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By Tetsuya Uda

Our recent achievements of rare earth separation technique[1,2] and new process idea for rare earth magnet recycling[3] are reviewed, (1) Binary chloride mixtures of rare earths were separated by a new selective reduction-vacuum distillation process. According to our experimental results, apparent separation factors were 8.1 for the Pr-Nd chloride mixture and 570 for the Nd-Sm chloride mixture. These values are much higher than conventional solvent extraction methods. (2) A study of recycling process of magnet sludge was carried out. The rare earths in the neodymium magnet sludge were extracted by chlorination with FeCI2, An activated carbon was used as a de-oxidation reagent Metallic iron in the sludge was not chlorinated because the iron monochloride is not stable, The extracted rare earth chlorides were easily separated from Fe-alloy and the excess of FeCh by vacuum distillation, 96 % of neodymium and 94 % of dysprosium in the sludge were extraeted into chloride phase, By the vacuum distillation, a mixture of neodymium and dysprosium trichlorides of 99.2 % purity was recovered, On the other hand, the rare earth chlorides can be converted to the corresponding oxides by a pyrohydrolysis reaction accompanied by a formation of HCl gas, The HCI gas can chlorinate metallic iron to FeCh, Therefore, a new recycling process for rare earth magnet waste can be realized as a chlorine circulation type process. During the process, only carbon and water are consumed and there are no toxic pollutants, Moreover, the obtained rare earth oxide can be directly used as raw material in the conventional oxide electrolysis process,

Jan 1, 2003

By Salustio s. Guzman

The standard .free energies of formation of tin chlorides were estimated with reviewed and estimated basic thermodynamic data, and measured reversible potentials for the disproportionation of tin dichloride into metallic tin and tin tetrachloride. Values for cºp, Sº, Hº?-Hº 298, -(Gº - Hº298) /T,.Hºf, Gºf, and log Kp are given in tabular form, these estimations are compared with estimations reported in the literature.

Jan 1, 1985

By F. J. J. van Loo, A. A. Kodentsov, J. A. van Beek, M. R. Rijnders

"A periodic layered morphology of the reaction zone has been observed in several annealed solid/solid diffusion couples, including metal/metal and metal/ceramic couples. This morphology is characterized by a regular array of alternating layers, which are either single-phase layers or bands of particles embedded in an intermetallic matrix phase. A description of several systems showing periodic layer formation is given. It is shown that the periodic layered structure with the single phase layers and the one with the bands of particles have a different mechanism of formation.IntroductionSolid state reactions in ternary systems can produce a variety of reaction zone morphologies if there are two or more reaction products. Three types of morphology have been described in detail: 1) simple layered; 2) isolated precipitates in a singlephase layer; 3) interpenetrating columnar (lamellar) or interwoven structure. Understanding the factors that govern the formation of different morphologies is of importance in many fields of engineering. For solid state displacement reactions the conditions governing the formation of these morphologies are well understood [1-4]. For example, the development of a layered or aggregate reaction zone depends on the relative diffusivities of the components through the reaction products.This paper is concerned with the periodic layered morphology which has been observed in various solid state systems. We consider this to be a fourth type of reaction layer morphology. Two manifestations of periodic layered morphology may be distinguished. One form consists of regularly spaced layers of particles of one reaction product embedded in a matrix phase (another reaction product). The other form consists of single-phase layers embedded in a matrix phase. It will be shown that each manifestation has its own mechanism of formation. In section A we consider a system (Ag/Ti-foil/Si) in which periodic layer formation will be explained as a special case of the Liesegang phenomenon. In section B we consider systems where the periodic layered structure has a different origin."

Jan 1, 1996

By H. Yin, T. Emi

"Advantages of gas/flux injection technology as materialized in the main stay unit processes for steelmaking are depicted covering hot metal pretreatment through secondary refining. Current status of micro-kinetic issues involved in the injection technology are reviewed including gas-in- metal, gas-in-slag, flux-in-metal, metal-in-flux and three-phase dispersion systems with reference to macro-kinetics. Key problems are briefly addressed to further develop injection technology for steelmaking processes.1. FROM PAST TO PRESENTApplication of gas injection to steel industry started in early 1950's when inert gas bubbling via stopper rod, lance, or porous refractory plug was practiced to make the temperature of steel melt in ladle uniform The gas bubbling in ladle was then extended to slightly removing hydrogen ti'om the steel melt tapped from Electric Arc Furnace (EAF) and Basic Open Hearth Furnace (BOH) when vacuum processing facilities were not popular. Later, oxygen gas injection via calorized steel pipe into molten steel bath in BOH Furnace was also put into operation to promote the decarburization to increase the productivity of the process. This line of development has been made in parallel with more profound processes, i.e, top blowing Basic Oxygen Furnace (BOF) for primary steelmaking and side blowing Argon Oxygen Oecarburization (AOD) vessel for decarburizing stainless steels.On the other hand, injection of fluxes into steel bath was first industrialized in Germany in 1960's, Primary objective was to desulfurize steel melt in ladle by injecting CaC2 or CaCrCaO mixture via lance under neutral slag cover with good success. Difficulties in injecting fluxes without clogging and rippling at a desired flux/gas ratio, and durability of injection lance were resolved in due time to bring forth many injection facilities to flourish for versatile refining operation. Top injection of fluxes from main oxygen lance to BOF was also industrialized as LDAC to promote early slag formation. A new process then emerged which injects oxygen gas and fluxes together through concentric annular tuyere, installed at the bottom of the BOE into steel melt. This process, developed in Germany [Oxygen Bottom Maxhutte (OBM)] and brought into maturity in USA (Q-BOP) and Japan in a large scale operation, became the predecessor of the combined blowing (top and bottom blown) BOF which dominates modern steelmaking."

Jan 1, 1996

By Xin Zhang, Mengqi Li, Hongxu Li, Xinrong Zhang, Hao Bai, Ning Li

"Organic Rankin Cycle (ORC) is an effective technology to transform low-grade energy resource into electricity. In this paper, based on thermodynamic principle, considering the waste heat resource lower than 120°C, thermodynamic properties of ORC with working fluids ofR245fa, mixed R21/R245fa and mixed Rl52a/R245fa were assessed. The results show that high evaporation temperature contributes to improved system performance. The Rankine Cycle that uses R21/R245fa can increase net cycle output, thermal efficiency and exergy efficiency by 3.02%, 2.35%, and 4.44%,respectively, as compared to that with pure R245fa. When using Rl52a/R245fa as working fluid, the net cycle output can increase by 3.83% at most, while the thermal efficiency decreases by 8.7%. These results indicate that R21/R245fa has a good advantage in improving the cycle thermodynamic performance.IntroductionOrganic Rankine cycle is usually used for low temperature power generation, and is applied to the conversion of geothermal energy, low-temperature solar energy, ocean thermal energy and industrial low-temperature waste heat etc. Traditional Rankine cycle is quite mature already, however, organic working fluids would affect significantly the general efficiency of the entire thermodynamic system. Thus, selection of proper working fluids and development of new highperformance cycle is becoming important."

Jan 1, 2013

By Kang Wan, Lei Tang, Jianchao Li, Jieyu Zhang, Minqi Sheng, Jifang Xu

"The viscous flow phenomenon in slag close to the liquidus temperature was considered. A simple approach that liquidus temperatures of melt could be derived from viscosity data was employed. The potential of this method for estimating the liquidus temperatures of pure water and binary alloy was demonstrated. The liquidus temperatures of the CaO-Alz03 based slags obtained from the second derivative method depends upon the number of viscosity values available at different temperature intervals. The results indicated that plots start deviating from the straight-line behavior at temperature as expect, and the second derivatives show the break points at a certain temperature, which is the liquidus temperature. Comparisons among the present observations as well as the characteristic temperature of the selected slags, which measured by the hemisphere method and DSC, indicated that it is possible to get a reasonable idea of estimate the liquidus temperatures from activation energies for viscous flow.IntroductionThe liquidus temperature of slag, which has a significant effect on the kinetics of chemical reactions and the slag-metal separation, is extremely important for metallurgical operations. Experimental measurements of the liquidus temperatures of slags are difficult, since slags invariable supercool. In addition, behavior of a single constituent in a multi-component slag is different in different circumstances due to its interaction with other constituents. Hence, it is essential to study the liquidus temperature of each particular slag resulting from a special process. Usually, the compositions of the slags aimed to the single liquid region of the phase diagram. However, the phase diagram of many slag systems, which back often to the 1950's, involves considerable uncertainties. Many liquidus temperatures are given as dotted lines in Slag Atlas [1]. Disagreements between the phase diagram and the reality have been found [2]."

Jan 1, 2013

By Mostafa O. El-Bealy

"To estimate the interdendritic cracking tendency in casting processes, a new model for interdendritic cracking criteria has been proposed. The model combines a concept of the alloying element effect on the interdendritic strain generation and therefore on the susceptibility of interdendritic cracking phenomena. A susceptibility of interdendritic cracking is modeled by using El-Bealy's interdendritic cracking susceptibility function ""BJCSF' and the opening displacement between the dendrites ""EIA "". These concepts are modeled based on the previous experimental observations and ElBealy' approach. The model is implemented numerically for a one-dimensional model problem with some similarities to the casting of steel. The variation of some key parameters that are known to influence the frequency and severity of the interdendritic cracking is then studied.I. INTRODUCTIONInterdendritic cracking ""hot tearing"" commonly encountered in both ferrous and nonferrous castings (1,2]. It is generally believed that interdendritic cracks start to nucleate and develop in the interdendritic strain region within the mushy zone [l-5]. The interdendritic strain region is then definitely coherent, but continuous films of liquid still exit (4,5]. This distinguishes interdendritic cracks from cold cracks forming during the casting process after complete solidification (6,7].Much effort has been put into the understanding of the interdendritic cracking phenomena, and several theories have been proposed. Fellini [8] stated that interdendritic crack ""hot tear"" will result if the material is subjected to too high of accumulated strain within so called vulnerable part of the solidification interval. Kinosita et. al. [9] and Campbell (10] also emphasized the role of tensile stresses in the forming of interdendritic cracks. Most interdendritic cracks criteria simply consider the size of solidification interval, stating that solidification range is associated with a lager interdendritic cracking susceptibility than a short range. Clyne and Davies (11] formulated a more refined such criteria based upon the time spent in different regimes of the solidification interval. They defined a vulnerable region in which thin continuous films of interdendritic liquid exist, and the permeability is low. When thermal strains are induced in this region, the film is not able to sustain the stresses, and an interdendritic crack will form."

Jan 1, 2001

By Guo Chen, Jin Chen, Jinhui Peng

In this paper, solving common problem of electrostatic precipitator (ESP), which was frequently ruptured of the cathode insulation in the production process were studied. The microwave heating airflow technology was introduced, which takes full advantage of its unique properties, solves the output problem of the high temperature air, achieves purpose of energy conservation, important economic significance and environmental significance. The mathematical models and designing of microwave high-temperature hot air system was calculated. The common forms of heat exchangers and comparative analysis were also introduced. The conditions found to be at the temperature of 240 °C. Under optimum conditions, the microwave heating power was 1482 W. Based on the mention results, this microwave heating method can be applied effectively and efficiently way for the production process of electrostatic precipitator.

Jan 1, 2015

By Yunhua Gan, Xiaowen Chen, Yang Tong

Experimental studies of electro-spraying were carried out using ethanol as fuel in a microcombustor under combined electric field. And the effects of different electro-spraying modes on the combustion efficiency were analyzed. Results showed that when ring electrode potential was invariant, there were four different electro-spraying modes with the variations of nozzle potentials, which were varying with the flow of ethanol. The cone-jet mode was the stablest one during the whole experimental process. The atomized ethanol was ignited and combusted stably near the steel mesh, the combustion efficiency increased firstly and then decreased along with the increasing of the equivalent ratios, reached the maximum values when the equivalent ratio equal to 1.0. And the maximum values were the highest at the cone-jet mode, and the lowest at the pulsed-jet mode.

Jan 1, 2016

By Shusen Cheng, Dongdong Zhou

The high temperature distribution in ironmaking and steelmaking industry is very important to control the smelting process. Although equipment is available to measure the temperature in the smelting process, in general it could just measure one certain point or only at discrete times. The real time temperature distribution in ironmaking and steelmaking is important because it could reflect reaction information and help to control the operation parameters. In this paper, a new method to detect the temperature distribution in ironmaking and steelmaking through the application of digital imaging system based on the color CCD was studied. In addition, the two-color method and partial least square method were used in the calculation model to improve the accuracy. The results agreed well with the measured temperature.

Mar 1, 2017

By L. E. Murr

Preliminary studies of bacterial attachment to MoSp (molybdenite) have indicated a low correlation between dislocation density in the (0001) basal plane and the density of attached microbes. In the present investigation, poly- crystalline thin sections of CuFeSp (chalcopyrite) have been ion-etched or carefully comminuted to electron transparency and observed in the transmission electron microscope. The thinned test sections were then immersed in a culture solution in which bacterial attachment occurred. The attached bacteria were biologically stained in a uranyl acetate solution and the entire thin CuFeSp sections or tiny particles containing thin, electron transparent edges with bacteria attached were observed in the transmission electron microscope, allowing the coincidence of bacteria and their density to be directly observed in relation to lattice dislocations and crystallographic orientations of the exposed surfaces. This technique has the advantage of exposing crystallographic orientations where dislocation lines intersect the free mineral surface, and the emergence sites of dislocations could in principle be directly investigated as a possible preferential attachment site for bacteria. Bacteria morphologies were also extensively observed in the scanning electron microscope. The implications of the results are that although a strong correlation between dislocation density and distribution and bacterial attachment, density, and distribution has not been established, systematic multiplication of dislocation densities in crystalline mineral particles to be leached could enhance leaching rates by increasing the reaction rates as well as the density of attached bacteria at crystalline, metal-rich phases. Techniques for dislocation production in mineral and ore bodies and the particular implications in chalcopyrite leaching are discussed in relation to in-situ leaching where comminution is attained by explosives and the generation of strong shock waves in an ore body. The present study demonstrates the use of microanalytical and microscopic techniques in the investigation of fundamental microstructural phenomena in hydrometallurgical processes.

Jan 1, 1976

By J. Wong

We report a successful use of x-ray absorption spectroscopy to probe the chemical and structural environment of trace elements in coal. When applied to vanadium in coal, it was found that vanadium exists in at least two environments: a trivalent site 6-fold coordinated by oxygens at ca. 2.0~ and a tetravalent site 5-or 6-fold coordinated also by oxygens, one of which forms a short V=O bond at ca. 1.6a. No evidence of nitrogen (porphyrin)1'or sulfide environment was found. It was also found that the vanadium environ-ments in the raw coal did not survive unchanged in a liquefaction process. These findings have implications for coal cleaning processes and for trace element release into liquefaction process streams.

Jan 1, 1982

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Niloy K. Nath

Two layer sintering by charging green sinter mix with normal coke rate in the upper layer and reduced coke rate in the lower layer, can substantially reduce the coke rate and also improve the sinter quality by producing more uniform thermal profile through out the bed height. The two-layer sintering process have been analyzed by numerical simulation of the process by a detailed CFD based model, considering all the important phenomena like gas-solid reaction, melting and solidification, flow through porous bed, heat and mass transfer etc. Optimization techniques like genetic algorithm, differential evolution is then applied to evaluate the optimum coke rate in the two layers of the bed to produce the ideal thermal profile and melting fraction in the sinter bed for optimum sinter quality. Through this optimization method both high quality sinter with minimum return fines can be achieved along with reduced coke rate. Application of a genetic algorithm for this type of process optimization has several advantages over the traditional optimization techniques since it can identify global optimum condition and perform multi-objective optimization much easily for complex industrial process like iron ore sintering. Keywords: Two-layer Sintering, Iron Ore Sinter Quality, Ergun's Equation, Gas-solid reaction, Melting Fraction, Multi Objective Optimization, Pareto Set, Genetic Algorithm

Jan 1, 2003

By S. R. Reddy, R. G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionIn most of the pyrometallurgical high temperatures processes, interactions of solutes such as oxygen, nitrogen and sulfur, with the solvent atoms are most important during refining processes. There are numerous theories are developed [1-25] to interpret the thermodynamics of solutes in multicomponent alloy systems. Which are mainly developed using statistical or Quasichemical equations.Wagner [4] developed one energy parameter ideal solvent model based on activity coefficient of solutes compositional dependency. He used one energy interaction term which is not able to account for interaction energy parameters for the same solute concentration at different solvent compositions and also it is ineffective model to predict for strong interacting systems."

Jan 1, 1996

By S. W. Ip

Over the years, the importance of surface and interfacial phenomena has been neglected by the copper-nickel industry. As a result, little data on the surface and interfacial tension of the Ni matte and slag system are available in the literature. In view of the scarcity of information in this area, the surface tensions of the Ni-Fe-S system together with the Ni-Fe-S and fayalite type slag system were measured using the sessile drop technique. Drop images were obtained by X-ray radiography. For the Ni-Fe-S system, the results showed that the surface tension of the matte increases with matte grade. The surface tension behavior with changing matte grade showed a slight negative deviation from ideality. This indicated that FeS is slightly surface active in the nickel matte system. Results also indicated that small increase in sulphur content in the matte can decrease the surface tension quite significantly. The measured surface tension of the Ni-Cu-S system showed a linear relationship with the Cu2S content in the matte. The surface tension decreased with Cu2S content. Interfacial tension measurements showed a similar trend. That is, interfacial tension increased with increasing matte grade. The presence of MgO (-1.5%) and A12O3 (-6%) in the slag does not affect the interfacial tension value. Effects of matte surface tension on phenomena such as entrainment of matte in slag and infiltration of matte into refractory pores are discussed. The calculated flotation coefficients indicated that flotation of nickel mattes cannot be avoided by changing the matte grade. Filming of matte on bubbles can occur below a matte grade of about 19% Ni3S2. As for infiltration, refractory bricks containing high Cr2O3 will be easily wetted by matte regardless of matte grade. Therefore, bricks containing high Cr2O3 can easily be infiltrated by liquid matte.

Jan 1, 1993

By K A. Pericieous

"Magnetic fields have many actual applications in the metals processing industry. Externally applied magnetic fields give rise to electromagnetic (Lorentz) forces formed by the cross product JxB, between the induced current density J and the magnetic field density B. When the metal is in liquid form, the Lorentz force generates motion in the fluid which in applications of practical interest becomes turbulent. In modelling terms, the Lorentz force appears as a source in the momentum equations. In addition, the induced current generates heat (Joule heating) in the metal that is in proportion to J2, with a corresponding source of heat in the energy equation. Whether as heat or as a force, these effects represent action at a distance - a most useful attribute when dealing with hot metal. The Lorentz force is used to stir solidifying alloys, pump liquid metal in conduits, dampen the flow in the meniscus of a continuous caster, levitate metal drops, induce artificial gravity conditions in suspensions or contain liquid metal. Elsewhere, the Lorentz force may be a by-product of some other operation, so leading to wave excitation in aluminium electrolysis cells, or altering the shape of the weld pool in arc welding. Joule heating is most commonly used with applied AC fields, to melt metal in induction furnaces.The author and his colleagues have been involved in the modelling of most of these processes in the past decade. Modelling is not however straightforward, since most of the examples mentioned represent genuine multi-physics challenges. There is a strong coupling between the flow field and electromagnetic field. The addition of a dynamically varying metal free surface and the moving solidus front means the flow, heat and electromagnetic fields need to be computed simultaneously. In situations involving metal containment, the metal free surface position is governed by the interplay of gravity, Lorentz force, surface tension and fluid inertia. Since all the interesting effects often happen in thin boundary layers at the surface due to the skin effect, mesh generation and mesh control during the computation become non trivial problems that need to be addressed. This paper presents a review of numerical methods used to model droplet levitation, semi-levitation melting and cold crucible induction melting of metals. The first method is based on spectral collocation techniques and the second is the traditional FV approach. Steps taken to validate the computations and typical transient results are also given."

Jan 1, 2001

By R. G. Reddy

Viscosities of alkaline metal oxide-silicate melts were estimated using our previously developed mathematical model. The structural based model considers depolymerization effects and related breakdown of the silicate network structure, on the addition of metal oxides to the melt. The developed expression: n =4.9x10 9 NO 0 T ½ exp(E/RT) poise was used to calculate the viscosities of various binary silicate systems such as, CaO-SiO,, MgO-SiO, and MnO-SiO,, as a function of temperature and composition. Excellent agreement was obtained between the calculated and experimentally determined viscosities.

Jan 1, 1991

By Zhao Guangwen, Wu Tan, Qiuzhan Tian, Duan Shuzhen

"A thorough study of lost currents in bipolar cells has been made for the development of the great potential of bipolar cells in energy saving. A proper equivalent circuit for bipolar cells has been found, and mathematic methods for computing lost currents at all kinds of polarization have been developed.At linear polarization, the lost currents can be computed by solving either a tridiagonal matrix or an ordinary differential equation of second order. This kind of values can be used to evaluate the minimal lost currents at given conditions. At other kinds of polarization, the lost currents can be computed by the same methods as above if the necessary experiments of measuring the cell voltages of every electrolytic compartment have been made. This kind of values can be used to design bipolar cells at practical conditions.Extensive experiments have been made to evaluate the effects of electrode polarization, emf of galvanic cell for the formation of electrolyzed substance, gaseous products, geometric dimensions of electrolytic cells, special resistance of electrolyte used, and the total and ordinal number of electrolytic compartments on lost currents. It is the first time to make such a systematic research by experiments in the world. Experiments showed that theoretic models were in good agreement with measured data. Experiments also showed that D.C. energy consumption of 0.45 kwh/kg of Pb for lead electrolysis from molten chlorides could be achieved in a cell with 7 bipolar electrodes.IntroductionIt is very promising to apply bipolar electrolytic cells to electrolysis of aluminum, magnesium, lead, zinc and perchlorinates for their great potential of energy saving for example, bipolar cells had been used in the production of magnesium and saved more than 30% of energy, being one of the three main techniques of energy saving in the production of titanium sponge (1)."

Jan 1, 1988

By David G. Dixon

A general, unsteady-state model for leaching of one or more solid reactant species from a non- reactive, porous, spherical pellet is derived in dimensionless form for the interpretation of leaching data, and for use in the design of coarse-ore leaching processes. The effects of diffusion rate, chemical reaction rate, variable reaction order, and competition between multiple solid reactants are examined using the concept of the effectiveness factor. It is shown that the model is capable of simulating both "reaction-zone" and "heterogeneous" kinetics, depending on the choice of three dimensionless parameters. Results of batch leaching tests of artificial ore pellets are presented, and their relationship to the model is discussed.

Jan 1, 1993