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By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By Courtney Young, Jerome Downey

"The various technologies developed for treating spent potlining (SPL) from primary aluminum smelters have been reviewed on several occasions. The technologies generally involve physical, chemical, and thermal processes, either individually or in combination, with the primary objective of total recycle, waste minimization, or complete disposal. In general, those technologies geared for recycling involve separations and are therefore subject to recovery inefficiencies that are attributed to several factors. However, the inefficiencies could be reduced or possibly eliminated if the pots were designed for recyclability. This concept is applied to SPLASH, a recently developed SPL management technology.IntroductionAluminum is produced by molten salt electrolysis via the Hall-Héroult process. The process is conducted in an electrolytic “pot,” which is comprised of a steel frame first lined with insulating refractory brick, and then conductive graphite blocks, which serves as the carbon cathode [1, 2]. These materials are collectively referred to as “potlining.” Anodes comprised of petroleum coke/pitch are suspended above the pot and extend down into the molten cryolite (Na3AlF6) electrolyte. The electrolyte temperature is maintained at approximately 980 °C by resistance heating as low voltage (4-5 volts) and high current (50,000-300,000 amps) are applied across the two electrodes.High purity alumina is added to the cryolite bath, where it dissolves and becomes amenable to aluminum reduction at the cathode:"

Jan 1, 2008

By L. Evrard, S. Brouwer, E. Bosly, E. Boydens

"A partial desulfurization roasting process has been tested on a typical copper-zinc sulfide concentrate in a Nichols Herreshoff monohearth pilot furnace whereby the su!fµr is partially removed and iron is to a certain degree preferentially oxidized. The phase changes that occur in the particles during selective roasting at 650°C and 800°C over a range of residence times were investigated by the use of chemical analysis, optical microscopy, X-ray diffraction and electron microprobe analyses. The purpose of this work was to get an insight into the mineral assemblages formed by controlled oxidation roasting and to evaluate if this non traditional approach could be afterwards used to recover zinc, copper and iron by a physical separation method. IntroductionThere has been considerable interest over the years in improving extraction and processing procedures for recovering non ferrous metals especially from polymetallic ores containing copper, lead, zinc and iron sulfides with very fine intergrown phases. Complex sulfide ores, which represent considerable reserves and resources in copper, lead and zinc, as well as precious metals and sulfur, are difficult to treat by conventional physical processes, leading to impure concentrates at low metal recovery. Some methods that can be used to treat such ores were described by G. Barbery (1). Various metallurgical routes generally combining pyro- and hydrometallurgical methods have been explored to develop new processes to recover the metals from zinc-bearing sulfidic ores and concentrates (2, 3, 4). The feasibility of partitioning complex sulfide minerals to simpler phases in order to improve selective extraction of mineral constituents has also been investigated (5)."

Jan 1, 1999

By J. D. Law

The presence of long-lived radionuclides presents a challenge to the management of radioactive wastes. Separation of the radionuclides from the waste solutions has the potential of significantly decreasing the costs associated with the immobilization and disposal of the waste by minimizing waste volumes. Several solvent extraction processes have been developed at the Idaho National Engineering and Environmental Laboratory for the separation of transuranic elements (TRUs), 90 Sr, and/or 137 Cs from acidic radioactive waste solutions. The TRUEX and POR processes for the separation of TRUs, the SREX process for the separation of 90Sr, the cobalt dicarbollide process for the separation of 137Cs and and a universal solvent extraction process for the simultaneous separation of TRUs, 90Sr, and 137Cs have all been developed in centrifugal contactors using actual liquid radioactive waste solutions and simulated dissolved calcine waste solution. In addition, the behavior of metals with each of the solvent extraction processes was evaluated. This article summarizes the most recent results of the each of the flowsheet demonstrations and provides Information on the centrifugal contactor equipment used for the testing.

Jan 1, 1999

By D. Q. Cang, G. Duan, H. X. Li, H. Bai

"Life cycle assessment (LCA) is a valid environmental evaluation method and enterprise environmental management tool used in industrial ecology areas. In this paper LCA was newly used to evaluate the environmental impact of manufacturing of alumina by Bayer process in china from two aspects of logistics and energy flow, GaBi software acted as analysis tools with evaluation model established, and several environmental impact assessment criteria were selected based on the actually typical date of Bayer alumina producing process. Evaluation results show that alumina manufacturing by the Bayer process has a great impact on the global warming and human health of respiration, even roasting process gives rise to the greatest impact of winter fog index. Scenario analysis proposed ways of reducing environmental load caused by Bayer process including: (1) the economic and efficient use of mineral processing technology; (2) optimization of energy use, saving power consumption or the use of new more economical source of energy; (3) actively promote the use of innovated technology and equipment in alumina manufacturing and waste such as red mud utilization process.1 IntroductionSince 2002, China is already the world's biggest producer of aluminium, in 2007, China aluminum production has accounted for above 1/3 all over the world, 2009 for 13 million tons and to the end of 2010, China aluminum production is expected increased to be over 15 million ton [1,2,3]. While as the raw material for producing aluminum the alumina production in china has up to 19.46 million tons of the world's total quarter in 2007, by the end of 2009 China alumina production has achieve to 23.78 million tons [4,5]. China has rich bauxite resources with proven reserves about 23 million tons, but the great majority of china bauxite is hard monohydrate diaspore type with low ratio of aluminium silicon, high impurity content and poor aluminum dissolution performance, that cause high energy consumption, long and complex process, high production costs and heavy environment load[6,7]. Before most used alumina production was sintering process rather than Bayer method in china, over the past decade Bayer method has been widely applied instead of sintering process or combination both forming joint process, premise is improving bauxite quality by mineral processing or adding imported rich bauxite mineral[6,8]. In general each ton production of alumina needs bauxite 1.6~2.20t, limestone 0.7~1.7t, soda 0.250kg, fresh water 12.30 cubic meters, in addition to consume large amounts of energy, and emission waste water over 8.0 cubic meters, dust 2.3~5.7 kg, red mud 0.8-1.5 tons. In china Red mud yield nearly 30.0 million tons every year, accumulated stock is approximately 0.2 billion tons, by 2015 accumulative total red mud is expected to reach 0.35 billion tons [9-13].We know aluminium industry and alumina production have produced large waste, make large energy consumption and its environmental impact could not be ignored. Expecting to optimize production processes and achieve resource recycling for this industrial process the proper environmental assessment is very necessary. Currently Life Cycle Assessment (LCA) is generally recognized as the approved tool to achieve the purpose. The essence of LCA tool is to examine, identify and evaluate a kind of materials, product, process, or a system of environmental impact in their whole life cycle. The life cycle of materials or products includes whole process from raw materials obtained to the final disposal, or more ideal with original or other forms of the whole process of recycling [14-17]."

Jan 1, 2011

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

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

Jan 1, 1988

By Ann E. Visser

Aqueous Biphasic Systems (ABS) form upon the admixture of certain water-soluble polymers or polymers and salts above critical concentrations, and thus represent liquid/liquid extraction systems whose nature is entirely aqueous. We are currently investigating the utility of ABS (and its solid phase analogs) as "green" alternatives to the use of volatile organic diluents in separations of metal ions. Chaotropic (water-destructuring) metal ions with small negative AGhyd (e.g., Tc04) tend to partition quantitatively to the PEG-rich phase of an ABS, but even hydrated metal cations can be partitioned to the PEG-rich phase if a suitable extractant (e.g., halide, dye, crown ether, etc.) is used to produce a more chaotropic ion-complex.

Jan 1, 1999

By Robert W. Bartlett, Keith A. Prisbrey

"Natural biooxidation of shallow, refractory ore heaps, relying on gaseous oxygen diffusion from the heap surface is attractive because of its simplicity and potential low cost, especially without using a lined pad, which is possible if percolation of leachate through the heap is avoided. In this case, the excess oxidation enthalpy must be removed by water evaporation from within the wet ore heap, and the rising water vapor flux within it will impede the downward oxygen flux. An analysis of this process shows that for typical values of pyrite grades and limited temperature increases in the ore heap, the oxidation rate and penetration into the heap is reduced to values between about 30 percent and 50 percent of those obtained when leachate percolation occurs and water evaporation is not a significant mechanism of heat removal.IntroductionHeap biooxidation of refractory gold ores, needed as a pretreatment step to liberate the gold for subsequent extraction by leaching, requires large amounts of oxygen for the normal amounts of sulfide minerals that are typically present, one to two percent pyrite and/or arsenopyrite.The importance and potential limitations of oxygen transport into commercial ore heaps, which are much larger than encountered with column tests of ore and with pilot heaps, has been recognized111 • Commercial ore heaps using radial stacking conveyors are typically about nine meters high and may be 100 meters or more in lateral dimension. Three oxygen transport mechanisms have been identified and analyzed: ( 1) natural convection, which arises from an increase in buoyancy caused by the temperature rise and gas composition changes associated with the exothermic oxidation of the sulfide minerals within the ore heap, (2) forced air ventilation, using low pressure fans and air distribution pipes within the heap, and (3) diffusion of oxygen in the gas-filled void spaces within the ore heap driven by the oxygen concentration gradient from the surface of the heap to the mineral oxidation loci within it."

Jan 1, 1997

By K. S. Raja, M. Misra, S. K. Mohapatra

"Ordered arrays of TiO2 nanotubular photocatalysts were prepared by a simple anodization process. Band gap states of the TiO2 were altered by controlling the anodization electrolyte composition and thermal annealing conditions that resulted in enhanced photo activity. These nanotubes were used for reducing CO2 to methanol either by photochemical or photo electrochemical routes. Pd nano-particle loaded TiO2 nanotubes were employed for photochemical reduction of CO2 to methanol that showed a conversion rate of 12 x 10-3 mol m- 2h-1. Carbon modified TiO2-xCx type nanotubes were used as photo anode and Ti as cathode for photo electrochemical reduction of CO2. The potential of Ti cathode was maintained at -0.5 V SCE. The formation rate of methanol was determined as 13 x 10-3 mol.m-2h-1.1. IntroductionGlobal warming due to emission of carbon dioxide is a serious environmental concern. The atmospheric concentration of CO2 is about 384 ppm by volume and about 3 x 1012 tonnes by weight. Burning of fossil fuels and deforestation are the leading causes for increase in the anthropogenic CO2. More than 32 x 109 tonnes of CO2 are released per year (based on 2006 data) worldwide from the fossil fuel. Pumping CO2 from the fossil fuel power plants into deep ocean basin is one of the most discussed disposal options. The other potential option is converting this green house gas into valuable fuels.Carbon dioxide feed stock can be converted into fuels of solid, liquid or gas phase by chemical, electrolytic, photocatalytic and photo-electrocatalytic methods. Reduction of CO2 to fuel form of any phase requires energy. The reduction process should be energy efficient so that we do not spend more energy and emit more (indirect) CO2 in the process of converting CO2. From this point of view, conversion processes occurring at room temperature look attractive.Electrolytic conversion of CO2 into various forms such as methane1, ethane2, ethylene3, methanol4,5, ethanol6, n-propanol, formic acid7, and formaldehyde has been widely reported. The standard equilibrium potential (at pH: 0) for reduction of CO2 to methanol is 0.14 VSHE and to methane is 0.2 VSHE which is thermodynamically more favorable than hydrogen reduction. However, the gas phase reduction is kinetically complex requiring effective electrocatalyst. The major issues with electrolytic conversion of CO2 to useful products are:"

Jan 1, 2010

Equilibrium calculational software programs can be effectively utilized to illustrate the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation to students studying hydrometallurgy. The calculational program STABCAL will be demonstrated. illustrative examples for the creation of diagrams such as EH-pH, activity or concentration-pH and activity or concentration-EH will be presented to demonstrate the fundamentals of real hydrometallurgical systems. Speciation, titration and mixing will be used to simulate or predict operational processes. Applications will include treatment of Acid Mine Drainage (Berkeley Pitlake water and sediments), mass balance potential/pH diagrams, leaching and selective separation of metals from electroplating sludge, metal adsorption at femhydrite surfaces, and flowsheet development for treating mercury sulfide K106 sludge.

Jan 1, 2002

By Kenneth N. Han

Ammonia has been found to be an effective leaching reagent for gold, silver and platinum group metals in the presence of appropriate oxidants. Electrochemical and kinetic aspects of the dissolution of elemental gold in ammoniacal solutions have been investigated. The cathodic reaction of aurous di-ammine on the gold cathode has been investigated first. From this investigation, the standard electro-potential of the cathodic reaction .and hence. the Gibbs free energy of formation of the aurous di-ammine were established. The solubility of gold in ammoniacal solutions was also examined in relation to ammonia concentration, temperature and concentration of various oxidants. The anodic reaction of the gold disk in ammonia? in the presence? of various oxidants including oxygen, ozon, hypochlorite, hydrogen peroxide, cupric and cobaltic ammine, and iodine was also examined and the results have been discussed. Excellent dissolution yielding of gold and many other metals, typically better than 95% recovery in 1'-2 'hours of leaching at a temperature ranging 80°C to 190°C has been observed. Test results of the dissolution of gold from elemental state as well as other sources including sulfidic ores and scrap are presented.

Jan 1, 1998

By A. A. Bustos

A model was developed to simulate the blow-by-blow operation of the converting process. From the weights, compositions and temperatures of all converter feeds the model calculates the composition and tonnage of both converter matte and slag as well as bath temperature at the end of each blow. The development of the model and its application to the converter aisle operation are described. There is good agreement between model predictions and observed results. At the present time the model is being used to investigate different converting schemes and their effect on pay metal recoveries, slag chemistry and temperature of the bath. Future work involves the use of the simulation model as a process control tool for the converting operation.

Jan 1, 1988

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By J. W. Perez

Raw coal will often break intragranularly in either a completely random way or in a differential mode where one species will have a different rate of breakage than another. Locked coal-ash and coal-pyrite particles can also break by the preferential detachment of one species from another along zones of inherent weakness in locked particle assemblages. The mode. cf breakage is largely a function of the nature of the feed, but it is also influenced by the comminution device and the operating variables. Evidence of breakage of particles in the various modes is seen in the crushing of raw coal and middlings particles with a rotary beaker, jaw crusher, rolls, hammer mill and rod mill. Evidence from the literature indicates the detachment mode is often important for coal, ores and metallurgical products. Further confirmation comes from the crushing of a specially prepared 'ore' of sized magnetite in plaster of Paris.

Jan 1, 1988

By Sergio T. Amancio-Filho

FricRiveting technique is an alternative new spot joining process developed for thermoplastic-lightweight alloy structures. In this technique a cylindrical metallic rivet is used to join one or more thermoplastic / metal components by means of plasticizing and deforming the tip of the rotating rivet through frictional heating. Advantages of this new technique are e.g. short joining cycles, minimal sample preparation, absence of environmental emissions and enhanced mechanical performance in comparison to base materials. Qualitative and quantitative synchrotron X-Ray microtomographic and light optical microscopic analysis of a case-study joint on aircraft materials polyetherimide and aluminum 2024 showed that joint strength is mainly dependent on aspect ratio of the rivet (geometrical dependence) and quality of joint, (microstructural dependence), whereby increasing aspect ratios and lowering the percentage of defects usually yield improved strength.

Jan 1, 2009

By C. Flores

A novel process using solid metals for the direct reduction of more noble metal ions from solvent extraction organics has been developed. Base metals recovery has been the principal focus of investigations to date but feasibility tests have now also been made on galvanically stripping selected precious metals. In this study gold (III) was loaded from an aqueous HAuCI4 .3H20 solution into a mixed organic 40 vol.% TBP, 10 vol. % D2EHPA in kerosene. The direct precipitation of metallic gold from the loaded organic phase using zinc powder and iron, aluminum and copper slabs at 70 °C was successfully demonstrated. The gold reduction rates were relatively fast even though the conductivity of the organic solutions is very low. The reaction rates were studied as a function of the variables zinc particulate size, oxygen and nitrogen atmosphere, water content in the organic phase, organic ratios and temperature. The gold morphology was usually powdery or dendritic in nature but continuous films were obtained in some instances. Activation energies were calculated and possible reaction mechanisms are discussed. In general, the results obtained were very promising and showed that gold can be successfully cemented from selected organic solvents by galvanic stripping using less noble solid metal reductants.

Jan 1, 1995

By Takashi Araki

In this work, we have elucidated the two-step oxidative reaction mechanism of 2,4,5-trichlorophenol by adsorbing oxygen atom for oxidative decomposition reaction of 2,4,5-trichlorophenol on oxide catalyst surface using ab initio molecular orbital calculation. In the first oxidation, total energies of reaction products have been shown extremely stabilized at all oxidation positions. This reaction occurs due to charge transfer from benzene ring to adsorbing oxygen atom. As a result, ? bonding of benzene ring are weakened. However, the benzene ring of 2,4,5-trichlorophenol does not perform cleavage reaction. In the second oxidation, the benzene ring of 2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

By Musa Karakus

The sedimentary iron ores of Alsace-Lorraine, France have very high phosphorous contents that average 0.7% and are as much as 2.19% P. Ores from the Tucquegnieux and Joeuf mines have been studied by cathodoluminescence microscopy, X-ray diffraction, scanning electron microscopy, and electron microprobe analysis in order to fully characterize the mineralogy, size, shape, and distribution of the deleterious phosphate grains. The phosphorous occurs as collophane, a carbonate fluorapatite, in ten morphological forms, most abundantly as microcoprolites, but also as intraclasts, concentric layers, and cortices in ooids, phosphate replaced ooids and bioclasts, phosphatiC shells, fossil infillings and internal molds, fish teeth, phosphatiC laminae, and cements between the goethite ooids. About 95% of the phosphate grains are sufficiently large that relatively fine grinding fol'lowed by reverse flotation would be expected to be effective in significantly diminishing the phosphorous content of the concentrates.

Jan 1, 1989

By Yoji Imai, Akio Watanabe, Masakazu Mukaida

"To clarify the feasibility of alkoxides and acetylacetonates as precursors for laser CVD of metal oxides, vapors of tantalum or titanium alkoxides and zirconium acetylacetonate were irradiated by KrF excimer laser and deposits were characterized by XRD and XPS measurements. As for tantalum and titanium, non-stoichiometric crystalline oxides grew nearly phototropically, however, zirconium oxides deposited showed only halo-pattern by XRD measurements. Electric conductivity measurements of tantalum oxides implied the improvement of the insulating properties by the addition of activated oxygen to the ambient.IntroductionThere has been renewed increasing attention to the metallic oxide thin films because ofits promising usefulness in many applications, such as high-Tc superconductors and ferroelectric devices. A variety of thin film preparation techniques have been studied such as sputtering, chemical liquid deposition (sol-gel and metalorganic decomposition), pulsed laser deposition and chemical vapor deposition (CVD). Among them, we think CVD is the most promising method because it offers a high controllability of morphology and good step coverage at relatively high growth rate. Preparation of oxide films by CVD can be achieved using a precursor containing metallic element and oxygen containing gas such as N20 at the same time. However, metalorganic (MO) compounds which contain both metallic element and oxygen, directly bonded to metallic element, seems to be more favorable because some of MO has a good properties for CVD such as a rather high vapor pressure, stability in ambient and low toxicity."

Jan 1, 1998