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By Shulan Wang, Xuan Liu, Li Li

"Electrochemistry of Fe(III) in 69CaCl2-12CaF2-19KF and 81CaCl2-19KF (mole percentage, %) was investigated at 827 oC on molybdenum electrode by cyclic voltammetry, chronoamperometry and galvanostatic electrolysis using Fe2O3 as the Fe(III) source. The reduction of Fe(III) to Fe was conducted in one step and controlled by diffusion process. Fe(III) shown greater reduction rate and diffusion coefficient in molten 81CaCl2-19KF than in 69CaCl2- 12CaF2-19KF. Galvanostic electrolysis of Fe was performed in both molten salts with a cylindrical cathode rotating at 200 r/min and dendritic iron deposit was obtained.Keywords: iron; electrolysis; electrochemistry; molten saltIntroductionThe production of iron and steel causes huge emissions of CO2. Iron electrowinning in molten salts with dissolved Fe2O3 using an inert oxygen evolving anode is an alternative process to reduce or eliminate the formation of CO2. Research on novel process of producing metal has been reported recently [1-2] by using CaCl2 as the main electrolyte and dissolving CaO in CaCl2 due to the high solubility of CaO in the melt. This process has been used in preparing many active metals and alloys [3-14]. In the present work, the electrochemical behavior of iron in CaCl2-KF was studied and transport property of iron ion in the melt was discussed.ExperimentalCaCl2,CaF2 and KF (in analytical purity) were dried in air for 48 h. Mixed salts used in experiments were placed in a graphite crucible (??58 mm inner diameter). The graphite crucible together with the salts was heated at 473 K for 12 h in a furnace with flowing Ar (99.99%) before further heating. Temperature inside the furnace was measured by an S type thermocouple. Electrochemical measurements, such as cyclic voltammetry and chronocoulometry, were performed in a three electrode cell by EG&G PAR273A potentiostat/galvanostatand. Galvanostatic electrodepositon of iron was conducted in a two electrode cell. Molybdenum (??2 mm) and iron (??5 mm) were used as the working electrode (WE) and the reference electrode, respectively. A graphite crucible and a magnetite rod (??25 mm ) consisted of 100% magnetite and sintered at 950 oC in argon atmosphere for 2 h with electrical conductivity of 366 O-1m-1 at room temperature were used as the counter electrodes in the galvanostatic electrolysis experiment. Carbon (??10 mm) was used as the counter electrode in electrochemical measurement. The deposits were washed in distilled water bubbled with argon and dried in air before being characterized by X-ray diffraction (PW3040/60 diffractometer) and scanning electron microscope (SEM, SSX-550)."

Jan 1, 2014

By Michael Heximer, Dominic Verfielst, Timothy Moore

"Teck's Trail Operations recently installed new pressure filters in the cold stage purification step in the zinc leaching plant. Alloy 2205 duplex stainless steel was chosen as the material of construction as it was in use in the hot stage purification operation. Within a year of commissioning, an unacceptably high rate (greater than 1 mm/y) of corrosion was observed on the weld heat affected zone (HAZ). Laboratory and field tests were conducted to establish the conditions under which the corrosion was occurring. The tests isolated the aggressive conditions to a unique combination of materials present during the filter regeneration stage. Furthermore, the change of the duplex grain structure of the alloy during welding resulted in the HAZ being more susceptible to the corrosive environment. A new material of construction was recommended as a result of the investigation.IntroductionThe sulphide leaching plant uses four horizontal tank pressure leaf filters to remove solids precipitated in the cold stage electrolyte purification process. The current filters were installed in 2007, and replaced a bank of filter presses. The material of construction for the filters - alloy 2205 duplex stainless steel - was selected based on its successful use in similar service areas of the leaching plant. However, within the first year, unexpected and rapid corrosion of the filter tank material was observed. Although moderate general corrosion was noted throughout the filters, the attack was particularly aggressive in the areas where intense heat was applied during fabrication, observed at the HAZs caused by welding, and on the exposed edge grain of the duplex plates. On the inaugural annual inspection of the filters in the first year of operation, a corrosion penetration rate of 1.0 to 1.5 mm/y was observed at the HAZs. The parent plate of the pressure tank was a minimum of 6 mm, with a minimum allowable thickness of 3 mm under the ASME pressure tank design rules. Therefore, the projected useful life of the filters could then be roughly calculated to be two to three years. Urgent action was required to understand and correct this problem."

Jan 1, 2012

By Linli Wu, Guangchun Yao

"The influence of deformation on the properties of short-carbon-fiber reinforced 2024 alloy matrix composites was investigated in this study. It was found that the distribution of carbon fibers changed from the random state before deformation to the ordered state that carbon fibers arranged along the direction of rolling and extruding after deformation. Under the temperature range in control, the increase of rolling and extruding temperature would benefit to improve strength and elongation of composites, but was not conductive to improve the hardness of composites. With the increment of total deformation, all the strength and the hardness of composites became greater, nevertheless the elongation decreased. After being rolled and extruded, the strength and the hardness of composites were all bigger than those of composites before being rolled and extruded; moreover, the strength of extruded 2024 alloy matrix composites was higher than that of rolled 2024 alloy matrix composites under the same heat treatment conditions.IntroductionCarbon fibers have been reckoned as very important reinforcements due to the high specific strength, specific modulus, high thermal and electric conductivity, low expansion coefficient and good self-lubricant properties [1-4]. Light metal composites reinforced with carbon fibers, such as carbon fibers in an aluminum matrix, are widely used and studied. Some studies have concentrated on the interfacial characteristic of CF/Al composites in order to search for the way of improving the bonding between carbon fibers and the matrix alloy [5-8], and on the influence of the carbon fiber percent composition in the composites [9-11]. Some researchers began to take interest in the deforming characteristic and failure behavior of carbon fiber reinforced metal matrix composites [12-16]. However, the same with other metal materials, most of CF/AI composites were prepared by some single processes, such as powder metallurgy, extrusion casting and vacuum press infiltration, which caused that the composites products could not be manufactured directly. In order to cover the shortage of the mentioned above processes and get composites products with perfect mechanical properties and dimensional accuracy, the composites should be reworked by rolling, extruding or forging process. Compared with research about manufacturing process, the correlative investigation on the reworking of CF/Al composites was much less evidently, which restricted the application and the further development of CF/Al composites."

Jan 1, 2012

By F. Qian

Direct impingement of molten metal baths by a gas jet is commonly encountered in such processes as BOF and electric arc furnace steelmaking. Shape and local fluid mechanics in the impinging region is important because it determines the interaction of the metal pool with the surroundings. Goal of the present work is to characterize and understand the interfaces at the impinging region. Using a physical model consisting of water/corn oil and water/kerosene as surrogates for metal/slag, interface shapes for slag-gas, slag-metal and metal-gas are investigated. Influence of transport properties of the two liquids on the shape and flow fields are also experimentally determined under various impinging jet conditions, namely jet momentum and jet height. The viscosity of the slag layer (corn oil or kerosene) has the most significant effect on the interface shape and the induced flow fields. The interface shapes were measured both photographically and by using a surface- tracking resistance probe. The limiting condition at which the jet breaks through the corn oil or kerosene layer and reaches the water layer was determined experimentally

Jan 1, 1994

By Keiji Okumura, Hong Lan, Masamichi Sano

"Magnesium has been well known as one of the excellent agent of desulfurization, deoxidation, etc. in iron- and steelmaking because of its high reactivity. Since its production is energy nitensive, the price is very high. Thus magnesium has not widely been used as an agent in metal refining ·processes. In the present work, reduction of magnesia by carbon and aluminum is examined. Because the reaction is very sensitive to temperature, non-isothermal technique is applied to investigate the reaction kinetics. The effects of heating rate .and reaction interface area on the reaction kinetics .are studied. .A kinetic model is proposed based on the experimental results.IntroductionFor the metal refining processes, the production of high purity metal has been one of the most important research subject. In order to produce the high purity metal, the amount of the refining agent and the consumed energy is increasing. Therefore, if the future earth environment is taken into consideration, the further efficient and energy saving processes are required. Generally, Cao slag has mainly been used for desulfurization of molten iron as a desulfurization agent. However, environmental problems, such as recycling of disposal slags, are still unsolved. On the other hand, the deoxidation of molten steel is mainly performed by addition of aluminum. Therefore, the alumina inclusions· remain in. molten steel and the great efforts have been made to the removal of the inclusions. The affinity of magnesium with sulfur and oxygen is strong, and magnesium is well known as a powerful desulfurization and deoxidation agent. However, magnesium has been seldom used for the steel' refining process. The following reasons are considered. Generally, magnesium is expensive. And at iron- and steelmaking temperatures, the refining efficiency becomes low due to its abruptly .evaporation."

Jan 1, 2000

By John J. Jonas, Sang-Hyun Cho, Ki-Bong Kang

"The recrystallization behavior of Nb micro alloyed steels containing Cr, Mo, Ni and Ti. was studied using hot torsion testing with the aim of modeling the recrystallization processes and the mean flow stress taking into account the microstructural behavior during hot rolling. The kinetics of static and metadynamic recrystallization were characterized and appropriate expressions were formulated for the recrystallization kinetics. These are shown that the recrystallization kinetics depend on steel composition and the processing conditions. The stress-strain curves were determined in order to derive new equations for the peak stress, peak strain, mean flow stress and softening kinetics. The peak strain is influenced by the presence of alloying elements; their addition, which has a solute drag effect, retards the rate of grain boundary motion, shifting the peak to the right. The addition of Nb to the steel results in a significant increment in the activation energy for hot deformation, and Mo has smaller effect than Nb, but Cr has the opposite effect. It was also found that the deformation activation energy in these steels was not altered by the addition of Ni. The rate of metadynamic recrystallization increases with strain rate and temperature and is observed to be independent of strain, in contrast to the observations for static recrystallization.The mean flow stress (MFS) calculations, based on the Sims analysis, are then compared with the predictions of a model based on an improved Misaka mean flow stress equation in which solute effects, strain accumulation, as well as the kinetics of static and metadynamic recrystallization are accounted for. Good agreement between the measured mean flow stresses, which is obtained from the mill logs of POSCO Kwangyang #3 HSM (hot strip mill), and 'predicted ones is obtained over the whole range of rolling temperatures. The results demonstrate that dynamic recrystallization followed by metadynamic recrystallization, supported by the unexpected load drops, sometimes occurs for the rolling schedules studied in the present analysis."

Jan 1, 2001

By James O'Brien, Lyman Frost, S. Elangovan, J. Stephen Herring, Joseph Hartvigsen, Carl Stoots, Anthony Nickens

"Carbon dioxide recovered from concentrated sources, such as metallurgical reduction furnaces, cement kilns and fossil power plants can provide a valuable feedstock for a synthetic fuels industry based on energy from nuclear, solar, wind and hydropower sources. High temperature co-electrolysis of CO2 and steam to produce synthesis gas has been demonstrated using reversible solid oxide fuel cell technology. Where a source of high temperature process heat is available, such as from an advanced high temperature nuclear reactor or solar dish concentrator, the endothermic electrolysis reactions can utilize both thermal and electrical inputs in such a way that the conversion efficiency within the cell is 100%. Synthesis gas produced in a coelectrolysis cell has been further reacted over a catalyst to produce conventional hydrocarbon fuels. Widespread implementation of synfuel production from CO2 will enable a much larger reliance on intermittent renewable energy than can be accommodated by conventional electric demand profiles.IntroductionFor the past several years, Ceramatec, Inc and the Idaho National Laboratory (INL), have been studying the feasibility of high temperature solid oxide electrolysis for large-scale, nuclearpowered hydrogen production under the U.S. DOE’s nuclear hydrogen initiative (NHI) as an alternative to the thermochemical process. Parallel to this effort, the INL and Ceramatec have been researching high temperature co-electrolysis of mixtures of steam and CO2 to produce syngas:"

Jan 1, 2008

By Robert Vidal

A model of the homogeneous chemistry and transport processes within the separator of a chrome-alum electrowinning cell is introduced, discussed, and compared to experiment. The influence of diffusion, electromigration, and convection are included; it is found that convection was the dominant mode of transport for the experimental conditions. Simulation results explain experimental observations concerning an apparent disappearance of dichromate ions produced at the cell anode. The relation between potential drop across the diaphragm and the current and fluid flow is also illustrated. The model is used to recommend future experimental and theoretical work.

Jan 1, 1994

By P. D. Ferro

The direct oxide reduction (DOR) of plutonium oxide generates significant amounts of contaminated waste. This waste primarily consists of calcium oxide-saturated calcium chloride salt. This investigation explores the possibility of recycling the salt, by the electroreduction of the calcium oxide. Fused salt electrolysis of a simulated salt mix (CaC12 + ~10 wt. pct. CaO) is being carried out to electrowin calcium, and the process is being optimized in terms of the calcium solubility, cell temperature, current density and cell design to maximize the current efficiency. This work identifies the major concerns in the development of a process to electrowin calcium from this simulated salt mix.

Jan 1, 1992

By N. A. Vatolin, L. I. Leontjev, S. V. Shavrin

The ever growing interest to the complex iron ores may be attributed to possible production of the naturally alloyed metals and the efficient recovery of the associated elements. However, the conventional technique for complex ore processing is complicated and in some cases even impossible. A pyrometallurgical benefiation of such ores without melted slag formation has been advanced. A version of the technique assumes pellet production with metal coagulated within a slag shell on grinding the pellets, the metal phase is mechanically separated from the slag shell. The technique has been run up with ferro chromo nickel, high-titanium, high-magnesia, alumina phosphorus ores and concentrates. Another version of the pyrometallurgical benefication without melted slag formation in a rotary kiln has been developed from the schemes for processing red mud of alumina manufacture and high-titanium concentrates. Means have been put up to improve schemes available for lex iron ore processing with primary emphasis on material pretreatment before blast furnace and steelmaking processes. Vanadium-bearing titanomagnetite conentrate oxidized pellets possess low strength at reduction. The technique suggested for pelletizing in the controlled atmosphere improves the afore said pellet metallurgical properties. Prodution of metallized pellets in a conveyor roasting machine holds considerable promise for blast furnace and steelmaking processes. In processing the high-sulphur iron ores still another technique is proposed to roast the fluxed pellets with 95% and more desulphuration.

Jan 1, 1988

By U. Meyer, A. Alonso, P. Banios

The sampling of cathodes has changed with the introduction of the ISA-process in copper refineries. A Jernkontoret joint working group of refineries and rod plants from both primary and recycled copper plants has been investigating whether the actual sampling of cathodes is representative for this type of cathodes. As a first stage, samples were sent to the members of the working group with the objective to find an easy basis for a comparison of the results of the next stages. All samples show the same tendency for nearly all elements. In some cases, there may exist differences in calibration and for some elements the detection limits are too high, especially when Optical Spectrometry is used. In the second stage, discs were compared with melted samples to answer the question whether the punching of discs is sufficient for the quality control of the cathode. The analyses of the discs represent fairly well the cathode quality. There are differences between cathodes from different crops. Three punches are sufficient to determine the cathode quality. Finally, samples from various lots of cathodes were compared with samples from the rod produced from these cathodes. The impurity content of the rod corresponds to the impurity content of the cathode.

Jan 1, 2000

By Harrison Hodge

In the Bayer process for alumina production, between 2–35% Al2O3 is lost with bauxite residue due primarily to incomplete dissolution of aluminiumbearing minerals during caustic leaching or the precipitation of sodium alumino-silicate solids. The recovery of sodium and aluminium from the residue, and particularly from the contained sodium alumino-silicates, is becoming an increasingly critical issue from both an environmental and economic standpoint. Lime-soda residue sintering followed by selective leaching has been proposed as a method to recover sodium and alumina. The factors influencing the sintering mechanisms and kinetics, and the subsequent leaching have not been well described to date. In this study, the physical and chemical changes taking place during isothermal sintering of bauxite residue in air, particularly at short reaction times are investigated using scanning electron microscope (SEM) and X-ray diffraction (XRD). The impacts of these changes on the recovery of valuable materials are reported.

By Tian Tang, Sergio D. Felicelli

"The laser cladding is an important surface treatment for enhancing resistance against corrosion, abrasion, and wear. The focus of the present study is to develop a three dimensional finite element model to analyze the temperature history and thermal stress evolution during multi-pass laser cladding process on H13-H13 tool steel sample. A sequentially coupled thermal-stress analysis methodology was adopted in this study. The thermal model was firstly established to investigate the temperature history of the laser cladding process. Then the temperature history was used as input to mechanical model to calculate the thermal stress evolution during the process and the residual stress after the sample completely cooled down to room temperature. The influences of process parameters including the scanning speed and scanning strategies on temperature history, thermal stress evolution, and residual stress were investigated in details.IntroductionLaser cladding is an advanced material process technique, which is often used to improve mechanical properties or increase corrosion resistance, repair worn out parts, and fabricate metal matrix composites. In this process, the injected powder or wire feedstock material and a thin layer of substrate are melted and consolidated by use of a laser in order to coat part of a substrate or fabricate a near-net shape part.Numerous mathematical models have been established for analyzing the effects of process parameters, microstructure evolution, and thermo-mechanical behavior of laser cladding. Zhou et al. [1] established an analytical model to investigate the laser induction hybrid rapid cladding for Ni-based WC composite coatings. Huang et al. [2] also developed an analytical model to theoretically investigate the interaction between the laser beam and the powder stream of laser cladding process. A simple and realistic model of laser cladding was proposed by Picasso et al. [3]. The cladding layer is very sensitive to cracks due to the accumulation of residual stress, caused by non-uniform temperature changes, which have limited the wide application of laser cladding technique in industry. Recently, fmite element method has been increasingly used to simulate the laser cladding process [ 4-6]."

Jan 1, 2014

By Animesh Jha, Catherine Davey

"Carbothermic reduction and nitridation reactions using synthetic kaolinite mineral were investigated for the formation of silicon based nitrogen ceramics. The temperature dependence of the reaction rate and its effect on phases formed are reported. The effect of the reactivity of carbon on the kinetics of formation of AIN and ShN4 is discussed. Using the standard Gibbs free energy values for the formation of nitrides and oxides of aluminium and silicon, a log po2 verses I/T diagram is constructed. The experimental data results are discussed and compared with the predicted phase equilibria. We also report the influence of sub-oxide gaseous species on the microstructure of the ceramic phases produced.IntroductionSynthetic kaolinite is a clay containing alumina, silica and water of crystallisation, and has a chemical formula 3(Al2O 3.2SiO2.2H2O). This mineral is relatively inexpensive and, is therefore an ideal candidate for use in the production of ceramic powder mixtures for example silicon nitride and aluminium nitride for composite material formation, When the mineral is heated, the water of crystallisation from the crystal lattice is lost via the 3(Al2O 3.2SiO2.2H2O) = 3(Al2O3.2SiO2) + 6H2O reaction. It has been shown [1·2j that on further heating to 1673K, the anhydrous kaolinite decomposes to a mixture of mulllte and silica, 3(Al2O3.2SiO2) = 3Al2O 3.2SiO2 + 4SiO2 which is consistent with the alumina-silica phase diagram, shown in figure 1.The binary alumina-silica phase diagram has a well-defined sub-eutectic immiscibility dome and this characteristic dernixing behaviour is reflected in the thermal decomposition of anhydrous kaolinite consequently the microstructural features resemble the spinodal decomposition process. It is well established that the spinodal decomposition process raises the nucleation frequency due to their low free energy barrier, (?G). The small magnitude of this barrier consequently promotes the evolution of a very fine microstructure. The process of spinodal decomposition is therefore expected to be influential during the reduction-nitridation of kaolinite minerals."

Jan 1, 1996

By Yousef Mohassab, Feng Chen, Hong Yong Sohn, Mohamed Elzohiery

The determination of reduction degree in a DR process is sensitive to the total iron in the ore and DRI. An accurate and high throughput analysis method for total iron has been developed. Titration of the solution after tin(II) chloride reduction of ferric ion is a widely used method for iron analysis. However, it is a multistep method that requires many chemical reagents and much time. In this work, an ICP-OES analysis method with higher or equivalent accuracy compared with the titrimetric method was developed. This method has much higher throughput and demands fewer chemical reagents compared with the titrimetric method. In this paper, a comparison of the two methods is presented.

Jan 1, 2016

By Yusuke Kimura, Ken-ichi Yamaguchi

"Secondary materials have long been processed at the S-furnace of the Mitsubishi continuous copper smelting and converting process at Naoshima Smelter and Refinery. Intensive recycling in the recent years has formed concerns that impurities in the secondary materials may cause drastic changes in the chemical properties of the CL-slag, which is separated from matte in the smelting stage. Among various impurities included in secondary materials, the authors have studied the influences of sodium oxides in the CL-slag because the behavior of sodium oxide has scarcely been studied with respect to the copper smelting slag. The examinations have been applied experimentally on the distribution between slag and matte of arsenic whose acidic characteristics suggest strong affinity to sodium-oxide of basic characteristics in silicate melts. The results have been discussed by thermodynamic evaluations and the results of pyro-tests at the commercial furnace.IntroductionAt Naoshima Smelter and Refinery, the existing line of the Mitsubishi continuous copper smelting and converting process has been operated since 1991. The Mitsubishi Process consists of three furnaces namely the S-, CL- and C-furnace as shown in Figure 1. In the S-furnace, copper concentrate and powdery secondary materials (scraps, sludges, etc) are charged through the top lances with oxygen enriched air. The other secondary materials of lumpy shapes are charged through the chute installed on the furnace roof. Charged materials are smelted by the reaction heat in accordance with the oxidization of copper concentrate. The mixed melt of matte and slag overflows through the launder into the CL-furnace, where the melt is separated into slag and matte by the difference of their specific gravity. Matte is siphoned out and sent to the C-furnace and converted to blister copper continuously. The CL-slag overflows continuously through the slag outlet to be water-granulated. Granulated slag is sold as a raw material used for the cement production and so on. Various secondary materials have been processed at the S-furnace of Naoshima Smelter and Refinery. Intensive recycling in the recent years has formed concerns that the chemical properties of the CL-slag may change drastically due to impurities originating from secondary materials. Among various impurities included in secondary materials, the authors have studied the influence of sodium oxide in the CL-slag because the impact of sodium oxide has scarcely been studied with respect to the copper smelting slag. The examinations have been applied experimentally on the distribution between slag and matte of arsenic whose acidic characteristics suggest strong affinity to sodium-oxide of basic characteristics in silicate melts."

Jan 1, 2012

By Susumu Okabe

Mitsubishi Continuous Copper Converter employs the top blowing lance system for the continuous supply of reaction gases into the molten bath. In order to avoid the excessive refractory wear caused by the melt splash without loss of the reaction efficiency, the furnace design and the blowing condition should be optimized. Empirical equations which correlate the splashing rate on the' side wall with the dimensions of the furnace, lance position, lance size, gas velocity and bath properties were obtained by by the physical model study, and compiled into a computer program. The computer program is effectively utilized for the analysis of the actual operation and for the optimum design of new furnaces.

Jan 1, 1998

By Jan G. H. du Preez, C. Viviers, B. J. A. M. van Brecht, H. E. Rohwer, Nicole M. Sumter

"At the basis of metal ion separation lies some particularly metal ion specific chemical property which lends itself towards exploitation. This could be in the form of an anionic complex or a neutral chelate complex. In the former a cationic centre with a particularly high affinity for the complex will have to be designed. In the latter case a stereospecific chelate ligand containing the correct symmetry and type of donor atoms will have to be designed. In both above cases the ""active centre"" can be entered in a from that it can function in different media of hydrophobicity, eg a precipitant, a resin or a solvent extractant. Recent results obtained in this laboratory will be used to illustrate how the above variables can be exploited to develop improved processes for the separation of base metal and platinum group metals.IntroductionThe separation of metal ions in hydrometallurgy can be performed broadly speaking with two major aims. Firstly the separation/removal of a certain group of metal ions, either as a means of preconcentration or as a removal from effluent as part of a purification process and, secondly the removal of a specific metal ion from an industrial stream in order to produce a specific metal in a pure form. This latter operation is by far the most difficult of the two and is becoming more so in the light of the fact that the world is moving in the direction of lower grade ores and increasing pollution. Such a process can be divided into three essential parts, firstly the molecular one in which an active centre is required to obtain specificity, secondly a matrix within which this active centre must function, i.e. as part of a resin or solvent extractant and thirdly the design of the total system to optimize the realization of the operation."

Jan 1, 1996

By Takeo Fujino, Nobuaki Sato, Yarong Wang, Kohta Yamada

"Ternary mixed sulfides of some transition metals MTS3 (M=Ba, ·Pb, T=Ti, Zr) were synthesized by a relatively low temperature process using sulfur melt. The mixture of starting materials, such as, metals and/or binary sulfides and a large excess of sulfur was reacted in a vacuum-sealed Pyrex or quartz ampoule at 350- 600 °C for one to three weeks. After the reaction, the remaining sulfur was completely removed by a process composed of filtration of sulfur melt and followed dissolution in CS2• The binary sulfides impurities coexisted in the products were removed by rinsing the products in water and acetone. By using the above method, BaTiS3, PbTiS3 and BaZrS3 'Were obtained in pure form. The effect of addition of halides on the yields of these ternary sulfides were also discussed.IntroductionThere have been a vast number of studies on the preparation and physical and /or chemical properties of mixed metal oxides. As is well known, some of such compounds exhibit excellent materials properties, causing them for use in mechanical, electronic, magnetic and chemical devices. Not a few mixed metal sulfides show similar physico-chemical properties to those of the corresponding mixed metal oxides. However, the study of the mixed sulfide crystals is rather sparse mainly due to difficulties in preparing these compounds. In various methods which have been adopted for preparing mixed sulfides, the simplest method would be the solid-solid reaction of the component binary sulfides or elements. However, there are always diffusional constraints with regard to the reactions in solid phases causing it necessary to heat the reactants at sufficiently high temperatures, viz. 800-1200°C. On the other hand, some mixed sulfides are unstable at high temperatures or to change their materials properties due to sulfur nonstoichiometry and structural modification depending on temperature, i.e., synthesis of such compounds needs to be made at lower temperatures. Processing in alkali halide melts is hopeful to overcome the above problems but to obtain the halide melts the temperatures above ~ 600 °C is needed. Low temperature reaction has been carried out for the preparation of Hg1.24TiS4, which was formed by the ·combination of TiS2 and molten Hg metal at 320°C[l]. Reaction of WS2 with LiBH4 melt at 350°C yielded LixWS2[2]. These sophisticated methods, however, can be applied only to the vary special cases."

Jan 1, 2000

By Hideaki Tokuyarna

Recovery of metal such as V, Ni and Fe from oil fly ash is important for efficient use of natural resources and protection of environment. Leaching of metals from fly ash followed by ion exchange of leached metals has been examined to develop a process which can selectively recover V and Ni from the fly ash. Experiment of leaching with water, HCI, H2S04 and NaOH leads us to propose a two-step leaching process as an effective and mild operation. The first step is leaching with water for removal of Ni, Mg, A1 and Zn and the second step is leaching with acidic solution for the recovery of V. The metals V and Ni are then separated from other metals in each leached liquor by ion exchange. Advantage of this separation process is that acidic leachant can be reused, which contribute to save separation energy.

Jan 1, 2002