phase present, by accounting for the transition in the properties and introducing terms that account for interfacial sources. The continuum surface force (CSF) model of Brackbill et al. [2], which accounts for surface tension, is an example of the latter. The volume-of-fluid (VOF), level set, and phase-field methods are all examples of diffuse interface approaches. The major advantage of diffuse interface methods is that explicit tracking of the interface and the application of traditional sharp interface conditions are avoided. A disadvantage can arise from the artificial smearing of what is in reality an interface of atomic-scale width; however, techniques have been developed to overcome this problem."

Jan 1, 2004

By Animesh Jha

Univariant diagrams are constructed for the reduction of nickel and cobalt oxide and sulphide minerals. The results from the carbothermic and hydrogen reduction of sulphide minerals are compared. The importance role of lime and calcium sulphate in controlling the emission of sulphurous- gases during reduction reaction is also explained. The mechanism of carbothermic reduction of nickel sulphide is explained by examining the sulphur exchange and reduction reactions. The phase equilibrium relationships that determine the formation of multicomponent liquid are characterised. Also the governing equilibria for inert atmosphere calcination- roasting of nickel and cobalt sulphide minerals are also described for the metallization of nickel and cobalt.

Jan 1, 1993

By Garrett May

We present a periodic technique for measuring the thermal conductivity of thin, disk-shaped samples. In samples of this type, temperature measurements must be made across the sample faces and are therefore subject to large error due to the interface resistance between the temperature sensor and the sample. The technique uses measurements of the amplitude and phase of the periodic temperature across both a reference sample and the unknown material at several different frequencies. Modeling of the heat flow in the sample allows the simultaneous determination of the thermal parameters of the sample as well as the interface resistance. The technique is demonstrated on nanocomposite samples less than 1.0 mm thick.

Jan 1, 2008

By Kexin Jiao, Huichang Song, Zhijia Zhang, Jianliang Zhang, Zhengjian Liu

A clear understanding of iron carburization reaction occurring between molten iron and carbonaceous materials is of great importance in blast furnace, and it is one of the hot spots that ironmaking workers pay close attention to. Although carburization rates between iron and coke have been studied, the factors directly controlling it have not been clearly identified. This study focused on the kinetics analysis of iron carburization reaction. Sulfur content was determined as having positive influence on graphite carburizing reaction rate in the range of 0.02% - 0.06%. The values of apparent activation energy calculated by the experiment are consistent with the existing literature, which in turn proved the reliability of the experimental data.

Jan 1, 2015

By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By Milton Manrique

The thermal decomposition of zircon concentrates in a non-transferred arc thermal plasma flow reactor was investigated. The plasma torch was operated using argon-helium and argon-nitrogen mixtures as plasma gases. The effect of power, feed rate and zircon particle size was studied. Products were characterized by XRD, SEM, TEM and chemical analytical techniques. The average size of the product was in the submicron range. Free energy minimization plots were used to predict the behavior of the system under different operating conditions. A kinetic model to describe the different stages of the thermal decomposition process is proposed. The results of this investigation showed a significant segregation process where the zirconia-rich product is collected in the reactor while the silica-rich product is collected in the filter. TEM analysis indicated that silica vapor is condensed on the surface of the zirconia particles.

Jan 1, 1996

By Zhou Shu-cai

"A method has been proposed for the pre-treatment of high phosphorus iron ore by carbothermic reduction assisted with microwave irradiation and magnetic separation on a laboratory scale. Chemical analysis of the reduced ore sample, the metal sample and the slag sample were conducted. Based on the above research, the influences of carbon addition, microwave power and microwave irradiation time on the recovery of Fe and dephosphorization were discussed. It indicated that the increase of microwave irradiation time and power had substantial effect on the recovery of Fe while the influence of carbon addition was not obvious and the highest iron recovery ratio reaches some 95.5% when the dephosphorization ratio was 37.68%. A high iron recovery ratio and a reasonable dephosphorization rate were incompatible under the conditions investigated in this study due to the reduced iron and because unreduced P-contained gangues were not efficiently separated. This method may provide a reference for the future utilisation of high-phosphorus iron ore.IntroductionWith the rapid growth of crude steel production in China, the source of iron ore tends to become increasingly strained and is facing the risks of raw material shortage for the iron and steel industry. In order to decrease the production cost, China has to focus on the utilization of its domestic low grade iron ores for the iron and steel plants [1-2]. China has a large deposit of high phosphorous iron ore with a reserve of 7.45 billion tons which is unused in any large scale [3]. Therefore, the development of a successful and economically viable technology for high phosphorus iron ore is of profound importance. To remove phosphorus from the high phosphorus iron ore, several mineral and metallurgical processes have been proposed, such as bio-leaching [4], roasting reduction plus melting separation [5], pre-reduction and screening methods combined with mechanical crushing or air jet milling[6] selective agglomeration plus reverse flotation [7]. However these processes are not cost effective or are time consuming. The traditional pyrometallurgical process( BF+ BOF) refuse this kind of ore mainly because that molten iron is saturated with carbon or high carbon content and thus all phosphor us in the burden goes to the molten iron[8]. Therefore, it is important to exploit the cheap and abundant high phosphorus iron ore as a resource in ironmaking. In recent years, the microwave was widely introduced as a heat resource for extractive metallurgy of iron ore or other minerals. For example, microwave assisted ore milling, microwave assisted carbothermic reduction of metal oxides and microwave assisted mineral leaching issues[9-10]"

Jan 1, 2014

By K. Sarveswara Rao

"Any innovative approach made in non-ferrous metallurgical industry centers upon developing new processes, saving materials, improving production quality, and bornagain materials. Aqueous processing is commonly used to treat lean grade or more complex ore bodies. Its sustenance largely depends on energy and environmental compliance including water and wastewater management. The present paper focuses the importance of using particle size distribution and surface area measurements during ammoniacal dissolution of a Cu-Pb-Zn sulphide bulk concentrate and with an overview of the effect of water salinity on the process chemistry and residue mineralogy. Accordingly, an effort is made here to discuss the emerging perspective and highlight the recent successes and trends in terms of energy savings in non-ferrous hydrometallurgy.IntroductionThe nature and structure of the global energy industry is likely to change significantly in the 21st Century. Rabago et al [1] have comprehensively discussed how the mining and minerals industries can adapt to the challenges and opportunities posed by trends and drivers in global energy use. According to the authors, the drivers of sustainability include water, efficient energy use, climate modification, transportation technologies and energy security. Sustainability and competitiveness for the minerals industry will depend on natural capitalism, resource efficiency, new processes, saving materials, improving production quality, born-again materials and the solutions economy. Based on this motivation, the theme of the present paper is centered upon applications as relevant to energy and sustainable development in non-ferrous hydrometallurgy."

Jan 1, 2009