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By M. Okido, H. Yamamoto, T. Sakamoto, R. Ichino, K. Kuroda

"Hydrogen absorption alloy films have been produced by molten salt electrolysis. Lanthanum-Nickel alloy film can be formed on a nickel substrate in KCl-NaCl-LaCb molten salts by electrolysis diffusion process. LaNi5 alloy was formed by mutual diffusion between La ·and Ni after La deposition on Ni substrate. Though several kinds of La-Ni compound existed in deposits, the alloy compounds on Ni substrate changed by electrolysis condition. According to the open-circuit potential measurement in molten salts after La electrodeposition, the formed compounds had a relation to the potential. In the case of the substrate electroplated a cobalt thin film on nickel, LaNi4_5Co0.5 was formed by the electrolysis in the molten salts with lanthanum ions. This ternary alloy film showed better hydrogen absorption behavior in cyclic charge/discharge test in alkaline solution.IntroductionHydrogen storage alloys have attracted attention as the active materials for batteries with the charge/discharge property at ambient temperature. The alloy of nickel and misch metal, mainly consisting of La and Ce, has been commercially 'used as a metal hydride with rechargeable property. In recent years, researches have been developed many kind of new alloys with better hydrogen absorption properties. The hydrogen absorbing alloy ingots are commonly produced by melting method of both metals in furnace, otherwise, prepared by mechanical grinding and metallurgical sintering technique with metal powders. The film is also made by vapor-phase techniques such as sputtering method, ion plating method, etc. ·We have proposed a new method to produce hydrogen absorbing alloy films by molten salts electrolysis technique [1-3]. The hydrogen absorbing film, LaNi5, Mg2Ni and CaNi5, were obtained in this process through controlling the electrolytic condition. The active metals, La, Mg and Ca, are electrodeposited on Ni substrate, diffuse into the substrate and form various kinds of intermetallic compounds. This technique provides a direct process using metal chlorides as resources to produce functional films without using active metals such as La, Ca and Mg."

Jan 1, 2000

By J H. Kyle

Cyanide is a significant cost in gold processing, as well as an environmentally sensitive issue. It has been suggested that precipitation of cyanide from leach liquors as copper-iron-cyanide compounds such as Cu2Fe(CN)6 may account for part of the total cyanide consumption. This may be especially true for ores that are rich in both copper and iron minerals. Ammonia addition has been shown to decrease the cyanide consumption by copper. Cu2Fe(CN)6.xNH3 precipitates have also been postulated to form during conventional cyanide detoxification processes, using oxidants such as SO2/air, with ammonia arising as a breakdown product from the oxidation of free cyanide. The present work has examined the conditions under which such precipitates may form, particularly in gold plant process and detoxification liquors. Ammonia and pH were found to have a large effect on the extent of precipitation. The compounds that were formed were found to comprise mainly Cu2Fe(CN)6.7H2O, as well as a range of NH3-bearing variants. The stabilities of the various precipitates are important from an environmental perspective. The long-term stability of copper ferrocyanide precipitates in tailings dams may be a problem under alkaline conditions and when some free cyanide is present, elevating the measured total cyanide in solution significantly. Case studies including data from actual plants are also considered, and the importance of these effects is reaffirmed from these results.

Jan 1, 2000

By Entov Vladimir M., Gilmer R. Burgos, Andreas N. Alexandrou

"Processing of metal alloys in their mushy state represents a new trend in metal processing. As part of this process, known also as thixocasting, a specially prepared slurry at a temperature in the mushy region is injected into a die. Parts produced using this technology offer better mechanical properties than those produced by casting, and comparable to those of forged alloys.In thixocasting, semisolid slurries are highly concentrated suspensions of rounded rosette-like crystals in eutectic liquid. The mechanical behavior of the slurry is determined by the structure and properties of the skeleton formed by the alpha phase particles. The skeleton structure is almost never at equilibrium, and its evolution is, governed by a number of kinetic phenomena of different c11'aracteristic time-scales. Therefore, the skeleton structure depends on the mechanical and thermal history of the material. As a result of these kinetic processes, the rheological properties of the material, such as effective viscosity and yield stress, decrease with structure breakdown, and increase with its development. In the present investigation, the behavior of semisolid slurries during processing is modeled using the conservation equations, and a Herschel-Bulkley fluid model. The rheological parameters are assumed to be functions of the solid volume fraction, and of a structural parameter that changes with processing history. The evolution of the structural parameter is described by a first order kinetic differential equation that relates the rate of build-up and break-down of the solid"

Jan 1, 2000

By Noboru Masuko, Sachiko Ono

"The structure and composition of anodic films formed on aluminum in a borate solution have been investigated by using TEM and SIMS with respect to the effect of current density and electrolyte temperature. The film is composed of a boron-containing outer layer and a boron-free inner layer with disc-like crystals present at the interface. The thickness of the film formed at constant current density up to an identical voltage, decreases with increasing current density. The thickness increases remarkably with elevated temperature. The transport number of Al3+ estimated from the thickness ratio .of the cuter to the inner layers is 0.4 when the film is formed at the current density of 20 Am-2 at 60°C. It increases slightly with increasing current density and decreases significantly with increasing temperature. Content of boron in the outer layer increases 1.5 times when current density .increases 10 times. These changes in film structure and composition with electrolysis conditions must have a significant role in the determination of electric properties of anodic alumina films as a capacitor material.IntroductionThe growth of anodic alumina film in ·a neutral electrolyte proceeds at both film/electrolyte and film/substrate interfaces giving a duplex structure. The oxide layer formed at the former interface includes electrolyte anions while a-pure alumina layer is formed at the latter interface. The thickness ratios of each layer respectively represent transport numbers of Al3+ and 0 2 - (1). The film thickness and the incorporated anion content as well as transport numbers of both ions must affect the dielectric properties of the film as a capacitor material. However, the correlation between film structure and electrolytic conditions is not fully understood (2). For the further clarification of anodic film growth mechanism, more detailed characterization of anodic films in relation to electrolytic conditions is advantageous. In the present paper, therefore, the effect of current density and electrolyte temperature on the microstructure and composition of anodic barrier films formed in a neutral borate solution was studied. The films were characterized by direct observation using transmission electron microscopy (TEM) and depth profiles of constituent elements obtained by secondary ion mass spectroscopy (SIMS)."

Jan 1, 2000

By Takafumi Kondo, Satoshi Yamashita, Noboru Masuko

"Aqueous oxidation of phosphite ions to phosphate ions with dissolved oxygen was examined at 80° C and pH 4.5 mainly from the stichiometric point of view. Dissolved oxygen alone can not oxidize sodilim phosphite in aqueous solution, but when sulfur dioxide is coexistent, cooperative oxidation for both sulfite and phosphite can occur in aqueous solution. Sulfur dioxide itself is well known as a reducing agent, but it also reacts as an oxidation-promoting agent for other species under a certain condition. So sulfur dioxide is· a promising cheap reagent for waste phosphite processing.IntroductionIn a liquid-phase oxidation reaction using the dissolved oxygen gas, the eoexistence of a copper salt is required generally. Recently, it was reported that the oxidation reaction progressed by using mixed gas of sulfur dioxide and oxygen without the copper catalysis, and the attention has been collected1·3). The present authors also noticed the phenomenon since the early time and have been studying on the reaction mechanism of sulfur dioxide in liquid phase oxidation 4l. It was found that; by using the SO2-O2 mixed gas, the oxidation of phosphite ions to phosphate ions proceeded efficiently in sulfuric acid solutions. In the present report, the applicability of SO2-O2 mixed gas as a cheap oxidizing agent to the industrial processing of the waste solution of electroless nickel· plating is investigated. It is well known that the sulfur oxide dissolved in aqueous solution is oxidized ·by the oxygen in the air to sulfuric acid according to the following equation"

Jan 1, 2000

By T McConachy

New opportunities for miners are beginning to appear through new discoveries, improved knowledge and access to vast unexplored areas of the deep sea and continental shelf. Recent discoveries of undersea hydrothermal deposits show evidence of high-grade mineralisation, although in many instances the extent of the resource is still unknown. The promise and the difficulties of undersea mining have been evident since attempts were first made to mine manganese nodules in the 1960s. The physical nature of the undersea resource is a key influence on its mining potential; and environmental issues will also become increasingly important. This paper explores these issues and concludes with a description of the immediate to medium term applied research required to develop this industry and the spin off that such research can provide.

Jan 1, 2000

By Toshio Kurikami, Koichi Yamazaki

"Toho Zinc Co., Ltd Chigirishima Refinery has the production capacity of electrolytic lead for 95000t/y by sintering- blast furnace electrolytic process. Lead raw materials are lead concentrates, spent batteries and dusts that contain lead from other companies, and these are handled by existing smelting process. There are many circulation materials in the process, because the system has been constructed with improving the recovery rate and protecting the environment. This report describes material balance in each process, distribution of the lead and various components, and it examines present state of the processing. In addition, we report the result that we have tried to improve the work environment.IntroductionThe Chigirishima Refinery of the Toho Zinc Co., Ltd. is located in Chigirishima, an island 4km off the coast of Takehara-city, Hiroshima, Japan. The Chigirishima Refinery began lead smelting operations in 1951.The Chigirishima Refinery adopted the sintering-blast furnace-electrolytic process and has an electrolytic lead production capacity of 95,000 tons/year. The existing smelting process handles raw materials from lead concentrates, spent batteries, and lead-bearing dust from other companies. This system was constructed with the intentions of improving material recovery ratios and protecting the environment; therefore, there are many materials recirculating throughout the smelting process. This report describes the material balance in each process and the distribution ciflead and various components, and it examines the present state of processing. In addition, we report the results of our attempts to improve the work environment."

Jan 1, 2000

By I. A. Ibrahim, A. K. Ismail, A. A. I. Afifi

"Synthetic rutile for paints industry is conventionally produced by a combined smelting and leaching process. Smelting process is an energy intensive step and represents economic burden in view of the increasing energy costs. Egyptian ilmenite ore containing 40% TiO2 and 38% total Fe was thus directly leached with sulphuric acid to produce eventually synthetic rutile. The process-involves digestion of the ore with sulphuric acid whereby both TiO2 and Fe are dissolved. The solution was then treated with iron powder to convert Fe3+ to Fe2+ to avoid co-precipitation of iron during the hydrolysis step. After solid/liquid separation and clarification, Fe was crystallized as ferrous sulphate hydrate by chilling. The titanium pregnant liquor was concentrated by evaporation and then hydrolyzed to precipitate hydrated titanium dioxide which was then calcined to produce synthetic rutile containing 98.6 TiO2 and 0.58% Fe2O 3. The optimum conditions of all the processing stages were determined.IntroductionSynthetic rutile for paints, welding rods and other industries could be produced from ilmenite ore by sulfuric acid leaching process. This process is a batch process and nearly 80% of all TiO2 produced in the world is made by this process [1]. Figure l shows simple block flowsheet of the process. The process involves the following stages.Digestion: In this stage, ilmenite ore is treated with concentrated sulfuric acid where both iron and titanium are converted to their respective sulfates according to the following equations:"

Jan 1, 2000

By P Tobar

The development plan (long-term plan) of El Teniente Mine, Codelco-Chile, includes 100 per cent primary ore, located at increasing depths, which may involve several difficulties related to the application of the current panel caving method, such as a high seismicity level, a coarse fragmentation and ore pass damage. Therefore, it is a strategic priority for the El Teniente mine, to design and to test alternative mining methods, at similar or lower costs to ensure an efficient and safe ore extraction. In this context, the Macrotrench method is developed, as a competitive alternative to the current method. The document describes the panel caving method, the experience achieved in the primary ore exploitation from the geomechanical point of view. It also describes the æmacrotrenchÆ method as an alternative to the current exploitation method. Finally, the comparative advantages of macrotrench in relation to panel caving are presented. The results obtained during the engineering stage include the following aspects:the mining design, the material handling, a geomechanical evaluation of the method, and a comparative analysis.

Jan 1, 2000

By Masami Taguchi

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

Jan 1, 2000

By Kostas Fytas, Pierre Bousquet, Bill Evanelou

Acid mine drainage (AMD) is a serious environmental problem that preoccupies the Canadian Mining Industry. Considerable amounts of money are spent every year in an effort to prevent or reduce the acid mine drainage phenomenon. AMD occurs when sulphide minerals (ex. pyrite) contained in rock are exposed to air and water and subsequently oxidise to produce low pH water. This acid effluent has the potential to mobilise any heavy metals contained in the rock. Coating the sulphide minerals with silicates is a new promising technology to reduce AMD. Pynte is treated with a solution containing H2O2, sodium silicate and a buffering agent. H2O2 oxidises a small part of pyrite producing ferric iron (Fe3+) ions. These ions subsequently react with the silicate ions to produce ferric hydroxide-silica that precipitates on the pyrite surface producing a passive coating. This silicate coating can protect the grains of pyrite from oxidation. This paper presents a series of experiments that confirm that silicate coating can considerably reduce AMD.

Jan 1, 2000

By R. L. Grayson

Conventional mine safety wisdom states that "the most efficient mines are also the safest." Since the 1980s, small mines (and contractors) have been targeted as the most dangerous because of their fatality records. However, statistical analysis of West Virginia safety and production data from 1993 indicated that, when considering the correlation between accident severity and tons mined per employee-hour worked, the most efficient mines were, with the exception of very small mines, not the safest operations. This paper presents the results of an extended analysis of West Virginia mine safety using 1993 and 1996 data and concludes with the method used to suggest current priorities for focusing interventions.

Jan 1, 2000

By M. Tamura, K. Fujita, K Shinozuka, H. Daimon, H. Esaka

"In-situ observation of unidirectional solidification using transparent substance has been performed to investigate the growth direction of solid phase. Cell or dendrite of which preferred growth direction is not parallel to the heat flow direction was observed with various solidification conditions. Dimensionless growth direction (p) changes from 0 to 1 with increasing growth velocity at a constant temperature gradient. Introducing the dimensionless growth velocity, the relation between p and growth condition could be correlated.IntroductionTransition in macroscopic solidified structure from chill to columnar zone which is found in normal castings takes place via grain selection1). Cast products such as turbine blades are unidirectionally solidified, grain selection plays an important role to choose suitable crystals which have reasonable orientation in the region called ""starter"", which is a very initial part of casting2). Therefore, grain selection is a very important process in the formation of casting structure. The present authors have been studying on the process of grain selection using succinonitrile, which is a transparent organic substance and have found that the growth distance necessary for grain selection depends upon the solidification condition3-5). When the solid/liquid interface is dendritic, the grain selection occurs quickly. On the other hand, when the solid/liquid interface is cellular, it occurs slowly. We supposed that the growth direction of dendrite is different from that of cell when the substance is unidirectionally solidified. Indeed, Kurz and Fisher wrote in their text book that dendrite grows along its preferred growth direction, <100>, regardless of heat flow direction and that cell grows along heat flow direction regardless of its preferred growth direction1). However, there is no quantitative description about the growth direction when the solid/liquid interfacial morphology is cellular. Furthermore, there have been little works6) to study the growth direction of cell and dendrite."

Jan 1, 2000

By M. Kobayashi, Y. Nishisu

"Fine multicomponent particles of yttrium and europium were synthesized through the precipitation from homogeneous solution, and the various characteristics related with the fluorescence were investigated. The morphology and the fluorescent characteristics of the synthesized particles were affected by ionic species in the stock solution. In the presence of sulfate ion, some parts of the precipitated particles were aggregated, and _the fluorescent characteristics were not good. On the other hand, in the presence of chloride ion or nitrate ion, the particles precipitated were almost monodispersed, and, the intensity of the fluorescent emission were strong after calcination. Further, these particles were also very attractive as the red phosphor in the mercury-free fluorescent systems.Introduction Eu doped Y oxide particles have been widely investigated for the application to the fluorescent lamps and displays: Recently, the fluorescent lamps are pointed as harmful electric equipments because of using mercury for excitation. Therefore, the use of the mercury in the fluorescent- system will be limited or prohibited worldwide in near future. Then, the development of the mercury-free fluorescent lamp is strongly required without delay. Inert gas such as neon and/or xenon seem to be applicable as new excitation element that replaces the mercury. However, in case xenon the excitation wavelength,' 146 and 172nm, is different from that of the mercury, 254nm, and then, the commercial phosphors which are used in the present fluorescent lamp system are not available. Therefore, the invention of the novel phosphors is essential for the development of the mercury-free fluorescent lamp. Further, the controls of the size and shape of the particles precipitated are also important, because the homogeneity of the size and the shape is very important for the fabrication of the layer of the phosphor particles. That is to say, the development of the phosphor particles with controlled components, size and shape is essential. The precise control of size and shape improves the packing density, and so, the screen performance of the lamp [1]. In addition, these phosphor particles should be also useful for the application of the flat-plane displays, for example, PDP, etc. [2,3]. In the present work, first, the particles including yttrium and europium for the precursor for red phosphor were prepared through precipitation from homogeneous solution. This process was precisely controlled for the control of the components, size and shape of the particles precipitated. Next, the particles precipitated were calcined, and then, their fluorescent properties were characterized. As a result, some of them showed the possibly available characteristics as the red phosphor for mercury-free fluorescent lamp system. These experimental results are presented in this paper."

Jan 1, 2000

By Fiona J. Stevens McFadden, Gregory J. Hardie, Mark P. Taylor, William Uru

"Over 20 million tonnes of installed aluminium smelting capacity exists worldwide, with smelter energy con.sumption in the range 14-17 kWh/kg aluminium. In terms of the reduction cell technology itself, the lowest sustained energy consumption is just below 13DC kWh/kg, or 50% energy efficient.For 15 years Comalco Aluminium Ltd. in Australia has been engaged in developing and testing reduction cells that use a refractory hard cathode, composed of a TiBif carbon composite coating over a carbon cathode. This technology has the potential to reduce energy consumption significantly while simultaneously increasing the life of the cells, which is currently limited by wear rate of the conventional carbon cathodes used throughout the worldIntroductionThe successful development of an aluminium wettable cathode technology affords the opportunity to the cell designer and smelter operator to fundamentally change the physical operating characteristics of the Hall-Heroult process. With this revolutionary capability in hand, published papers and patents have indicated that the technology may be exploited in a wide variety of ways to improve the economic performance of aluminium smelting process. Comalco has been developing refractory hard cathode technology for more than 15 years and has been exploring a number of ways that the technology may be commercially applied in a smelter operation [l]."

Jan 1, 2000

By A G. Grice

WMC Resources Pty Ltd û Copper Uranium Division operates the large underground Olympic Dam Mine at Roxby Downs, South Australia. These operations mine and process the ore to produce refined copper, uranium oxide, gold and silver. In mid-1996, the company committed to the Olympic Dam Expansion Project (OEP) to expand production from 3.0 million tonnes per annum of ore (85 000 tonnes per annum of copper metal) to over 9.0 million tonnes per annum of ore (over 200 000 tonnes per annum of copper metal). Along with the increase in the ore production capacity of the underground mine and the surface ore handling and processing facilities, expansion of the backfill system was required. The target backfill placement rate was 2.0 million cubic metres of backfill per annum which was to be predominantly delivered as cemented aggregate fill (CAF). This paper discusses the engineering activities undertaken to assess and change the method of designing the required strength of fill exposures. In addition, the operational changes that were introduced to achieve the required fill quantities and the mix designs to meet the specified strengths, including the use of alternate binders, are discussed. This work resulted in a large increase in the fill placement rate and a reduction in the overall unit cost of fill.

Jan 1, 2000

By J. H. Ahn, J. K. Yoon, Jung-Eui Lee

"A concentration change during grade transition operation in steel thin slab casting is predicted with computer simulation, water model and plant trial. Fluid flow and mixing patterns in various tundish levels and flow rates were analyzed through three-dimensional mathematical modeling. Comparing with water model experiments, a simple, efficient and accurate computational model has been suggested to predict the concentration profile at outlet of tundish. Based on the model, mixing in/below the mold was analyzed considering EMBR. The predicted concentration profiles show good agreements with the measured values. It is found that the lower vortices in the mold are suppressed by the electromagnetic field and the plug-like flow region develops which decreases the intermixing of two different grades of steel and shortens the length of transition region.1. IntroductionContinuous casting is the primary mode of production of semifinished steel products as it offers tremendous advantages in terms of energy savings, increased yield and higher productivity over the traditional ingot casting process. Efforts have to be made constantly to improve the quality of the cast product, reduce costs and thus increase the competitiveness of the steel manufacturer. One way of reducing costs is to reduce the amount of intermixed steel during the grade transition operation.Several different procedures exist to handle the casting of dissimilar grades for the conventional slab casting. Each procedure has its own merits and demerits. In order to choose the best method for a particular operation, there are a lot of researches. In the case of present continuous thin slab casting of POSCO mini mill, the only possible method is to change ladle during the grade transition. Due to the high casting speed (3.8m/min-4.4m/min) it is impossible to change the tundish and due to the thin thickness of slab it is also impossible to insert grade separator."

Jan 1, 2000

By Brian Stump, David Anderson, D. Craig Pearson, Robert Martin

Mining explosions designed to move, bulk or fracture rock are often composed of a number of explosions arranged in a complex spatial and temporal pattern. The effects of the explosions are strongly dependent upon the design and implementation of this blasting pattern. This paper describes the collection, combination and visual display of multiple types of data from these explosions for the purposes of understanding the relationships between the blast design, implementation, and observations. Data sets consist of three-component ground motion, acoustic, video and high speed film, three-dimensional topography, geological and geophysical properties, design blast pattern and timing, and velocity of detonation in the explosive for individual borehole detonation times. The explosions studied include simple single-fired contained explosions, ones designed to bulk and fracture rocks and those that cast material.

Jan 1, 2000

Open pit mining at Bingham Canyon commenced in 1904 and about two billion tonnes of ore have been extracted since then. There remain just under one billion tonnes of ore in the pit and this will be mined by 2015. Because the porphyry system extends below the ultimate pit limits, Kennecott Utah Copper Corporation initiated a study in 1997 to determine the viability of underground mining. The study was initiated at that time because the results were to be used to compare the economics of a further pit expansion to that of an underground mine. If a pit expansion was viable then overburden removal would have to start in the near future. This paper is a summary of the work that was carried out for the underground study. Block cave mining was determined to be the most appropriate method to mine the deposit. Two block cave areas have been planned with a total production rate of 72 500 tpd. Additional sources of ore will come from skarn orebodies that are associated with the porphyry deposit. The geology of the deposits is described together with the geotechnical techniques that were used to characterise the rock in the absence of more detailed data that are normally available. A general description of the mine plan is given along with the reasons for selecting the particular methodology used. The study was completed at the end of 1998 and demonstrated the viability of underground mining at Bingham Canyon. Funds have been approved for further drilling and technical studies, which will lead up to a feasibility study in 2004/5.

Jan 1, 2000

By Tadafumi Adschiri

"Supercritical water can provide an unique reaction atmosphere for synthesizing metal oxide nanoparticles. Due to the drastic change of properties of water around the critical point, including density, dielectric constant and ionic product, the reaction phase with O 2 or H2 gas and the reaction rate and equilibrium can be varied to synthesize new materials or define particle morphologies. In this work, hydrothermal crystallization experiments are performed with several types of flow apparatus that allow convenient manipulation of variables such as temperature, pressure, and residence time. Key features in the flow modes and material preparation are discussed. The proposed supercritical hydrothermal synthesis method has the following desirable features: i) nanoparticles can be produced, ii) morphology of the produced particles can be controlled with small changes in pressure or temperature, and iii) a reducing or oxidizing atmosphere can be applied by introducing oxygen or hydrogen or other gases. An overview of this method is given for functional material synthesis of significant industrial interest including barium hexaferrite magnetic particles, YAO/Tb phosphor fine particles and lithium cobalt fine crystals.IntroductionHydrothermal crystallization, a method of metal oxide formation from metal salt solutions, is typically used at temperatures ranging from 373 K to 473 K. We are developing a new process for hydrothermal crystallizations that uses temperatures in the range of 673 K to 723 K, which is just above the critical temperature of water1 • 8 • In this work, we refer to this process as supercritical hydrothermal synthesis. The supercritical state of water allows one to vary reaction rate and reaction equilibrium by shifting the dielectric constant and solvent density with pressure and temperature. From of our research on material production in supercritical water, we have identified the following specific features of the supercritical hydrothermal synthesis method: (i) ultrafine particles can be produced, (ii) morphology of the produced particles can be controlled to some extent with pressure and/or temperature, and (iii) a homogeneous reducing or oxidizing atmospheres can be provided by introducing gases, such as O 2, H2, H2O 2• and so on.1"

Jan 1, 2000