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By Defeng Zhou, N. Trubaki, Jian Meng, Fanzhi Menga, Xiaojuan Liu, Yanjie Xia

"The microstructure and the electric conductivity of (Ce0.9Nd0.1)1 xMxO2 d (M=Mo, W) solid solutions were investigated. It has been found that their conductivity containing the grain (s gi ), the grain boundary (s gb) and the total conductivity (s t ) at 300°C- 700°C can be ranked as: (Ce 0. 9Nd 0. 1 ) 0.99 W 0.01 02- d (s gi = 0.065 S.cm·1, (s gb = 0.265 S.cm·1, s t = 0.039 S.cm-1) > (Ce0.9Nd0.1)0.99Mo0.01O2- d (s gi = 0.053 S.cm·1, s gb = 0.142 S.cm·1, s t = 0.029 S.cm-1) > Ce0.9Nd0.1 s 2- d (s gi 0.045 S.cm-1, s gb = 0.091 S.cm-1, s t = 0.018 S.cm-1) measured at 700°C. The highest conductivity is obtained in (Ceo.9Ndo.1)0.99W0.01O2 d. These results indicate that (Ceo.9Nd0.1)0.99W0.01O2- d is the most promising electrolyte materials of intermediate-temperature solid oxide fuel cells among (Ce0.9Nd0.1)1-xMxO2- d. IntroductionRare-earth (e.g. La3+, Nd3+, Gd3+ and Sm3l doped ceria-based ceramic materials have been acknowledged to be attractive electrolytes for solid oxide fuel cells operating below 600°C due to their high ionic conductivity [1, 2]. In order to improve ionic conductivity of these electrolytes further, in recent reports [3-6], some aids such as Mo03 [3] etc. in a limited amount can be used which causes extremely high conductivity. For example, Zhou et al. found that with MoO3 doping, the grain boundary conductivity of Nd3+ doped CeO2- d increased notably especially at lower temperatures due to the effect of severely undersized do pants [3]. It is well known that the size of W6+ (rw6+ = 0.60 Å) is close to Mo6+ (rMo6+ = 0.62A) because of lanthanide shrinkage. Thus, rare-earth doped ceria e.g. Nd3+ doped CeO2g with WO3 in a limited amount will be probably good and even better electrolytes. However, much less information is available about these materials. Therefore, in our paper, (Ce0.9Nd0.1)0.99 1-xMxO2- d (M=Mo, W) solid solutions have been prepared and characterized. Much higher conductive electrolytes are found in the series of (Ce0.9Nd0.1)0.99 M0.01O02- d particularly (Ce0.9Nd0.1)0.99W0.01O2- d"

Jan 1, 2012

By Xin Wang, Hongmin Zhu, Shuqiang Jiao

"The behavior of electrochemically depositing silicon in a molten high-melting-point fluoride electrolyte was studied at 1300 °C. The cathodic product was characterized by XRD, SEM and EDS. Though the analysis of structure and composition of deposition, it could certify that silicon deposited on the Mo rod and alloyed with molybdenum. A series of tests had been performed on the cathodic behavior of Si4+ ions in BaF 2-CaF 2-Na2S iF 6 molten salt. The influence of electrochemical parameters on the cathodic deposition of silicon was also investigated. The electrochemical behavior of Si4+ ions in applied fluoride melts was observed to proceed according to one-step reaction.IntroductionGreenhouse warming has been a serious global issue. lt is increasingly urgent for clean and renewable energy. Effective utilization of clean and inexhaustible solar energy has become very important. Solar cell (especially poly-Si solar cell) production has significantly increased this decade, as there is a growing demand for clean energy. Since the early 1980s, the annual growth of the photovoltaic (PY) solar cell industry is more than 30%. More than 90% of the annual solar cell production is based on crystalline silicon wafers. This rapid growth leads to a shortage of silicon of the adequate quality and price for the continued growth of this industry [I , 2J. The most conunonly used technology to produce silicon is the so-called Siemens process. This technology, involves the forming of gaseous Si compounds such as trichlorosilane (SiHCli) or silane (SiH4) with subsequent thermal decomposition of these back to Si. This technology is associated with transformations from solid to gas, and then back to solid phase, which lead to high irreversible thermodynamic losses and subsequent high energy consumption, the energy cost being around 200kWh/kg Si [3l_ The purity of the material from this process is very high (9 to 11 N). In general, what is needed for solar cell purposes are reported to require 4 to 6 N quality. To promote continued growth of the silicon-based PY industry, there is need for a low-energy silicon production process which can produce large amounts of silicon with an acceptable quality and a lower price particularly."

Jan 1, 2012

By R. Nilsson

In the present work, an assessment of the sulphide capacities of a number of binary and ternary slag systems have been carried out in the light of a sulphide capacity model. The model is based on the expression: {CS- exp (-A G °/R T) ? ao2 / fs2-} where AGO is the standard Gibbs energy change for the above reaction, ao2 is the activity of oxygen ions and f, is the activity coefficient of the sulphide ion in the slag. In the present model, the ratio (ao2/fs2) is optimized for the experimental data available in literature. The systems assessed are the binaries MnO-SiO2, CaO-SiO2, Al2O3-CaO, as well as the ternaries CaO-Al2O3-SiO2 and CaO-MnO-SiO2. In the case of all these systems, the experimental data available in literature were complemented by measurements carried out at the Division of Theoretical Metallurgy. The sulphide capacities of some FeO- containing binary, ternary and quaternary slags are also examined. The potentiality of the model to estimate the sulphide capacities of complex slag systems from binary and ternary data is demonstrated.

Jan 1, 1996

By Paul S. Korinko, Simona E. Hunyadi Murph

To address a radiological contamination event, a materials and process project was initiated. During the course of this project, processes and materials were developed that successfully captured zinc vapors physically and chemically, respectively. However, the physical traps were placed in an undesirable area and it was determined that the chemically captured zinc reactions was reversible. Consequently, advanced nanomaterials are being developed to capture zinc vapors. The current state of the art of the science and engineering of these materials and their efficacy for zinc capture and retention is discussed in this paper.

Jan 1, 2015

By XUEWEN WANG, Bowen Li, Mingyu Wang

A novel technology characterized by higher extraction of vanadium and recovery of valuable elements was developed to recover vanadium from stone coal. The brief flow of the novel technology mainly includes low temperature sulphation roasting, water leaching, recovering potassium, aluminum, copper and selenium, solvent extraction enrichment vanadium, precipitation of red vanadium, removal sodium from red vanadium and calcinations. The total recovery of vanadium reached 76.3%, which was higher than the current applied technology. The novel technology was environmentally-friendly and could extract vanadium from the stone coal, in which the content of V2O5 was less than 0.8%.

Jan 1, 2015

By Shunhong Huang

Thirty-five soils were sampled from three sites at different distances from chromium slag heap of a Iron-alloy factory, namely, nine from site A located under the chromium slag and eighteen from Site B in the vicinity of the factory and eight from site C far from the factory. The contents of total Cr in these soils from site A, B and C were 1666.0±1310.9 mg? kg - 1,1136.2±1844.6 mg? kg - 1 ,300.4 ±165.1 mg? kg ? 1, respectively. The contents of water soluble Cr were 59.3±77.57 mg? kg ? 1,0.6 ±0.3 mg? kg - 1 ,0.5±0.3 mg? kg - 1 , respectively. In order to evaluate soil health, the activities of four soil enzymes (catalase, polyphenol oxidase, dehydrogenase, alkaline phosphatases) were analyzed. The results have shown that dehydrogenase activity was greatly depressed by conditions in the heavy chromium-contaminated sites. Negative correlation was observed between dehydrogenase activity and the distance from the chromium slag heap, however, the activities of catalase, polyphenol oxidase, alkaline phosphatases in soils from the three sampling sites mentioned above did not differ significantly. The result imply that of dehydrogenase activity could be used as an indicator for the chromium pollution level in the area of Iron-Alloy factory and for the stability level of the soil ecosystem.

Jan 1, 2008

By Raj P. Singh

Applications of cementation in the recovery of metal ions from process solutions have been known for a long time. Cementation reactions involve electrochemical precipitation of a noble metal from solutions of its salts on a more electropositive metal which, in tum, progressively dissolves. For example, addition of zinc metal powder in a solution containing zinc and cobalt ions would allow for the precipitation (separation) of cobalt according to the following chemical reaction. This paper pertains to the recovery of cobalt from cobalt process solutions via a cementation reaction on aluminum shavings (metal scraps from cans etc). Specifically, we report on the characterization of cobalt process solutions, a by-product obtained from cobalt chemicals, and the kinetics of cobalt, nickel and manganese cementation from process solutions on aluminum shavings.

Jan 1, 2000

By Zenjiro Asaki, Teruo Tanabe

"To clarify the formation of light rare earth (R =Ce, Pr, Nd or Sm) -Fe compounds in the reduction-diffusion (RD) process, two kinds of experiments were carried out: (a) RD experiment in which briquettes composed of R oxide powder, Fe (particles or wire) and CaH2 were reacted, and (b) immersion experiment, where an Fe plate was immersed into R-Fe melt having the composition of Fe-side liquidus line in Fe crucible. The compound formation was examined by using XRD, SEM and EPMA. The formation rates of RzFe17 measured by the RD experiment were compared with those obtained by the immersion experiment. The growth rates of compounds obtained in the RD experiment for Pr-Fe and Nd-Fe systems were much lower than those obtained in the immersion experiment. This result was explained by the difference of the reduction rates of R oxides by Ca. The parabolic rate constants for the formation of RzFe17 were separated in two groups of (a) Pr-Fe and Nd-Fe systems and (b) Ce-Fe and Sm-Fe systems. This was discussed in connection with the difference of their crystal structures and the driving force of diffusion. The parabolic rate constants for the formation of compounds in Ce-Fe and Sm-Fe systems decreased in the order of RFez, RFe3 and RzFe17.IntroductionTo understand reaction behaviors in the production of rare earth (R) -iron intermetallic compounds, which have excellent magnetic properties, is very important from engineering point of view. And the reduction-diffusion (RD) process<O has recently attracted attention as one of the promising processes to economically produce R-related materials. A few fundamental studies on the compounds formation in the RD process have previously been reported. Qi, Hino and Yazawa(2) observed the formation of R(Nd, Sm)-Fe and R-Co compounds in the process from various view points. Song and Ogawa(3) measured the growth rates of Nd-Fe and Sm-Fe compounds by using Nd or Sm vapor supplied from Nd-Ca or Sm-Ca melts. The authors have also carried out fundamental studies (4)-(8) to clarify the rate and mechanism in the production of R-Fe intermetallic compounds."

Jan 1, 1998

By H. Fukuyama

The wetting behavior of single crystalline MgO by fayalite-type slag melts has been studied by the sessile drop technique incorporated with high temperature X-ray radiography. The experiments were performed under oxygen partial pressures of 10-6 and 10-4 Pa at 1473 K. Mass ratios of iron to silica, Fe/Si~, in the slag employed were 1.4 and 2.0. To investigate the interfacial reaction, experiments using high density MgO crucibles were also conducted. The reactions at the interfaces were examined by Electron Probe Microanalysis. The contact angles between the slag melts and the MgO substrates were found to be relatively low, ranging from 30 to 10 degrees. The surface tension of the slag was 0.4 N/m for a slag of Fe/Si02 = 2.0. Two phases, magnesiowiistite and olivine, were observed at the interface. Interdiffusivity in magnesiowiistite solid solution was determined as a function of iron oxide content. Phase relations between magnesiowilstite and olivine, and the growth rates of both phases, are also discussed

Jan 1, 1996

By Takao Yasugi

The majority of copper in the raw material migrates to the de-copperized dross that forms when the crude lead produced in the blast furnace is treated in the de-copperizing process. The de-copperized dross is treated in the electric furnace producing matte, speiss, and crude lead. The de-copperized dross also contains the silver. Therefore, it is important to improve the rate of silver migration to the crude lead. For this reason, the behavior of silver between the matte, speiss and crude lead phases was examined. At the same time, several tests to improve the percentage of silver migrating to crude lead were conducted.

Jan 1, 2003

By Varadarajan Seshadri

A physical model based on similarity principles was constructed for simulating the RH degasser of CST (Companhia Siderurgica Tubarao, Vitoria, ES, Brazil) to evaluate the circulation rate of the metal which essentially defines the degree of exposure of the metal to vacuum in the chamber and thus of the refining rate. The circulation rate on the other hand will influence the decarburization rate and removal of dissolved gases like nitrogen and hence it is essential to optimise this parameter to get maximum refining efficiency with minimum refming times, thus improving the productivity of the secondary refining process. Mixing characteristics in the ladle is evaluated by pulse tracer addition using conductivity-meters located at the down leg as well as at several locations in the ladle. The influence of gas injection through nozzles in the upleg with simultaneous bottom injection of gas as well as nozzle blockage on the circulation rates were investigated. Also simulation experiments of kinetics of decarburization were carried out using C02 adsorption-desorption process in sodium hydroxide solution as circulating fluid and the effect of, bottom gas flow rate in this case was also evaluated. The results were carried over to prototype and to optimize the process.

Jan 1, 2003

By Chan. C. L., Zehr. R., M. M. Chen, J. Mazumder

"Two three-dimensional models of a surface tension gradient driven flow during laser surface heating are developed. The first model is based on a perturbation solution. The basic solution corresponds to the stationary axisynwnetric case and perturbation is based on a small scanning velocity. The advantage of seeking a perturbation solution, as it turns out, is that the three-dimensional flow is modeled by two sets of two-dimensional equations which are presumably much more tractable than the original three-dimensional equations. Numerical solutions are obtained and discussed. The second model is a full three-dimensional numerical solution of the Navier-Stokes equations, using a point-by-point partially vectorized iteration scheme. Surface shape is also determined in a self-consistent manner. The effect of the presence of convection on pool geometry, cooling rate and solute redistribution is presented and discussed.IntroductionThe existence of fluid flow and convection and their effects were first reported in the fifties (1,2). The role of convection in controlling pool geometry such as pool shape, undercut and ripples, and defects such as variable penetration, porosity and lack of fusion and weld properties such as weld homogeneity and bead formation is studied by a number of researchers and is reviewed by the authors in a recent paper (3).Recently, surface tension gradient driven flow has been identified as one of the forces responsible for convection within the molten pool (4,5). It is postulated that surface tension gradient driven flow is responsible for the surface ripple formation in the weld pool (6-8). Oreper, et al. (9) developed a two-dimensional convection model. Buoyancy, electromagnetic and surface tension gradient forces were considered. The formulation was based on a specified pool profile. It was found that the surface tension gradient is the dominant force in most cases. However, the solid-liquid interface is not known a priori. In fact, the solid-liquid interface, i.e. the pool shape, is a piece of information that the model should be able to predict. A two-dimensional transient self-consistent (i.e. the solid-liquid interface is solved as part of the solution] model for laser surface melted pool was first developed by Chan, Mazumder, and Chen (3)). This model predicted a non-uniform cooling rate, hence non-uniform microstructure. Depending on the Prandtl number (i.e. material) and surface tension number, the shape of the molten region as well as the cooling rate changes. It was also predicted that the recirculating velocity is of one or two order of magnitude higher than that of the scanning velocity. This model provides the detail of the flow field and heat transfer on a plane perpendicular to the scanning direction. However, the front-to-back motion and its effect on heat transfer also play important roles in the physical process, especially for the fact that the recirculating velocity is so much higher than the scanning velocity. Such a motion cannot be obtained from two-dimensional models."

Jan 1, 1986

By Jorge Alberto Soares Tenório, Romano Espinosa, Felipe Fardin Grillo, José Roberto de Oliveira, Denise Crocce

"The aim of this work was evaluation of the recovery of Zn and Fe of the EAFD added to the hot metal in the form of briquette at temperature of 1500°C. The EAFD was agglomerated by cold briquetting and introduced in the hot metal. This study utilized a bench-scale equipment to melt, during this process to kept a flow rate of inert gas above the bath. Were collected periodically metal samples and the samples were analyzed for determination of the content of total silicon and carbon by chemical analysis. Zinc oxide, zinc ferrite and other oxides were reduced and were volatized and collected by a cleaning system of dust (baghouse) located on top of the oven. More than 98% of iron were recovered from EAFD during the test. It was possible to produce a dust containing about 68% zinc by means of adding of EAFD.IntroductionIn the first semester of 2010, steel production was about 706 million tons, 27.9 % more than in the first half of 2009. Not a significantly increase if 2010 data is compared with the first semester of 2007 (only 7.2 % higher), before the world’s economic crises. Steel production is divided into two main routes. The first one, and most used, is the Basic Oxygen Furnace Process (BOF process), which in 2008 accounted for approximately 67.1 % of steel production. The second route is carried out in the Electric Arc Furnace (EAF) that in 2008 represented 30.6 % [1 ].Electric arc furnace dust (EAFD) is a solid waste generated during the steel making process. It is classi?ed according to NBR 10004 as dangerous solid waste-class I, because the elements Pb e Cd leach in water exceeding the maximum limits permitted by the NBR 10004 [2 ]."

Jan 1, 2012

By Mingming Zhang, Mallikharjuna R. Bogala, Ramana G. Reddy

Steelmaking desulfurization slag samples were characterized using chemical, X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) methods. The objective of this work is to investigate the occurrence of sulfur and phosphorus components in the slag samples and to identify their origin and associations with the iron phases. Thermodynamic calculations results confirm the presence of phosphorus and sulfur components in the slag sample at high temperatures (1400 to 1800oC). The main constituents of slag include Ca3SiO5 (28.1%), MgO (9.31%), Ca3(PO4)2 (9.18%), CaS (8.39%) and CaO (5.68%). The major phosphorus and sulfur components of the slag are Ca3PO4 (99.2%) and CaS (79.3%) respectively. Characterization studies indicate the presence of microparticles of different sizes and shapes in the slag sample. Elemental analysis of these particles confirm the presence of major elements (O, Mg, Al, Si, S, Ca and Fe) in the slag sample.

Jan 1, 2015

By Singareddy R. Reddy, Ramana G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. An expression for the activity coefficient of a dilute solute, 2(oxygen), in a binary solvent 1-3 is derived. It is used to calculate the logarithmic activity coefficient of oxygen in Pb-O-Gu, Pb-O-Bi, AgO- Sn, Pb-O-Sn and Ag-O-Pb metallic systems. Self interaction parameter of the solute is derived from the partial Gibbs energy of solute using constant compositional path. The derived equation is used successfully to deduce the self interaction parameter of oxygen in Pb-O-Gu and Pb-O-Bi metallic systems. The predicted thermodynamic parameter data i.e activity coefficient and self-interaction parameters are in an excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionThe nature of solute interactions such as oxygen, nitrogen and sulfur with the metallic solutions are important for a number of chemical and metallurgical processes. Several theories [1-23] have been developed to evaluate fundamental thermodynamic properties of solutes constituting two elements. The activity of solutes has been calculated using statisticalor quasi- chemical approach.Wagner's [4] Ideal Solvent Model is based on one energy parameter to describe the compositional dependencies of the activity coefficient of nonmetallic solutes such as oxygen in binary metallic solutions. This model depends on a constant energy of interaction for the exchange of atoms from the coordination shell of an oxygen atom to the shell of an interstitial site and cannot account for properties of strongly interacting systems [4]. Therefore, several attempts have been made to improve the Wagner's model for the strongly interacting systems. [10-16]."

Jan 1, 1996

By John J. Moore

This paper discusses the application of a video technique to construct stability diagrams for the combustion synthesis of ceramic-metal composites. Several model exothermic combustion synthesis reactions have been used to investigate the effect of the reaction parameters, eg. stoichiometry, green density, etc, on the stability of the propagating combustion reaction front and subsequent product morphology. The effect of varying the reactants and their stoichiometry to provide a range of reactant and product species ie. solids, liquids and gases, in the synthesis of both dense and expanded (foamed) ceramic and ceramic-metal composites was also investigated with respect to their corresponding combustion front stabilities.

Jan 1, 1993

By Denise Corrêa de Oliveira

Common dry batteries use zinc as the negative electrode. Producers commonly use additives such as mercury to prevent corrosion and to increase the mechanical resistance of the zinc anode. Alkaline batteries also contain it, as an anti-corrosive agent. When mixed with the common municipal solid waste, heavy metals as zinc and mercury pollute soil and ground water supplies, moving to the food-chain and affecting human health. Due to these possible damages, this kind of waste must be properly disposed, or recycled. Thus, even in low amounts (ppm) in batteries, mercury has to be eliminated or, at least, its content should be reduced. This work presents the use of pyromettalurgical processes, to reduce mercury content and recover zinc. The tests involved batteries treatment at temperatures from 300° to 1000°C. Mercury is eliminated up to 650°C, and zinc is evaporated at higher temperature treatment. C

Jan 1, 2001

By J. -S. Park, H. -S. Jeon

This study has been carried out to develop a relatively simple hydrometallurgical process for recovering nickel as nickel sulfate from the spent nickel-cadmium battery residue in which cadmium was removed by vacuum distillation. This residue is composed of 36 % nickel, 20 % iron, and other metals such as cobalt. First, crushing and selective classification were performed to separate iron to produce a nickel-rich product (over 40 % nickel). This product was dissolved in sulfuric acid to obtain a nickel sulfate solution. During the dissolution, nitric acid and air were added to the system to enhance the iron oxidation reaction rate. The free acid remaining in the dissolved solution was neutralized by adding nickel carbonate. Iron was precipitated as iron hydroxide and removed from the solution. The nickel sulfate solution was then fed to a vacuum evaporator to concentrate the solution by evaporation of water and crystallized at around 45°C to obtain nickel sulfate hexahydrate. A recrystallization process could remove other impurities such as zinc and manganese.

Jan 1, 2000

Physical and chemical properties of the salt flux phase play a significant role in the recycling of UBC in Aluminum melting processes. Particularly knowledge of several properties such as salt vapor pressure, melting temperature, loss of aluminum, corrosion of refractories are useful for the process control decisions in order to attain a good quality of aluminum produced. A literature review and analysis of several salt flux systems for the selection of a flux for the Aluminum melter (low temperature natural gas bath melting) process were made. Based on these analysis two salt flux systems are recommended for further studies. These are NaCl?KCl?LiF system and NaF?LiF?KCl system with small amounts of other salt additives. Application of these fluxes to Al industrial processes are discussed.

Jan 1, 1996

By Katsuya Kase, Kaname Takeya, Keaji Ohmori, Yoshiyuki Asakawa

"The reduction-diffusion process (the R-D process) using Ca as a reducing agent has been practiced in industry in the production of the SmCos type, the Nd-Fe-B type and the 1b-Fe-Co type magnetic materials. The advantages of the R-D process are the generally high yield of rare earth metals and the single-stage conversion of a mixture of oxides and metal powders into a product of rare earth alloy powders. On the other hand, one of its disadvantages is the slightly high contents of oxygen and calcium. This disadvantage is remarkable in the Nd-Fe-B type. Singe-phase Nd2Fe14B alloy powders with low content of 0 and Ca, is obtained by choosing appropriate raw materials and performing the R-D process in a controlled way. These alloy powders are very suitable for the production of Nd-Fe-B sintered magnets and expected higher magnetic properties by adopting advanced magnet production method.IntroductionThe hard magnetic rare earth transition metal intermetallics, especially, have attained considerable technical importance. Examples are the alloys based on the intermetallics SmCo5[1], SmC017[2], NchFet4B[3], or the recently developed alloy SnuFe11Nx[4]. The reduction-diffusion process using Ca as a reducing agent has been well known as an economical method of producing rare earth based magnet materials[5]. The reduction-diffusion process has been practiced in industry in the production of the SmCos type, the Nd-Fe-B type and the 1b-Fe-Co type magnetic materials. The advantages of the reduction-diffusion process are the generally high yield of rare earth metals, the single-stage conversion of a mixture of oxides and metal powders into a product of rare earth alloy powders, the elimination of the crushing process of the alloy ingot, the inessentiality to special equipment, etc. On the other hand, one of its disadvantages is the slightly high content of oxygen and calcium. This disadvantage is remarkable in the Nd-Fe-B type. An outline of basic studies of the reduction-diffusion process was reviewed from the particular viewpoint of the production of magnet materials by Ogawa [6]."

Jan 1, 1998