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By Hiroaki Kawamura, Takeshi Yoshikawa, Kazuki Morita, Yutaka Yanaba

"To develop an alternative metallurgical process for phosphorus removal in the production of solar-grade silicon (SOG-Si), slag treatment of metallurgical-grade silicon (MG-Si) was conducted, followed by acid leaching. Phosphorus-doped silicon alloy or MG-Si containing certain amounts of phosphorus and calcium was reacted at 1723 K and 1773 K with CaO--CaF2 of several compositions. Phosphorus removal from the molten silicon into the slag phase was confirmed by reduction to phosphide ions, P3-, and phosphate ions, P3-. These ions were separately determined using a wet chemical analysis method developed by ourselves. The highest phosphorus distribution ratio obtained was 2. 7 after reaction for 18 h with 17.5 mass% CaO--CaF2 slag. We then conducted acid leaching of the silicon and achieved removal of a large fraction (over 90 % ) of the phosphorus, which was much higher than that obtained by ordinary oxidizing slag treatment.IntroductionIn recent years, the production of solar cells has been increasing rapidly. Because of this, the demand for solar-grade silicon (SOG-Si) has also been growing rapidly. The development of lower-cost mass production processes is therefore needed to provide silicon feedstock. Phosphorus is one of the impurities in metallurgical-grade silicon (MG-Si). Because of its large segregation coefficient (kp = 0.35) [l ], it is difficult to remove phosphorus using a solidification refining process. Vacuum melting is considered to be a promising method for removing phosphorous from MG-Si [2], but the issues of high cost and large energy consumption have still to be resolved.Slag treatment is often used to remove impurity elements by oxidizing reactions during general oxidation refining processes. For example, phosphorus in molten steel is removed into a slag phase as phosphate ions, PO4 3-l-, by the following reaction:"

Jan 1, 2013

By Hongmin Zhu, Guihua Wang, Xiangsheng Wang

"The anode process of carbon electrode in fluoride melt was studied by voltammetry and chronoamperometry. Anode gases were analyzed by gas chromatography on-line during controlled-potential electrolysis. Two peaks were observed on the cyclic voltammograms. According to the results of gas chromatography, the first peak was corresponded to the discharge of residual oxide ions, with the formation of CO and CO2. Discharge of fluoride ions occurred at 4.1 V vs. Li+/Li, and leading to the anode effect. With the occurrence of anode effect, small amount of CF4 was detected. As the potential reached 4.5 V, CF4 and C2F6 gas evolution occurred, and the current increased to form the second peak.1.IntroductionIn the primary production of Aluminum and some rare earth metals like neodymium, a departure from normal cell operation known as anode effect results in the generation of perfluorocarbons (PFCs), which have high global warming potentials [1]. Owing to the pressure of environmental protection, considerable research has been carried out to clarify the mechanism of anode effect and PFC generation of industry and laboratory cells in the aluminum electrolysis system [2-9]. The common result on PFC generation is that the PFCs are emitted from Hall-Heroult cells only when they are on anode effect. In this article, we selected LiF, the main electrolyte for the neodymium electrolysis [10-11], to perform further investigation on the underlying kinetics of PFC generation and the nature of the reactions at the electrode.2. ExperimentalAll experiments were carried out in an alumina tube reactor, which was filled with high purity helium atmosphere. Spectrographic graphite crucibles were used, which played the dual role of molten fluoride container and the counter electrode. Lithium fluoride was analytical grade. The experiments were carried out at 900 °C."

Jan 1, 2011

By M. Vijayalakshmi, S. Saroja, C. Sudha, T. N. Prasanthi

"Ti-5Ta-2Nb alloy and 304L austenitic stainless steel were joined by explosive cladding process. Investigations on 'as received' explosive clad revealed high hardness very near the interface due to martensitic transformation of 304L steel base plate. To improve ductility, explosive clads were heat treated in the temperature range of 823 to 1073 K for 1 to 20 h. Consequent change in the microstructure and microchemistry of the clad interface was studied. No change in the interface microstructure was observed for heat treatment at 823 K. Increase in temperature lead to the formation of various reaction zones at the interface, their number and width increase with temperature and time of thermal exposure. Growth kinetics of the reaction zones was monitored and activation energy required for formation was calculated. From elemental redistribution profiles, effective inter-diffusivities of alloying elements were calculated as a function of concentration and activation energy required for inter-diffusion was evaluated.IntroductionFor engineering components exposed to highly oxidizing and corrosive environments, a titanium based alloy i.e Ti-5Ta-2Nb (Ti-Ta-Nb) is often chosen as a structural material [1,2]. For economic consideration, vessels and piping exposed to non-oxidizing conditions are fabricated from 304L austenitic stainless steel (304L SS). Hence, dissimilar joint of Ti-5Ta-2Nb alloy and austenitic stainless steel becomes unavoidable. Fusion welding processes are not suitable for joining Ti and Fe based alloys due to the propensity for the formation of intermetallic phases and subsequent reduction in the bond strength [3,4]. Hence, explosive cladding, a solid state welding technique, was used to achieve high integrity, corrosion resistant joints between the two alloys."

Jan 1, 2012

By A. Pagliero

The coulombimetric reduction method has been used as an evaluation technique for Pb-Ca-Sn anode corrosion in the LIX-SX-EW process. The proposed methodology involves three consecutive steps, i.e., cleaning, oxidation and reduction. They are carried out in the same experimental unit, in solutions containing 180 g/L H2S04 with and without the addition of cobalt. The authors have worked in a wide range of oxidation current densities, from 150 to 500 A/m2 for in a period from 0.5 to 120 hours. It can be concluded from the results that there would be a linear relationship between the applied electrical charge I*T (Coulomb) and the anode corrosion expressed as transformed Pb mass (mg), for solutions with or without the addition of cobalt. The exception is that for the last one the corrosion rate is 5 times faster, which was observed for every layer. From the evaluation of different corrosion layers, one can point out that its composition is mainly in the form of sulphate. In the presence of cobalt, about 67% of Pb would be as sulphate (PbSO4), about 27% as a basic oxide (PbO) and only 6% as oxide PbO2 on the surface. From this result, it appears that great transformations occurred in the metal/sulphate interface. Without the addition of cobalt, the proportion of oxide Pb02 on the surface increased up to 11.5%. According to the previous statement and considering that Pb was found mainly as sulphate, the authors recommend its determination be used as quality selection criterion. Its evaluation should be performed in the acid solutions with 200 ppm cobalt addition at an oxidation current density of 300 A/m2 for a period of 24 hours.

Jan 1, 1999

By I. Kim, J. C. Choi, W. D. Cho

"The effect of yttrium addition on the oxidation behavior of Fe3Al intermetallic compound was investigated in the range of temperature 800 to 1100 °C in 0.2 atm 02 in terms of oxidation rate and oxide adhesion. The oxidation rate of alloys, Fe-14.3 wt% Al and Fe-14.1 wt% Al-0.3 wt% Y, was nearly identical and the parabolic rate constant calculated as a function of temperature is Kp=5128 exp[-39506(cal/mol)/RT] mg2/cm4 hr.Rapid cooling and ultrasonic stress tests were carried out to test adhesion of scale formed on the alloys. While the oxide layer formed on the Fe-Al alloy without Y was found to be fragile and detached easily during the tests, the oxide layer formed on the Fe-Al alloy containing Y was protective, dense, and adhesive. The following two mechanisms were proposed to explain the adhesion improvement of Ah03 formed on the Fe3Al containing yttrium : (1) the addition of yttrium decrease generation of growth stress in alumina scale because the preferential diffusion of yttrium through grain boundary in alumina scale prevent internal oxidation of Al, one of main causes of growth stress, and (2) the second phase formed on the oxide scales prevents crack propagation through the scales, leading to better mechanical stability of the oxide scales.IntroductionIron aluminides have attracted the attention of many researchers as a candidate for use at high temperature because of their excellent oxidation resistance due to the formation of protective alumina scale. In order to resist aggressive environments at elevated temperatures, oxide scale formed on iron-uluminum alloy must satisfy the following three requirements : (1) thermodynamic stability (2) slow growth rate (3) adherence on substrate. According to Wallwork and Hed [l], the most suitable alloys for high temperature application are Fe, Ni, and Co alloys with the protection of Si02, Cr203, and Ah03 scales. While chromium oxide can vaporize as Cr03 above 1000 °C and silicon oxide may form low melting silicate [2,3], Alz03 has a high melting point and is the most stable among the three oxides thermodynamically [6]. In this respect, iron aluminides forming alumina seem to be most suitable for use at high temperature. However, alumina scale formed on the iron aluminum alloys tends to be easily spalled during oxidation due to the combination of growth stress and thermal stress."

Jan 1, 1998

By Shadia J. Ikhmayies

"Nanocrystalline fluorine doped tin oxide (Sn02:F) thin films were produced by the spray pyrolysis technique (SP) on glass substrates at a substrate temperature T, = 450 ° C. The hydrated stannous chloride (SnClz.2H20) was used as a precursor and ammonium fluoride (NH4F) and hydrofluoric acid (HF) were used as the doping compounds. A comparison between the compositional, morphological and optical properties of the films obtained by using the two doping compounds was performed by using scanning electron microscope (SEM) observations, energy dispersive spectroscopy by X-rays (EDAX) and transmittance measurements. It is found that the films prepared by using HF have larger grain size, and higher fluorine content than the films prepared by using ~- In addition these films have higher transmittance and higher direct optical bandgap energy. These results are interesting for the use of Sn02:F as a forecontact in CdS/CdTe solar cells.IntroductionTin dioxide is an n-type, wide bandgap semiconductor (about 3.5 eV) and in the form of thin films, it is a transparent conducting material, characterized by high optical transmission (80- 90%) [l]. Sn02:F is the most widely used transparent-conducting oxide material. The transparent-conducting thin films of this oxide are used as electrodes in a variety of optoelectronic devices, as heat mirror coatings in 'smart windows' for buildings, in automobile and airplane windshields, in incandescent light bulbs, in flat-plate and concentrating solar collectors. Tin oxide and zinc oxide, in thin film configuration are technologically important materials because of their applications in photovoltaic cells [2].Among various dopants for Sn02, fluorine is often preferred, because fluorine doping results in films with high transparency and good conductivity [3]. By exploring the literatures, it was found that different sources of fluorine were used to produce Sn02:F thin fihns, among which are ammonium fluoride (NH4F) and hydrofluoric acid (HF) are the most used. Some researchers used~ [2, 4-7] and others used HF [3, 6-8] for doping Sn02 films. Gordillo et al.[7] used both of NH4F and HF and showed that the resistivity of thin films obtained by using HF was lower than that of similar films obtained by using NH4F by a factor of 2.2. They also found that the films obtained by using HF have more random orientations."

Jan 1, 2013

By Tugba Basargan Çagatay Morall, Gülhayat Nasun-Saygili

"The aim of this study is to prepare the apatitic material using colemanite mineral (2CaO.3B2O3.5H2O) which was obtained from Eastern Anatolia, Turkey. For this purpose, colemanite mineral was reacted with different phosphate sources, namely, dipotassiumhydrogen phosphate, ammoniumhydrogen phosphate and ortophosphoric acid at various temperatures and time periods. Experiments were run in batch system. The apatitic material was prepared by a wet method and followed by heat treatment at various temperatures. Structure of the samples was analyzed by XRD, FTIR, XRF and SEM. The particle size analysis was also made for the result product. The experiments showed that reaction temperature, contact time and heating temperature are important parameters to transform the colemanite into apatitic structure. Reaction of colemanite with dipotassiumhydrogen phosphate and ammoniumhydrogen phosphate results in amorphous, non-stoichiometric hydroxyapatite type structure, while acid based phosphate source gives brushite and monetite type product before and after heat treatment, respectively.IntroductionBoron which has properties intermediate between metals and non-metals is a member of semiconductor group of elements. Its atom is very small and has three valence electrons. Boron exists in Earth's crust (from 5 mg/kg in basalts to 100 mg/kg in shale) and in the oceans (4.5 mg/l) [1]. Turkey has 60% of world's boron reserves which is mostly in the form of colemanite (2Ca0.3B203.5H20). Colemanite is the most important calcium containing commercial borate mineral with 5 mol of crystal water [2].Calcium phosphate cements are very useful for bone repair applications because of its chemical structure. They are injectable, easy to shape and can be maintained locally. Because of those reasons calcium phosphate cements are very effective to fill bone defects with an irregular shape [3]. Hydroxyapatite (Ca10(PO)6(OHh) is the major component of the bone (70 wt%). However, hydroxyapatite stoichiometry, composition and crystallinity differ in human skeleton system [4, 5].The main objective of the present work was to study the transformation of colemanite to apatitic material using different phosphate solutions at several time spans and temperatures. The experiments were run in a batch system, change in pH and also weight loss were measured after the experiments. Several analysis methods were used to investigate the chemical and structural changes."

Jan 1, 2012

By M. C. Ruiz

The conventional pyrometallurgical methods to treat copper sulfide concentrates include generally, one or more oxidizing steps where the formation of SO2 gas can not be prevented. From the economical point of view and the nature of some of the processes in which SO2 is produced, its complete capture is not feasible; therefore an important fraction is released to the atmosphere as fugitive emissions. In this research, the reduction of chalcocite was studied in the presence of lime as an alternative method, which overcomes the pollution problems related to SO2 emissions. The effect of temperature, time, concentration of carbon and CaO on the reduction rate were studied. Among these variables, temperature affects most the reduction rate. Conversions over 95 % can be obtained in less that 20 minutes at temperatures over 1000 ° C. The measured partial pressures of the gaseous components indicated that the chalcocite reduction proceeded through the gaseous intermediate species CO, C02, and the overall kinetics was controlled by the Boudouard reaction. The kinetic model In(1-X)= kt fits well the experimental data. Apparent activation energy of 3 14 kJ/mol was calculated for the temperature range of 900 0C-1050 °C.

Jan 1, 1999

By D. M. Hausen

A refractory siliceous low-grade silver ore (265 g/t Ag) from a prospect in Sonora, Mexico was investigated mineralogically and metallurgically to evaluate extraction of the silver by conventional methods. Approximately half of the silver was recoverable, occurring as coarsely crystalline acanthite (70-300 Am) that was liberated in material crushed to minus 10 mesh. The remaining silver is refractory and occurs mostly as finely locked (-2 to 0.2 Am) acanthite in cherty quartz, and as minor amounts of finely disseminated stylotypite or freibergite in fluorite. The mineralogic data have thus served to explain the 50-60% recovery of silver by flotation and cyanidation.

Jan 1, 1991

By Rafael Padilla

The recovery of copper from chalcopyrite concentrates by leaching is difficult due to the slow dissolution kinetics of this mineral in most leaching media. However, recovery of copper from sulfidized chalcopyrite (a mixture of CuS and FeS2) by leaching is faster and could be selective depending on the leaching media. In this paper, the result of an investigation on the H2SO4-O2 pressure leaching of sulfidized chalcopyrite is presented. The variables considered in the study were stirring speed, concentration of sulfuric acid, temperature, and partial pressure of oxygen. The experimental data indicated that stirring speed over 500 rpm and sulfuric acid concentration over 0.1 M had very little effect on the leaching rate. An increase in temperature from 90 to 100 ºC increased both copper and iron dissolution; however, further increase to 120 ºC affected negatively the copper dissolution. Oxygen partial pressure was found to be the main variable that controls the copper/iron selectivity of the leaching. An increase in oxygen partial pressure increased significantly the rate of copper dissolution but deteriorated the copper/iron selectivity. The analysis for sulfur of the leaching solid residues indicated that most of the copper sulfide sulfur in the sulfidized concentrate oxidized to elemental sulfur.

Jan 1, 2006

By James A. Sommers

Combustion of niobium nitride powder in a stream of oxygen results in several niobium oxide phases, depending upon reaction parameters. Under rapid oxygen flow, the oxidation produces a molten mass which coalesces into droplets of ca. 2 mm dimension and effectively quenches to leave NbO2 and other lower oxides of niobium, despite the ambient atmosphere of oxygen. A preliminary survey of reaction parameters which govern the split between reduced and oxidized products is presented. This technique offers novel synthesis means for binary oxides when mixtures of NbN and other materials are combusted together, since the niobium moiety is generated in a molten state.

Jan 1, 1995

By Kenshi Kawabata, Mitsuji Ueda, Junko Umeda, Katsuyoshi Kondoh, Kantarou Kaneko

Solid-state recycling process of in-house scraps of machined magnesium (Mg) alloy wastes has been established to directly produce wrought materials via the repetitively plastic deformation by Roll-compaction (RCP) and the conventional hot extrusion. The coarse chips, wasted in machining AMX602 (Mg-6Al-0.2Mn-2Ca) cast billets used for the gate bar used in Electronic Toll Collection (ETC) of the high-way system, were employed as the input materials in this study. RCP process enabled to serve coarse Mg alloy powder consisting of refined grains and intermetallics with no re-melting. They were easily consolidated by hot extrusion, and their wrought alloys showed both homogeneously refined grains less than 1~2 µm by dynamic recrystallization and randomized texture by repetitive plastic deformation on the input wastes. These materials revealed extremely advanced mechanical properties of high tensile strength of 356MPa and high ductility of 14.8%, compared to the originally virgin materials with 270MPa TS and 5% elongation. When applying the same Mg alloy wastes via RCP process to the mass production in the company, the large-scale extruded materials also indicated the superior tensile properties. It means that this direct solid-state process is held as “Up-grade recycle of metal wastes”.

Jan 1, 2008

By A. S. Mustafinova, A. A. Zharmenov

"Production of electrolytic copper is characterized by large volumes of acidic spent solutions the utilization of which requires considerable expenditures of neutralizing agents. At present, an economically substantiated technology does not exist for treatment of sulfuric acid rinse solutions and spent copper electrolyte which will allow for repeated use of the acid and the metal salts. Therefore, for this aim the most advantageous is the use of electromembrane methods. In the paper there is stated the essence of developed technologies which are distinguished by low waste and provide the extraction from the solutions of metallic copper, nickel and sulphuric acid. There are also considered methods of copper electrolyte processing allowing to regulate its composition by that or another component (H2S04, Cu, Ni, As).On the base of the detailed study of the behaviour of various types of ion- exchanger membranes in copper-, nickel-, zinc-, arsenic- bearing sulphate solutions there is realized the selection of the most suitable membranes (MK -401, MA-411, MB-2 and MKL-l/MAL-2).Some variants of electro membrane processing of spent solutions of the hydrometallurgy process have passed productions tests on a number of copper-electrolyte enterprises of the countries of CIS (cooperation of Independent States). These tests showed high efficiency of developed methods."

Jan 1, 1997

By C. A. Morais

The present work describes the development of an efficient and relatively simple process to obtain high grade CeO2 from a mixed rare earth chloride solution. The process involves cerium oxidation and precipitation by addition of a KMnO4-NaCO3 solution. The experiments were carried out at room temperature (25 1° C). The results indicated that the major parameters affecting cerium recovery are the molar ratio of KMnO4/Ce, the initial acidity of the chloride feed solution and final pH of Ce(OH)4 precipitation. In strong acid solutions (pH < 1), the oxidation of Cl to Clo took place in addition to the oxidation of Ce(III) to Ce(IV), so increasing the permanganate consumption. Conversely, low acidity (pH >3) led to coprecipitation of the other rare earth elements. Under the selected conditions, cerium was selectively precipitated as ceric hydroxide, together with some manganese dioxide. Further purification was carried out by the dissolution of Ce(OH)4 in HCl, followed by precipitation as cerium carbonate. The filtrate was neutralised with a Na2CO3 solution in order to recover the associated rare earth elements for further separation. The final product, assaying 99.7 % CeO2, was obtained with a recovery of nearly 100%.

Jan 1, 2003

By Shinya Hodoshima

A catalysis pair of tetralin dehydrogenation / naphthalene hydrogenation has been proposed in the present paper as a liquid organic hydride for operating stationary fuel cells. Catalytic naphthalene hydrogenation, having been commercialized since the 1940s, proceeds to generate decalin via tetralin as an intermediate. The storage capacities of tetralin (3.0 wt%, 28.2 kg-H2 / m3) are lower than decalin (7.3 wt%, 64.8 kg-H2 / m3) but both tetralin dehydrogenation and naphthalene hydrogenation are much faster than the decalin / naphthalene pair. Moreover, existing infrastructures such as gas stations, chemical tankers and tank lorries are available for storage, transportation and supply of hydrogen. With respect to the stationary fuel cells with large space for hydrogen storage, tetralin as a hydrogen carrier is superior to decalin in terms of fast hydrogen supply or power density. Rapid hydrogen supply from tetralin under mild conditions was only accomplished with the carbon-supported metal catalysts in the ?superheated liquid-film states? under reactive distillation conditions. In contrast to the ordinary suspended states, the catalyst layers superheated in the liquid-film state gave high catalytic performances at around 250OC. As a consequence, both serious coke formation over the catalyst surface and excessive consumption of exergy were prevented simultaneously.

Jan 1, 2006

By Huaming Yang

The vanadium-doped SnO2 nanoparticle was synthesized by the co-precipitation reaction and subsequent calcination from the vanadium(III) chloride and tin(IV) chloride. The crystal size, pore size distribution, micrograph and properties of the nanocrystalline powders were examined by differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD), desorption isotherm (Barrett-Joyner-Halenda method) and transmission electron microscopy(TEM). Thermal treatment of the precipitate powder at 600°C led to the formation of V -SnO2 nanoparticle of -10mm in crystal size. Most of the pores in the nanoparticle are about 5~15nm in diameter. Effect of doped vanadium on the crystal size of the nanopartic1e was discussed.

Jan 1, 2003

By Karel Verscheure

Hydrometallurgical zinc leach residue, EAF dust and other Zn-bearing by-products pose potentially serious environmental problems that threaten the sustainability of the operations. A pyrometallurgical process designed for treatment of such residues is the high-temperature submerged plasma Zn-fuming process. The successful operation of this process requires high Zn fuming rates whilst retaining vessel integrity through stable freeze-lining. A Zn-fuming model has been developed and used to systematically investigate a range of operating scenarios and to identify potential fluxing parameters such as CaO/SiO2, Fe/SiO2, MgO/feed-ratios in the input and fluxing additions of dolomite for maximum fuming rates and stable freeze-lining.

Jan 1, 2006

By XUEWEN WANG, Xingming Wang, Xuehui Liu, Mingyu Wang

The Panzhihua titanium concentrate contains high contents impurity of Mg and Al, and it is difficult to prepare high grade titanium slag. To solve this problem, a sodium salt roasting-acid leaching process was proposed for removing the impurities in titanium concentrate. Na2CO3 and titanium concentrate were mixed with the proportion of 1:4, and then the mixture was roasted at 700 for 2h. After roasting, the calcine was leached with HCl solution. The experimental results showed that the removal rate of silicon and aluminum can reach more than 85% and 80%, respectively, at leaching temperature of 70 , leaching time of 4h, HCl addition of 5ml and liquid-solid ratio of 4:1.

Jan 1, 2016

By H. L. Ludtke

Microlaminate composites were fabricated by electron-beam physical vapor deposition. The microlaminates consisted of five layers, each 2 to 4 pm thick, and were composed of either pure metal layers (Cu-Ag), or alternated between metal and intermetallic layers (Nb(Al)- Nb3Al). The microlaminates were heat treated in an Ar atmosphere for 2 to 12 hours, at temperatures of 600°C for the Cu-Ag and 1000°C to 1200°C for the Nb(Al)-NbsAl. Microlaminates were examined after deposition and after heat treatment by scanning electron microscopy and energy dispersive x-ray spectrometry. The effects of heat treatment on the morphological stability of these composites will be described.

Jan 1, 1999

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