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By J. D. Scott

The counter-current jarosite acid wash circuit presently in operation in the zinc plant produces a combined jarosite plus Pb/Ag residue which is discarded. Extensive pilot-scale testwork, and some past in-plant operational experience, has shown that the zinc plant can be easily reconfigured to produce two residues during periods of high silver feeds and/or prices. Plant.optimized circuit configurations are available for silver recovery to a Pb/Ag residue and are in use for the prevention of Pb/Ag-jarosite formation in both the neutral and high-acid leaching circuits. Silver in the zinc plant undergoes several changes in state as it proceeds through these circuits. The roaster calcine is ~3:1 silver sulfate: silver metal, with metallic silver mainly as micro-Inclusions In an aluminosilicate phase. In neutral leach residue, the majority is as silver sulfide or Pb/Ag/Zn-sulfide coatings on unroasted sphalerite grains, with minor Pb/Ag-jarosite and some residual metallic silver in unreacted alumina-silicate grains. In high-acid leach residue, silver occurs as Se-rich silver sulfide particles in sulfur/jarosite ball aggregates, as silver sulfate impregnations in silica-gel masses and in solid solution in Pb/K/Zn~jarosite. Silver concentrations in solution range from 20 to 60 ppb.

Jan 1, 1990

By Thomas E. Weyand

Prior to 1975, lead-based paints were commonly used in protecting steel structures. Because of the toxic effects of lead on human health and the environment, their use has been significantly reduced. However, problems with these paints persist when they are removed during normal maintenance by pneumatic blasting with mineral abrasives. Technologies are developed to contain the spent abrasive and paint during blasting operations. This paper reports on A study to identify beneficial reuses for the spent blasting material. Nine samples were gathered from different projects within Pennsylvania. The samples were thoroughly characterized with regard to composition, morphology, and EP and TCLP leach test performance. Potential reuse applications will be reviewed with regard to technical adequacy, economics, and environmental constraints.

Jan 1, 1992

By J. Borlée, J. P. Birat

"ULCOS is a large European program launched by a consortium of 48 partners led by arcelor and a core group of steel producers, which was started in 2004 with the support of the European Commission (RFCS and 6FP programs) to search for breakthrough process routes that could, in the future, when fully developed, demonstrate the potential of large cuts in CO2 emissions for the production of steel from iron ore.The timescale for commercial implementation is the post-Kyoto period, i.e. 15 to 20 years from today.The present paper presents the progress made in the first 2 years of this 5 year program.Several concepts are being investigated in parallel: re-engineering of the blast furnace to incorporate CCS in the core of the process, smelting reduction with CCS capabilities, massive use of natural with more CO2-lean technologies than today, hydrogen steelmaking and electrolysis of iron ore. Biomass also offers very attractive perspectives, while raising major challenges.None of these new steelmaking routes are ""no regret"", which means that the European Steel Industry has already incorporated extensive energy saving steps in its present process technology and is working as close to thermodynamics limits as is cinematically and economically feasible, and that decreasing GHG emissions further means introducing breakthrough technologies that add significant costs to the operation of the Steel Mills.They will also require much research and development before they can be proven and implemented commercially.IntroductionThe ULCOS program (Ultra Low CO2 Steelmaking) is a large research program of the European Steel Industry and its industrial and research partners launched in September 2004 to investigate steelmaking technologies that have the potential of reducing the CO2 emission of the Industry by a large amount, typically in the order of 50%. It is supported in the European Community by the 6th Framework and the RFCS programs through 3 complementary European projects [1,2].The present paper summarizes the work carried out in the phase 1 of ULCOS and in framing the program of phase 2."

Jan 1, 2008

By Yuanbo Zhang, Zhixiong You, Daoxian Duan, Guanghui Li, Tao Jiang

"Manganese is mainly consumed by steel and battery industries. In recent years, it is essential to utilize the low-grade manganese oxide ores with total manganese grade below 25%, as the high quality manganese ore resources are becoming scarce with the rapid development of the steel industry. Conventional pyro-metallurgical processes for utilizing manganese oxide ores are characterized by high production cost and energy consumption, low productivity, serious environmental pollution, etc. In this study, reduction thermodynamic of MnO2 reduced by sulfur was firstly carried out. Then, a novel process of reduction roasting with sulfur followed by acid leaching was developed to recover manganese from the very low-grade manganese oxide ores. Effects of main factors, including temperature, reduction time and S/Mn mole ratio, were investigated, and a high leaching efficiency of Mn above 95% was obtained under optimal conditions.IntroductionHigh/middle-grade manganese oxide ores are generally used in the metallurgical industries, particularly in steel plants and ferro-alloy units. The consumption of metal manganese in the ferro-alloy industry accounts for 85- 90% of the total Mn demanded [1]. Therefore, high quality manganese ore resources are becoming scarce with the rapid development of steel industry. It is essential to make good use of large quantity of low-grade manganese ores (TMn < 25%) presently available."

Jan 1, 2012

By Shilai Yuan, Huimin Lu, Liyuan Zhao, Zhijiang Gao

"A purification process was developed to removal impurity element boron from metallurgical grade silicon by electromagnetic induction slag melting. Vacuum melting furnace was used to purify boron in both Al2O3-MgO-CaO-SiO2 slag system and Al2O3-CaO-SiO2 slag system. The relationship between different slag chemistry and the removal of boron in silicon were studied using Back Propagation (BP) Neural Network model. The best slag chemistry for the removal of boron was predicted by Genetic Algorithm (GA) contributed by the use of Matlab. The results show that the mass fraction of Boron in silicon is reduced from 11.7496×10-6 to 2.3259×10-6 after slag melting in 28.96%Al2O3-3.43%MgO-36.24%CaO-31.37%SiO2 slag system. The relative error obtained with GA-BP Neural Network model was below 0.35%.IntroductionSolar energy, due to its low green house gas emissions, has been paid great attention. Accordingly, the demand for solar grade silicon (SoG-Si) has been growing rapidly. The quest for developing a low-cost method of producing SoG-Si has been moving forward in the last decade. Refining of metallurgical-grade silicon (MG-Si) attracts research interest due to its low material and energy costs, and more environmentally friendly technology in comparison to the traditional Simens process. As such, impurity elements in MG-Si must be removed to low levels for the photovoltaics (PV) cell to operate at optimum efficiency. Most impurities in metallurgical-grade silicon (MG-Si), especially metal elements, can be separated by directional solidification and the zone refining plasma-arc method [1, 2]. The main focus in refining MG-Si to SoG-Si is on the impurities which are the most difficult to remove. Boron has relatively high segregation coefficients (KB=0.8, concentration of Boron in solid silicon divided by its concentration in liquid silicon) [3] and higher vapor tension (the saturated vapor pressure of boron and silicon are 6.78×10-7 Pa and 0.4 Pa, respectively). The vacuum melting and directional solidification methods hence have no effects on boron removal.Slag refining involves melting MG-Si in the presence of a flux to produce a slag phase that can take up the impurity elements. The mechanism of slag refining is considered to include two main steps: the oxidation of boron and the absorption of boron oxide by slag materials. The oxidation of boron, described by the oxygen potential (PO2), resulting from the equilibrium Si and SiO2. The absorption of boron oxide, described as the slag basicity, is interpreted as expected to facilitate their extraction to alkali and alkali-earth oxides in the slag phase. Thus, effective removal may be obtained for a certain slag composition. Researchers [4-5] examined the effect of boron removal in CaO-SiO2 based ternary systems and showed that the addition of excess CaO can decrease the activity of SiO2. Researchers [6-8] studied the boron behaviors in CaO-SiO2-Al2O3, CaO-SiO2-Na2O, Al2O3-BaO-SiO2, CaO-SiO2-Li2O and Al2O3-CaO-MgO-SiO2 slag systems by adding boron in the silicon to a degree. Li2O, Na2O, MgO and BaO are thought to be associated with B2O3."

Jan 1, 2014

By Hong Yong Sohn

A novel flash ironmaking technology is under development at the University of Utah under the support of U.S. Department of Energy (DOE) and American Iron and Steel Institute (AISI). The history of the development from the conception of the idea to the current status will be discussed. The flash ironmaking process produces iron directly from fine iron ore concentrates without requiring cokemaking and pelletization/sintering, which will enable the technology to significantly reduce energy consumption and carbon dioxide emissions compared with blast furnace ironmaking. Unlike other gas-based ironmaking processes, this technology will not suffer from the problems of solid sticking and fusion. Current work is focused on the method of supplying the energy required to maintain the necessary temperature, as an intermediate step to determine the scalability for larger, industrial-scale pilot trials.

Jan 1, 2014

By Zhiqiang Han, Anil K. Sachdev, Baicheng Liu, Guomin Han, Alan A. Luo

The growth of precipitate phase ,B-Mg11Al12 in Mg-Al alloy is closely related to interface anisotropy and elastic interaction. The aim of this work is to investigate the effects of the interface anisotropy and elastic interaction on the morphology evolution and growth kinetics of the precipitate. In the work, the precipitation of ,B was studied using phase field modeling. In the model, the chemical free energy of the precipitate and the matrix were obtained via thermodynamic calculation. It is demonstrated that the interface anisotropy results in lath-shaped precipitate and the elastic interaction affects the shape of the end of the precipitate. The interface anisotropy causes uneven growth in different directions and the elastic interaction influences its preferential growth orientation. By combining the interface anisotropy and elastic interaction in the phase field modeling, the results showed that the precipitate phase has a lath-shape with lozenge ends, which is in agreement with experimental observations.

Jan 1, 2013

By Orlando C. Rojas

The Potrerillos Smelter commissioned a new El Teniente converter in 1985. As a result of the use of this technology, the Peirce-Smith converters have been processing only high grade matte or white metal. These operational changes resulted in damages to the converter shells, excessive splashing and cold dope generation and very short refractory campaigns. The paper shows the modifications to the tuyere angle, mouth design changes and new techniques for mouth cleaning and gas handling. Operational results up to 1991 are also shown.

Jan 1, 1993

By Craig A. Johnson

Cyanide speciation and behavior have been examined at three active heap leach operations, three heaps undergoing rinsing, and three sites with cyanide contaminated groundwater, all in the southwestern U.S. Data from these studies demonstrate that strong cyanometallic complexes of iron and cobalt can play ?an important role in cyanide behavior throughout the lifetimes of heap leach operations. In active circuits, we find evidence that significant amounts of cyanide combine with iron and cobalt to form strong cyanometallic complexes, and that these species can be adsorbed, probably onto iron hydroxides, or precipitated as insoluble cyanometallic compounds. When spent heaps are rinsed, the release of this cyanide is likely controlled by the slow kinetics of desorption from, or dissolution of, solids that have gone largely uncharacterized. We find evidence that strong cyanometallic complexes can give rise to transient free cyanide in some settings by rapid photo dissociation where heap rinse effluent is exposed to sunlight in open channels or translucent sample bottles. Thus, these species can complicate the ,preparation of spent heaps for decommissioning, even where regulatory standards ?are based on weak acid dissociable cyanide. There is a critical need for information on the form and stability of adsorbed and precipitated cyanide in spent ore heaps, on the concentrations of strong cyanometallic complexes in mineral processing effluents -particularly the complexes of cobalt, and on the natural attenuation of iron and cobalt cyanometallic complexes in both surface and subsurface waters.

Jan 1, 1998

By Binxu Zeng, Mark Jolly, Xiaojun Dai

"The traditional investment casting foundries use batch melting and chunky running systems to produce casting components. This method leaves the energy saving issue as subsidiary one. In our research project, one of the partners, the AEROMET international PLC provides the thin wall aluminium component ""filter housing"" for test. The AERO MET uses traditional casting route to produce the filter housing, which only gives 5% --10% yield. In this paper, numerical simulation method is used to analyse filling and solidification of the casting running system. The CRIMSON running system of the filter housing is designed by using casting simulation software, MAGMAS and Flow3D. By working with AEROMET, various configurations of the casting running systems were tested and analysed. Using them ultiple life cycle approach, the energy content of new process is compared with traditional one. It indicates that the CRIMSON process only uses 36% of energy consumed by the traditional route.IntroductionThe investrnent casting is a metal for ming process using expendable patterns, which is a standard casting technique and is widely used to produce quality parts. Its accuracy, versatility and integrity tie itself to important and precious engineering components in Aerospace industry. However, traditional investrnent casting process usually uses chunky runner system and gravity filling method. It not only reduces the casting yield of the product but also causes the pouring defect during the casting. As author's previous research showed that gravity filling method pouring basin and down sprue are two main resources of entraimnent defects generation. No matter how good the running system is, entraimnent defects such as double oxide films (DOF) and bubbles will I get into the casting to cause problem."

Jan 1, 2013

By Sue Ritz

Gold extraction has relied on coconut carbon in adsorption circuits for several decades. IXOS®, invented by 6th Wave Innovations of Salt Lake City, Utah, is a new type of adsorbent that exceeds the selectivity of carbon and improves on the mechanical properties of other available resins. IXOS selectivity against copper cyanide complexes allows it to be used in circuits that currently struggle with copper contamination. IXOS potential to eliminate or reduce the application of SART technology will expand the opportunities to exploit more complex precious metals deposits. This paper will describe the technology behind IXOS molecular imprint, its comparison to carbon adsorption in the field, and the effect of efficiency on long-term recovery from heap leach METSIM simulation software.

By Wenjun Duan, Kun Wang, Qingbo Yu, Qin Qin

"A novel oxygen production technology noted chemical looping air separation (CLAS) was introduced and properties of Cu-based oxygen carriers used were investigated. The oxygen carriers were prepared by mechanical mixing. Al2O3, Fe2O3, ZrO2, TiO2 and SiO2 were used as binders during the preparation. XRD patterns show that spine! oxides are formed using Al2O3 and Fe2O3 as binders. Phases of CuO and binders keep stable using ZrO2, TiO2 and SiO2 as binders. BET values of oxygen carriers increase in the order of ZrO2>TiO2>SiO2>Fe2O3>Al2O3. The effects of temperatures, binders, particle sizes and flow rates on reduction/oxidation reaction rates were studied in TG experiments. The reduction reaction rate increases in the order of ZrO2>TiO2>SiO2. The effect of binders on the reactivity of oxidation is not obvious. The reduction and oxidation reaction rates both have the tendencies of increasing with the temperature increasing and with gas flow decreasing. However, the effects of gas flow and particle size are little.IntroductionChemical looping air separation (CLAS) is a novel oxygen production technology. The oxygen carriers used in CLAS release oxygen in reduction reactor and regenerate in the oxidation reactor. Selecting suitable oxygen carriers is the key for CLAS. Oxides of CuO, Mn2O3, Co3O4, Pb3O4, CrO2, SrO2, PdO2 and CeO2 have the property of releasing oxygen at suitable temperature and oxygen partial pressure [1]. Among these oxides, CuO, Mn2O3, Co3O4 are the most common compositions used to prepared oxygen carriers for chemical looping combustion (CLC) or chemical looping with oxygen uncoupling (CLOU) [2-5]. Moreover, thermodynamic calculations and preliminary experiments were carried out on oxides of Cu (CuO/Cu2O), Mn (Mn2O3/Mn3O4) and Co (Co3OJCoO) by Moghtaderi to ascertain their feasibility for CLAS process [6]. CuO has the highest oxygen transport capacity (0.1 g 02/g CuO compared to 0.03 g 02/g Mn2O3 and 0.06 g 02/g Co3O4). However, agglomeration is the biggest issue for copper oxides used at high temperature because of its low melting point (l 450°C for CuO, 1235°C for Cu2O and 1075°C for the mixture of CuO and Cu2O) [7]. In order to improve the capability of anti-sintering and stability ofCuO, binders (ZrO2, MgAl2O4, TiO2, SiO2, Fe2O3, Al2O3, cement) are added during the preparation of Cu-based oxygen carriers [8]. In this paper, the Cu-based oxygen carriers were prepared by mechanical mixing method. TiO2, Al2O3, Fe2O3, ZrO2 and SiO2 were selected as binder. XRD, BET and SEM were used to analyze the phase, surface area and surface morphology of oxygen carrier prepared. The reactivity of oxygen reduction and oxidation of oxygen carriers prepared were investigated in STA409PC thermal analyzer."

Jan 1, 2014

By Zengjie Wang

Investigation on hydrochloric acid leaching of the ilmenite from Panzhihua, China was carried out to prepare synthetic rutile. The leaching parameters were optimized to obtain high content of TiO2 in the products. The experimental data suggest that an optimum leaching can be realized with 30% acid, a solid/liquid ratio of 1/4 at 95°C for 4h, and ore ground for -400 mesh size. After the acid leaching, an additional alkaline leaching process using hot NaOH solution was performed, and then the products was in grain form followed by heat treated at 900°C for 2h in order to extract Si and increase the particle size of synthetic rutile. The final product has a high content of TiO2 (about 95%), a low content of chlorine consuming elements (total CaO+MgO =0.07%) and a suitable particle size distribution for chlorination process.

Jan 1, 2008

By Dong Liang, Honggang Zhong, Zhenxing Yin, Qijie Zhai

"2507 super duplex stainless steel (SDSS) has been widely applied in a marine environment, attributing to its excellent pitting corrosion resistance and mechanical properties which are particularly determined by the nitrogen precipitation behaviors and volume fraction of ferrite. In this paper, various cooling rates were obtained by applying four different moulds with the common gating system. By which the influence of cooling rates on nitrogen precipitation behaviors and the ferrite fraction in cast 2507 SDSS was comparatively investigated. The results showed that nitrogen porosity could easily precipitate in cast 2507 SDSS under standard atmospheric pressure. The number of nitrogen holes increased with decreasing the cooling rates, and the holes mainly distributed in three zones, i.e. the interface between the horizontal and vertical columnar grains, top vertical columnar grains and the final solidification region. Additionally, higher ferrite fraction was obtained with lower cooling rates.IntroductionDuplex stainless steels (DSS) have a dual-phase microstructure consisting of ferrite (d) and aus-tenite (?). Due to the combined advantageous properties of d and ? phase, their application rapid-ly increased in industry [1, 2]. Super duplex Stainless Steel (SDSS) is the third generation of du-plex stainless steels, of which the alloy elements Cr, Ni and N content are higher than the stand-ard 2205 DSS. Because it has high contents of alloy elements, the SDSS has better mechanical properties, and its pitting resistance equivalent number (PREN) reached a point 43. Hence SDSS has been used in petroleum chemical industry, the marine equipment and harsh corrosion environments [3]. SDSS contains ferrite stabilizing elements, such as Cr, Mo and Si, and austenite stabilizing elements like Ni, Mn and N [4]. Many researchers have studied the effects of these elements on the stabilization of d and ? phase and the ratio of the two phases. High nitrogen con-tent is another prominent feature of SDSS. Nitrogen addition to SDSS is very effective for improving its mechanical properties [5] and corrosion resistance [6], such as pitting resistance in NOx environment. To increase the nitrogen content in steels, a lot of work had been done. N. Nakamura and S. Takaki [7] examined the behavior of nitrogen absorption in Fe-23Cr alloy powder by sintering in nitrogen gas atmosphere, they found nitrogen content easily up to 1.0 wt. %. Using devised NH3 gas injection system, W. Park et al. [8] successfully produced austenitic Fe–23.5Cr alloys containing over 3 wt. % of nitrogen. Further-more, W.P. Tong et al. [9] stated that nitrogen percent was extraordinary high (about 10 wt. %) in pure iron plate. However, the above methods are difficult to be applied to large-scale industrial production."

Jan 1, 2012

By Michael J. Nicol

The teaching of courses in geology, mining and extractive metallurgy in Australian universities is undergoing significant change largely as a result of the initiative taken by the Minerals Council of Australia (MCA). This has resulted in a major program aimed at developing national under- and postgraduate courses in selected areas with the aim of making these available to a consortium of participating universities. Murdoch University, together with the A J Parker CRC for Hydrometallurgy has been commissioned to develop the course in hydrometallurgy. Progress in the development of this course will be discussed in terms of overall philosophy, content and mode of delivery. Aspects of the extension to a Web-based course will also be summarized. Murdoch University has also established a hydrometallurgical pilot plant on the campus and the results of the first continuous operation for several months using under- and postgraduate students as operators will be discussed from the point of view of practical training and providing an interface with the local industry.

Jan 1, 2002

By H. Y. Sohn, M. K. McCarter, Bradley C. Paul

"A computer model was constructed for bacterial leaching of the major sulfides found in porphyry deposits, including bornite, chalcocite, chalcopyrite, covellite, cubanite, enargite, native copper, pyrite, and pyrrhotite. The model incorporates equations for the sulfide minerals dispersed in the rock matrix. Leaching occurs by reactions with ferric ion diffusing into the rock fragment: Ferrous ion is resenerated to ferric with oxygen by bacteria at a temperature dependent rate. The model keeps track of the net acid generated, oxygen consumed by the bacterial oxidation of ferrous ion, heat generated, jarosite and hematite precipitated, and copper leached. The model was used to predict the rate of copper recovery, heat generation and oxygen demand for a variety of run-of-mine sized porphyry ores. These results were used in the design of a ventilation system and the economic analysis of a modified in situ extraction method that may be cost competitive with conventional copper production involving open pit mining.IntroductionA study was undertaken at the University of Utah to evaluate the technological and economic feasibility of mining copper by a method referred to as Flood Drain Leach Cell (FDLC) mining. Cells 60 by 75 meters in plan and 70 meters in height are created throughout the ore body by a modified Vertical Retreat Mining technique that includes the removal of 25% swell material. The swell material is leached in finger dumps on the surface while the cells underground are bulkheaded, flooded, drained, and artificially aerated to promote bacterial ferric sulfate leaching. Solutions are cycled through several cells to reach pregnant grade of 1 gram copper per liter of solution. These solutions are then fed to an underground solvent extraction plant and then a surface electrowinning tankhouse."

Jan 1, 1988

By L. Lewczuk

A detailed mineralogical and liberation study was performed on the iron ore mill products from the Scully concentrator of Wabush Mines, Newfoundland. Automated image analysis techniques were applied to deter-mine grain size distribution and liberation of all mineral components of the ore. As a result of the study it was indicated that iron recovery can be improved and the Mn minerals reduced in the iron ore concentrate by (a) increasing spiral middlings, (b) regrinding the middlings, and (c) separating the Mn minerals from the iron minerals in the reground middlings.

Jan 1, 1988

By K. Adham

"Fluidized beds are utilized in a wide range of high-temperature applications throughout the metals and materials industry. Their main advantage is the fast and uniform heat and mass transfer between the hot combustion gases and the particulate solid feed. A further benefit can be the lowering of the processing plant's energy consumption, through heat recovery from the fluid bed processes used for solids heating. Here, the enhanced energy efficiency of fluidized systems is investigated and the modeling results are discussed for three configurations: the flash tube, the single bubbling bed and the multi-stage fluid bed. Key thermal design aspects of each system are identified based on results from process simulations, in order to benchmark their main operating features and overall energy efficiency. Suitability and applicability of each configuration is also discussed based on a number of process and material property considerations.IntroductionCombustion based heating of particulate solids is commonly done using three different types of fluidized beds. The flash tube (FT) is similar to a hot pneumatic transport system. The single-stage fluidized bed (FB) typically uses in-bed combustion. The multi-stage fluidized bed (MSFB) can have two or more stages stacked into a tower.Flash tube (FT) suspends the incoming solid charge in a high-velocity stream of hot combustion gases. To maintain the solids suspension in the FT, two parameters are required: high velocity for elutriation of the particles and adequate solid-to-gas ratio for avoiding high pressure drops and solids drop-out [l].The fluid bed (FB) works at much lower velocities than the flash tube. Therefore, most of the solids are not conveyed in the gas stream, but are only suspended in a liquid-like manner. At minimum fluidization velocity (Umr), the gas flow exerts just enough force on the solids to keep them suspended in place [2].Multi-stage fluid bed (MSFB) heats up the solids as they are transferred from an upper bed level to a lower one, counter-current to the rising flow of hot gases generated at the lowest stage. As the temperature and volumetric flow of the gases decrease from bottom to the top stage, smaller bed diameters can be used in the energy recovery stages [3]."

Jan 1, 2014

By C. Pichler, A. Ressler, D. Gregurek, A. Spanring

In order to improve the refractory lining life at one of the RHI key customer test procedures were developed within a two years collaboration project. In the first year of cooperation detailed refractory corrosion work in the rotary kiln with Ca-ferritic slag was performed. The main results of the second year of cooperation, reported in this article, involve a detailed testing work with nickel matte and pre-selected refractory brands which was performed in TBRC. A first part of this work was a complete chemical and mineralogical characterization as well as FactSage calculations carried out on provided matte samples. According to these results testing in the TBRC was realized at different process temperatures with several magnesia-chromite bricks. Based on the mineralogical investigation a high chemothermal load caused by sulfidic matte resulted in a deep reaching infiltration of the brick microstructure and partly corrosion of main brick components.

Jan 1, 2015

By Nagahiro Saito, Takashi Nishimura, Takamichi Ichikawa, Akio Fuwa

"Yttria-stabilized zircohia (YSZ) has high potential to be used as solid-oxide fuel cell (SOFC) electrolyte. However, the high efficiency of SOFC has not been yet achieved due to the high internal resistance of bulk electrolyte. The resistance becomes lower with the decrease in the electrolyte thickness. Thus, the decrease in electrolyte thickness leads to lower internal resistance. . The aim of this study is as follows: (a) to prepare the thin films of YSZ by inductively-coupled RF plasma-enhanced metal organic chemical vapor deposition (PEMOCVD) process using Zr(t-OC4H9)4,Y(DPMh and oxygeil, and (b) to reveal the relationship between the structural characterizations and the process parameters.1. IntroductionYttia-stabilized zirconia (YSZ) has, been widely used as not only heat-resistant materials but also the components in automotive oxygen sensors, electrolytes of solid-oxide fuel cell (SOFC)(1)(2) and the buffer layers for the high-temperature superconductor because of its low thermal conductivity, good mechanical properties and high ionic conductivity. However, it is said that the internal resistance of the bulk electrolyte is too high to be appropriate as a solid electrolyte for high-efficient SOFC. The authors believe that the thin YSZ electrolyte can give a high performance to characteristics SOFC, since the internal resistance becomes lower with the decrease of electrolyte thickness. Thus the process technology to prepare YSZ thin films is desirable and must be established.In recent years, the YSZ thin films have been reported by chemical vapor deposition (CVD), thermal CVD using metal chlorides (MC) of ZrCl4 and YC(3)(4), thermal CVD using metal organic compounds (MO)(5)(10) Zr(t-OC4H9)4 and Y(C11H19O2)(11) and plasma-enhanced (PE) CVD using MO. Here, these methods are called MCCVD, MOCVD and PEMOCVD. MCCVD has two disadvantages; a large quantity of chlorinated impurities in deposited films and high processing temperature (> 1273K). This high processing temperature leads to damage of substrates in particular, so the application of this technology is limited. On the other hands, the processing temperature by MOCVD becomes and is lower. Unfortunately, the accurate vapor pressures of these metal organic compounds have not been, known so: that it is difficult to control the composition and the film thickness by MOCVD method well. Moreover, the large amount of carbonic compounds in the films prepared by MOCVD method is produced. However, plasma-effect has been reported to decrease large amount of the carbonic impurities by PEMOCVD. However, PEMOCVD has many reaction parameters in plasma processing; the geometry of experimental apparatus, radio frequency, electronic power input and so on. Thus, the general understanding about the relationship among reaction parameters, the composition and crystal structure of thin deposit film by this method has not yet been established."

Jan 1, 2000