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By Toshitaka Ota, Hisao Suzuki, Minoru Takahashi

"Perovskite-type lead zinc niobate (PZN) exhibits excellent electrical properties such as high dielectric constant, high electrostrictive coefficient and superior piezoelectricity. Therefore, PZN ceramics are very promising for high performance electronic devices. However, perovskite phase PZN is not stable under the ambient atmosphere. Accordingly, it is very difficult to prepare single-phase perovskite PZN ceramics. In this study, A-site cation of lead was partially substituted for barium to stabilize the perovskite phase of the PZN (Ba-doped PZN) powder. In addition, molecular design of an alkoxide precursor was controlled for a low-temperature processing. As a result, molecular design to suppress the lead-volatilization during calcination was preferred for a low-temperature processing. Processing temperature for a single-phase perovskite was depended on the amount of barium dopant. Doping of20 mole% of barium resulted in the single phase perovskite at 900 °C. The temperature for the single phase perovskite of Ba-doped PZN powder, which depended upon the amount of Ba-doping, was lower than that of the powder prepared by the atmosphere controlled conventional powder processing at least by 150 °C.IntroductionFerroelectric thin films and powders with perovskite structure are of renewed interest for micro-electronic applications, including ferroelectric random access memory (FRAM), dynamic random access memory (DRAM), and thin-layer capacitors integrated onto a silicon wafer [1-3]. In addition, recent advancement in micro-machine requires a high performance micro-actuator [4]. A perovskite type relaxor of Pb(Zn113 Nb213)03 is one of the promising materials for a high performance capacitor and microactuator because of their high permittivity and electrostrictive coefficient [5]. Therefore, this paper focuses on the low temperature processing of Ba-doped PZN powders.Chemical solution deposition (CSD) from molecular-designed alkoxide precursor solution is one of the most promising techniques for processing high-performance powders and thin films because it offers precise control of compositions on a molecular scale as well as a low processing temperature [6]. However, chemical solution deposition of perovskite type PZN powders and ceramics are very difficult because of the formation of stable pyrochlore phases. Therefore in the past, PZN powders and single crystal have been prepared by the hydrothermal method or flux method as well as the partial substitution method of a A-site cation [7-10]. In this study, a suitable molecular design for a preparation of perovskite type Ba-doped PZN powders with a chemical solution deposition process is investigated as well as the effect of A-site cation substitution. Chemical solution deposition from molecular-designed alkoxide precursor solution is expected to decrease the amount of a A-site substitution and/or a crystallization temperature for a single phase perovskite. This paper describes ""the relation between molecular-design and processing temperatures for a single-phase perovskite of Ba-doped PZN powders in comparison with the conventional oxides mixing method."

Jan 1, 2000

By Zhendong Tao, Wei Huang, Zhongxi Yang, Hang Guo, Haoran Geng, Jingxiang Yao

"CaSO3.0.5H2O typed Flue Gas Desulfurization (FGD) gypsum is a by-product formed in flue gas desulfuration by double-cycle fluid bed method, its composition is different remarkably from that of gypsum yield by normal desulfuration methods, and few studies using it as cement retarder have been carried out. In this paper, the experimental study using CaSO3•0.5H2O typed FGD gypsum as cement retarder was carried out. The experimental results indicate that, when FGD gypsum is added solely into cement, the retarding action is not satisfactory because of its slow dissolution rate; The composite retarder composed of FGD gypsum and natural gypsum can regulate efficiently setting time of cement over a wide range of addition and rate of both each other, and the mechanical property of cement can be improved significantly.Fire-power plants have discharged a lot of harmful gases such as SO2 etc., which has resulted in serious pollution on the environment. To reduce harmful gas containing sulfur in the flue gas, various flue gas desulfuration (FGD) techniques have been developed. At present, the FGD method used widely is to add desulfuration agents such as limestone powder or other calcareous-contained materials during the coal burning or in the flue gas so that the components containing sulfur react with them to form solid sulfate or sulfite and to be separated from the flue gas by collectors. CaSO3•0.5H2O and CaSO4•2H2O typed FGDgypsum can be obtained respectively by dry and wet FGD process[1,2]. As a by-product of fire-power plant, features of of FGD gypsum and its applications have been paid great attention. Pavel Tesa'rek et al [3] presented in full the characters and properties of FGD gypsum; Zofia Konik et al[4] prepared expansive additive used to cemnent industry by using FGD gypsum and aluminate clinker; A. K. Alva et al [5] investigated the effects of FGD gypsum and fly ash on soil properties and found the growth of seedlings of either rootstock improved significantly in soils amended with FGD gypsum and fly ash. FGD gypsum also can be used in gypsum binders, plasters and plasterboard manufacture [2.6]. C. S. Poon et al [7] investigated the effects of FGD sludge on the pozzolanic reaction of reject-fly-ash-blended cement pastes. Many studies using CaSO4•2H2O typed FGD gypsum as cement retarder has been reported[2,8-12]. Howevere, few studies using FGDG as retarder were reported so far. In present study, the chemical compositon, phase composition, structure and features of CaSO3•0.5H2O typed FGD gypsum have been analyzed, and its application characters used as cement retarder have been investigated experimentally."

Jan 1, 2008

By Hongmin Zhu, Kai Huang, Shuqiang Jiao

"Garlic peel was used as the raw material to synthesize the biosorbent for the selective recovery of precious metals from the acid chloride solution. Garlic peel is rich in carboxyl-, amino- and thiol-groups, has the potential of exhibiting high affinity to Au(III) when appropriate chemical modification process was employed. Here in the present study, the biosorbent was prepared by cross-linking garlic peel particles with concentrated sulfuric acid. Adsorption tests for mixing different metal ions such as Au(III), Fe(III), Cu(II), Ni(II) and Zn(II) from various concentrations of hydrochloric acid media indicated that Au(III) was selectively adsorbed on the cross-linked garlic peel gel over the other coexisting base metal ions investigated. The crosslinking mechanism and selective adsorption of Au(III) were also investigated briefly.IntroductionPrecious metals are quite popularly applied in the modern industries such as jewelry, electronics and electrical devices, catalysts in chemical industry, etc. While their high values, limited deposit and quite large demand in industry makes its recovery from the industrial wastes, typically e-wastes, quite necessary. Actually, many techniques have been developed to recycle and recover the precious metals from various industrial wastes effectively in last decades, but the cleaning and ecofriendly processes are still seriously scarce [1]. Taking into account of the typical recovery processes using cyanide lixiviant in the alkaline media, or aqua regia, followed by the further recovery process using activated carbon adsorption or cementation with zinc, iron or aluminum plate or powder, though they both are quite effective recovery processes, if considering the special requirements on safety and ecofriendliness for the modern hydrometallurgical processes, various improved or novel extraction processes are greatly demanded [2]. Recently, the biosorption technology applied to the recover precious metals in the hydrometallurgical process has become a concern [3,4]. Inoue’s research group made great progress in the recovery of precious metals such as gold, palladium and platinum from the e-wastes such as spent mobile phone by using biosorption from the hydrochloric acid media [5,6]. This new hydrometallurgical process exhibits the prominent advantages of being cost-effective for its short process, easy operation and near-zero emission. In the above recycling process for e-wastes treatment, the preparation of biosorbents is the key and backbone of the whole recovery process. For this purpose, they developed a series of suitable sorbents for precious metals recovery by using the tanning-based or cellulose-based biomass such as persimmon peel, grape peel, orange juicing residue, waste cotton, waste paper through the crosslinking process with concentrated sulfuric acid and relative chemical modification processes [7-10]. In the present study, we also applied this technique to prepare the biosorbent of precious metal uptaking by using garlic peels as the raw materials, and investigated the adsorption properties of such-obtained gel in the hydrochloric acid media."

Jan 1, 2012

By Wenbo Luo, Kang Liu, Jilai Xue

"Coal fly-ash(CFA) from thermal power plants is rich in Al2O3, which has great potential as an alternative resource for alumina production. In this work, Alz03 contained in the coal fly-ash was extracted using an acid sintering-leaching process. This process was enhanced by aid of power ultrasound during the leaching. The recovery rate of Al2O3 was increased with ultrasound, compared with the similar process without ultrasound under the identical operation conditions. Leaching temperature can be lowered by about 10-l5°C and the processing time reduced by about 50%. The process kinetics were investigated in details for a better understanding of the fundamentals on the effects of power ultrasound. The obtained results demonstrate the potential application in reducing processing energy and increasing production rate.Introduction Coal fly ash is a typical solid waste generated from coal combustion in thermal power station. Vast amount of CF A accumulation lead to serious environmental problems such as air and water pollution, cropland occupation, radioactive contamination, etc. However, CFA is rich in Al2O3 and SiO2 content, so that it has a potential use as recourses for alumina and silica production [1]. Aluminum industry, especially in China, has made a rapid expansion in recent years accompanying with a large amount of bauxite consumption, resulting a urgent demand to develop secondary alumina resources like CF A to maintain a sustainable development of aluminum industry that faces grim challenge [2].Acid leaching is an efficient technology to use in alumina extraction from CF A. Since the particle of CF A is not naturally existed mineral but was formed in molten state at high temperature, the internal Al-O-Si bonds are so strong to separate alumina from the ash particle. Because of this reason, the direct acid leaching [3-6] operated at ambient temperature has low extraction efficiency, approximate 30% to 40%, which is attributed to self inhibition effect from CaS04 generated by reaction between CaO and H2S04 [7-8]. High pressure leaching can efficiently decompose mullite to release A12O 3 content in the fly ash particles, but this requires autoclave material having strong acid corrosion resistance, high temperature (100°C-300°C) and pressure (1.0MPa-2.SMPa) resistance while its operating security is low and its acid consumption is large [9]. Concentrated acid boil process is conducted at near acid boiling point (200 °C - 300 °C) in 4 mouth flask wrapped by electric heating jacket with high mass ratio of acid and ash to achieve high Al203 recovery rate from CFA. Its disadvantages are similar to the high pressure leaching technology except no-pressure, and also the operating solution at nearly boiling point acid may easily spill and splash with additional acid loss and potential safety hazard [10]."

Jan 1, 2014

By Min Chen, Zhen Tian, Hongxu Cui

"The effects of adjusting technology on the phosphorous enrichment in converter slag were investigated. The results showed that the grain size of 2CaO·SiO2 with high phosphorus containing content increased slightly with the decreasing of cooling rate, and the proper cooling rate was confirmed to be about l.0°C.min-1. Moreover, the morphology of the phosphorus-rich phase of 2CaO·SiO2-3CaO·P2O 5 was changed from granular for the higher basicity of converter slag to the coexistence of granular shape and rod-like for the lower basicity of adjusted slag. With the addition of adjusting agent such as SiO2 to lower the basicity of converter slag, the phosphorus in converter slag could be transferred into 2CaO·Si02 phase effectively, and P2O 5 content in high phosphorus containing phase reached to above 30%.IntroductionThe yield of converter slag is very large in China, but most of the slag is stacked usually after the separation of iron, which not only takes up a lot of land, but also affects the ecological environment seriously. Therefore, improving the comprehensive utilization and value-added products of converter slag is of great significance to recycle the steelmaking slag[l-3]. On the other hand, the refining of hot metal with high phosphorous content is an unavoidable problem with the decreasing of high grade iron ore, and as a result, more amounts of high phosphorus containing steelmaking slag are produced. However, the current recycle of converter slag is more focused on the emission reduction and reuse of steelmaking slag inside the iron and steelmaking process without considering the recycle of phosphorous resources[4-6]. At the same time, the development and utilization of phosphate ore as a strategic resource is drawing more and more attention, but the phosphate ore in China is mostly low grade and significant amounts of tailings are produced which is harmful to the environment. Therefore, it is important to separate phosphorous resources in steelmaking slag which can be used as phosphate ore for fertilizer material[7-9].Literature studies showed that most of the phosphorus in steelmaking slag existing as 2CaO·SiO2-3CaO·P2O 5 solid solution phase in 2CaO·SiO2 particle. The P2O 5 content in the phosphorus containing phase is very low due to the fact that the basicity of converter slag is usually high and the precipitated amounts of 2CaO·SiO2 particles during cooling are very large, resulting in the fact that the P2O 5 contents in 2CaO·SiO2-3CaO·P2O 5 solid solution phase are much lower which is impossible to be used as phosphorous resources instead of phosphate ore. Thus, the enrichment of phosphorus in steelmaking slag is need[ 10-14]."

Jan 1, 2011

By Mei Yang, Wei Gao, Jian Yang, Qingcai Liu, Wenchang Xi

"TiO2 has been loaded on cordierite porous ceramic to prepare the SCR catalyst carrier by using both APCVD and sol-gel technology. In APCVD method, TiC14 and O 2 were used as reaction precursor. TiC14 was gasified by using N2 as carrier gas which was controlled to 500sccm. Its reaction temperature and reaction time were limited to 773K and 30min respectively. The physical properties, SEM and SEM-EDX of the TiO2-cordierite carrier and the properties of SCR catalysts prepared by these carriers have been tested. The tests showed that TiO2 loaded by APCVD method were of graininess shape and even accumulation. The loading rate of TiO2 and the specific area of carrier sample were increased 114% and 21 % respectively comparing with sol-gel technology. In the result of sol-gel method, the maximal difference of Ti content was 66.92%, while the result of APCVD method was 18.89%. It demonstrated that TiO2 was uniformly attached with the cordierite ceramic by using APCVD method, which would ensure more active ingredients well loaded on the Ti02-cordierite carrier. This difference made the denitrification ratio of catalyst prepared by APCVD method was 8.1 % higher than that of catalyst prepared by sol-gel method.IntroductionIn recent years, the emission of NOx, which were caused by coal-fired power plants, has gotten more and more attention. SCR (selective catalytic reduction) is the most effective technology to DeNOx [ll. The core technology of it is the catalyst. The SCR catalyst usually uses Ti02 as the carrier, and V2O 5 as the active component [2, 3] . However, the thermal stability and mechanical properties of TiO2 carrier are unstable, which would influence the performances of the catalyst. The commercial catalyst generally uses WO3 or MoO3 to promote its heat stability at present [4-7] Besides, TiO2 is expensive. Compared with TiO2, the cordierite is of good thermal stability and lower price. So loading Ti02 on cordierite porous ceramic as carrier to produce SCR catalyst is of good prospects [S, 91 • Currently, TiO2 is usually loaded on cordierite by the sol-gel method. But some research has shown that the sol-gel method easily reduced the loading performances of TiO2, such as distribution, combination, etc. APCVD (atmospheric pressure chemical vapor deposition) has many advantages to preparing TiO2 films, such as high bonding strength, fast reaction rate and so on [l0-13l_ In this paper, TiO2 has been loaded on cordierite porous ceramic to prepare the SCR catalyst carrier by using both APCVD and sol-gel methods. The properties of the carriers prepared by the two processes have also been compared."

Jan 1, 2011

By Do-Hyeong Kim, Jong-Jin Pak, Jung-Mock Jang, Min-Kyu Paek

"Thermodynamic relations among Mn, Al and N in liquid iron were studied by measuring the effect of Mn on the solubility product of AlN in liquid Fe-Mn-Al-N alloys in the temperature range from 1773 to 1873 K. The critical Al and N contents for AlN formation were determined by the metal-nitride-gas equilibration technique over wide ranges of melt composition and temperature. The effects of Mn on N solubility in Fe-Mn and Fe-Mn-Al melts containing Mn up to 26 mass% were separately determined in the same temperature range. The experimental results were thermodynamically analyzed using the Wagner's formalism to estimate the critical Al and N contents for the onset of A1N formation. The validity was checked by the observation of inclusion evolution in Fe-20%Mn-1.5%Al-0.6%C-0.3%Si-0.012%N melt during cooling and solidification.IntroductionRecently, high manganese steels such as Twinning Induced Plasticity (TWIP) steels have been developed as next generation steels because of their high formability as well as excellent strength and ductility.[1•2l In these steel grades, a large amount of Mn (15-20 mass%) and Al (1-2 mass%) are added to liquid steels, and such high Mn and Al concentration bring the great challenges to the steelmaking and casting processes. Mn significantly increases the N solubility in liquid iron and the AlN inclusions can be easily formed at such high Al concentrations due to high affinity of Al and Mn with N in liquid steels. Although the AlN inclusion is known to be a dominating and considered as a detrimental phase for the hot ductility of steels,l3l thermodynamics of AlN formation in high Mn-Al alloyed liquid steels was not well known.Moreover, the melting point of these steels decreases down to near 1623 K as increasing Mn content up to 20 mass%. However, most of thermodynamic data has been measured at the steelmaking temperature around 1873 K. Even at steelmaking temperature, there are huge scatters in thermodynamic interactions of Mn and Al on N in liquid iron. The nitrogen solubility in Fe-Mn alloy melts has been measured using the Sieverts' method[4l and the samplinij method[5-7J in the temperature range of 1813 to 1973 K. In the authors' recent study,[8•9 the N solubility in Fe-Al alloy melts was measured using the sampling method in the temperature range of 1823 to 1973 K. However, the simultaneous effect of Mn and Al at high concentrations on Nin liquid Fe-Mn-Al-N alloys is still not known. Also, there remains uncertainty about the temperature dependence of the interaction parameter of Mn on N in liquid Fe-Mn alloys. Therefore, it is worthwhile to check the temperature dependence of this parameter at a low temperature near the melting point of Fe-Mn alloys. There have been few studies on the characterization of non-metallic"

Jan 1, 2014

By Kun Wang, Xinhui Li, Huaqing Xie, Qingbo Yu, Qin Qin

"Three typical model compounds of bio-oil (ethanol, acetone and phenol) were studied in the steam reforming process for hydrogen production. In the thermodynamic analysis, the three componds showed the similar trends. The hydrogen yields increased with the increase of steam/carbon (S/C) ratios, and the temperatures of the maximum hydrogen yields moved afterward to low temperature zone. However, the hydrogen contents were just about 70%. For improving hydrogen yield, a new system for steam reforming of bio-oil with site CO2 capture was put forward. This system required the catalst with the larger granularity having greater mechanical strength and higher abrasion resistance. So, six Ni-base catalysts loaded on Al2O3 particles prepared were used and among them, Mg-Ni/Co catalyst showed the best catalytic performance. For the simulated bio-oil (the mixture of the compounds), the hydrogen yield can attain 63% with Mg-Ni/Co catalyst with the good stability and regeneration ability.IntroductionCurrently the interest in the use of hydrogen as a clean energy carrier is increasing, and the main way for producing hydrogen is steam reforming of fossil fuels, containing steam reforming of nature gas, naphtha and coal. But this way caused substantial amounts of CO2 emitted, and these sources of hydrogen which are non-renewable energy will eventually be used up [1, 2]. As a kind of renewable energy, biomass is recognized as an attractive alternative to fossil fuels, because of its neutral CO2 emissions [3]. There are mainly two thermochemical processes using biomass to produce hydrogen, gasification and flash pyrolysis followed by steam reforming (SR) of the biooil produced in the flash pryolysis process [4]. The latter was known as one of the most promising and economically viable methods for hydrogen production [5]. In the last decades, the biomass flash pyrolysis technology was adequately developed and fairly mature [6]. But the steam reforming of bio-oil is still at the research stage and yet has been leading to more and more concerns by the researchers. In their research, the catalysts were widely studied and yet mainly were powdery[7-10], and the reactors manily were fixed bed reactors[11-13], readly causing the carbon deposition and the catalyst deactivation, against the continuous running. In this paper, a new systerm was put forward and could realize continuous production of hydrogen, yet needed catalysts with the larger granularity having greater mechanical strength and higher abrasion resistance, as well as powdery CO2 sorbents which mainly calcium oxide based ones.In this paper, the thermodynamic analysis of the steam reforming processes of three typical bio-oil model compounds (ethanol, acetone, phenol) was performed, and the effect of S/C ratio and temperature on the hydrogen yield and the compositions of gaseous products were investigated. Then, a new systerm for steam reforming of bio-oil with site CO2 capture was put forward, and the catalysts with a certain granularity were prepared and studied."

Jan 1, 2014

By Ryszard Prajsnar

During copper production in shaft and flash smelting processes at KGHM Polska Miedz S.A., lead bearing material of sulfide, sulfate, and oxide character is generated in forms such as slime from shaft furnace gas handling systems, converter dusts, and dusts from an electric furnace for copper removal from flash smelting slag. These materials are polymetallic concentrates of Pb, Zn, and Cu, with As, Cl, and Cd as impurities. Shaft furnace slime, containing. about 50% PbS and 15% bituminous substances, is the main lead-bearing material. At the Glogów copper mill, a new plant was commissioned in June 2001 to process 80,000 tonnes per year of lead bearing materials to produce 26,000 tonnes per year of crude lead. The plant consists of a feed conditioning system, three (3) rotary rocking furnaces with a capacity of sixteen (16) tonnes of lead feed fired with natural gas and oxygen-enriched air containing up to 45 vol% O2, and a gas handling system. The gas handling system includes a post-combustion chamber, a gas cooling chamber with Cl neutralization, gas mixing chamber, bag filter, and dry limestone scrubbing system for SO2 removal. The lead-bearing feed is smelted with five (5) wt% Na2CO3 and thirteen (13) wt% iron scrap at a temperature of 950 to 1050°C for three (3) hours. The smelting process consists of four (4) stages; feed drying, firing of gaseous hydrocarbons and solid coal from the feed, lead reduction from slag, and separation of molten products. The flow rates of natural gas and oxygen to the burners are controlled to ensure combustion of the bituminous material in the furnace. The process produces crude lead bullion containing (wt%) 0.1 to 0.5% Cu, 0.02 to 0.5% As, 0.05 to 0.07% Bi, 0.1 to 0.5% Sb, and 0.1 to 0.6%Sn. The process also produces a mixture of sodium silicate slag, Fe-Zn-Pb-Cu-S matte, and Fe-As speiss containing (wt%) 5 to 10% Pb, 2 to 6% Cu, 10 to 15% Zn, 1 to 3% As, 10 to 15% S, 0.5 to 3.0% Cl, 2 to 4% K, 4 to 7% Na, 20 to 30% Fe, and 5 to 10% SiO2. The dust is made up of PbO, ZnO, PbSO4, and PbCI2, KCI, and NaCI with a chemical composition (wt%) of 35 to 50% Pb, 5 to 15% Zn, 3 to 6% As, 4 to 8% Cl, 2 to 5% K, and 2 to 5% Na. The construction of the new lead production plant at the Glogów copper mill will process both current lead-bearing materials as well as lead-bearing material that have been stockpiled over the last fifteen (15) years to give a significant improvement in protection of the natural environment.

Jan 1, 2002

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By Nobuyuki Higashiyama, Ikuo Yonezu

"Hydrogen-absorbing alloys containing rare-earth elements are used in high capacity nickel-metal hydride secondary batteries,' hydrogen storage systems for portable fuel cells, and refrigeration systems. New hydrogen-absorbing alloys containing rare-earth elements have also been developed and introduced into these applications. High performance in nickel-metal hydride secondary batteries is strongly demanded because of the remarkable advancements in portable electric appliances. A large hydrogen absorption capacity, high electrochemical reactivity and superior corrosion resistance in an alkaline solution are required for hydrogen-absorbing alloys used in nickel-metal hydride batteries. The aim of this investigation is to improve the performance of conventional LaNi5 type hydrogen-absorbing alloys. For example, Mm(Ni-Co-Al-Mn)„ type hydrogen-absorbing alloys with various non-stoichiometric compositions were developed. In addition, a new process of rapid quenching process was applied for preparing these hydrogen-absorbing alloys in order to improve their performance.IntroductionRecently, the trend in electronic appliances toward portability has increased the demand for high capacity of secondary batteries as power sources. Since nickel-metal hydride batteries were first commercialized in 1990 in Japan, they have become increasingly popular as power sources for cellular phones, portable computers, electric shavers, and other, products.The performance of a nickel-metal hydride battery, such as its discharge capacity, high rate capability, and charge-discharge cycle life, strongly depends on the characteristics of the hydrogen-absorbing alloy negative electrode. Many types of hydrogen-absorbing alloys have been developed so far. For a hydrogen absorbing alloy to be used as the negative electrode material, (1) it must allow a large amount of hydrogen to be absorbed and desorbed in an alkaline solution, (2) its reaction rate should be high, and. (3) it must have long term durability under repeated charge-discharge cycling. However, LaNi5, a typical rare earth-nickel type alloy, shows significant capacity deterioration during repeated charge-discharge cycling. Therefore the first step in its development was to obtain sufficient corrosion resistance of the LaNi5 alloy for its use as an electrode material. A partial replacement of nickel with cobalt and a substitution of the lanthanum- content with misch metal (Mm), a mixture of rare earth elements such as lanthanum, cerium, praseodymium and neodymium, were very useful in improving the charge-discharge cycle life. However, the discharge capacity of the alloy was still not sufficient for a practical battery. A study of the effect of the partial substitution of aluminum and manganese showed that the best alloy composition was Mm(Ni-Co-Al-Mn)x, as follows.The stoichiometry x of Mm(Ni-Co-Al-Mn)x largely affects the discharge capacity and cycle life. Theose alloys with non-stoichiometric alloys with the compositions of [Mm(Ni-Co-AMn)x: 4.7<x<4.8] have a large capacity and a long cycle life. Nogami' et al. reported that 'a non-stoichiometric alloy with a Mm(Ni-Co-Al-Mn)x (x=4.76) composition showed approximately 10% higher discharge capacity than the stoichiometric alloy (x=5) [1] and greater influence of x on the electrochemical properties of multi-component AB„ type hydrogen-absorbing alloys for batteries."

Jan 1, 2000

By H. Y. Sohn, M. Y. Mohassab-Ahmed

"As part of research to develop a novel flash ironmaking process using reduction of iron ore concentrate by natural gas or hydrogen, sulfur and phosphorus distribution ratios between MgOsaturated slag and iron were determined in the temperature range 1550-1650°C under three different gas atmospheres: H2/H2O, H2/H2O/CO/CO2, and CO/CO2. The distribution coefficients of sulfur (Ls) were 4.0, 2.0, and 0.8, respectively, under these atmospheres. The distribution coefficients of phosphorus (Lp) were, respectively, 8, 17, and 20 under these atmospheres. In the flash process over -25 wt% P and S volatilize during ore concentrate downward flight in the reactor shaft in addition to avoiding coke. Therefore, iron produced by the flash ironmaking process would have much lower sulfur contents than the typical hot metal produced by the BF.IntroductionGiven the issues related to large carbon dioxide emissions and energy consumption in the existing ironmaking technologies, a novel flash ironmaking technology was conceived by Sohn [1-3] at the University of Utah. This technology is the first ironmaking process that will convert iron ore concentrate directly to metallic iron in-flight. This process will produce iron directly from concentrate without requiring pelletization or sintering and avoid the need for coke. In addition, this process concept takes full advantage of the fine particle size of concentrate with a large surface area, which permits rapid reduction by a gas. In this novel ironmaking process, potential reductants and fuels are H2, natural gas, and coal gas. Therefore, an iron-slag bath is expected to be at equilibrium with gas atmospheres of mainly H2/H2O or CO/CO2/H2/H2O, respectively, corresponding to the use of H2 or natural gas/coal gas. Since the effects of an H2O- containing atmosphere on slag properties have not been studied before, it is critical for the development of the novel flash process to determine these effects. In H2-H2O-CO-CO2 gas mixtures under ironmaking conditions, H20 was found to have the most pronounced effect on the slag chemistry [ 4, 5]. In addition, it was found in this laboratory that water in the gas atmosphere affected the distribution of Mn between slag and molten iron [6]. Most previous work used CO/CO2 gas mixture to control oxygen partial pressure (p02) [7, 8]. Others used only inert atmospheres [9], although Kor and Richardson [10] used a mixture of C02/H2 to control p02. For phosphorus, previous research focused on Ar [11], Ar-CO mixture [12], CO [13], CO/CO2 [14] or N2/CO [15]. Therefore, it was necessary to investigate the effect of water vapor content in H2-H2O-CO-CO2 mixtures on the equilibrium distribution of sulfur and phosphorus between CaO-MgOsatSiO2-Al2O3-FeO- MnO (0.2-0.8 wt%)-P2O5 (0.1-0.9 wt%) slag and molten iron as part of the development of the novel flash ironmaking technology."

Jan 1, 2014

By Anand Kumar, Pradeep kumar Jha, Suman Kant, Pradeep Kumar

"It has been a major challenge to reduce the intermixed grade formation during ladle change-over operation in continuous casting process of tundish steelmaking. The F-curve generated by step input of the tracer (new grade steel) tells about the intermixed grade amount for different grade specifications. Use of flow modifiers is beneficial in reducing the intermixed grade because of the change in slope (in different time zones) and position of the F-curve due to their placement at tundish bottom. Present study aims at investigating the role of dam placed before the outlet in a multi-strand tundish with reference to the slope behavior of F-curve in different time zones during the teeming operation plays an important role in determining the intermixed amount.Introduction In Continuous casting process, the old grade steel remaining in the tundish (reservoir between ladle and mould) from the old ladle gets mixed with new grade steel from new ladle and leads to intermixed grade which is considered to be of inferior quality. Although formation of intermixed grade is inevitable with the sequential method of casting, its amount can be controlled by changing the flow behavior of steel inside the steel. Intermixing in a slab caster tundish was simulated using 3-D numerical model based on k-å turbulence equation and compared their result with that of water model experiment Yeh and Hwang [1]. Huang and Thomas [2] reported that quantity of residual fluid in tundish affects the composition distribution in the transitional slab and thus the intermixed length. Huang and Thomas [3] developed three sub models to predict mixing in tundish, liquid core of strand and solidification. Thomas [4] developed a one dimensional model to simulate the final composition distributions in slab caster of continuous casting and investigated the effect of process variables on the intermixing. Alizadeh mehdi et al., [5] simulated of the intermixing phenomenon for slab casting for three different sub models. Goldschmidt et al. [6] developed a numerical model that predicted the location of the intermixed steel in a four line round caster. Lan and Khodadadi [7] studied for the transient fluid flow of liquid steel, heat transfer and solidification during the flying tundish change process. Cho and Kim [8] developed a mixing model to predict the outlet concentration of the tundish during grade transition. Most of the work reported in the literature has dealt with intermixing in slab caster tundish. Billet caster units are more often being used by steel industries due to growing demand of billets. The multiple outlets lead to varying degree of intermixing with time owing to their different distance (location) from the inlet. Use of flow modifier to minimize the intermixed amount, however has also not been discussed in detail so far. Further no work has been reported regarding effect of slope of F-curves obtained through different outlets on intermixing. Hence keeping these objectives in mind attempt has been made by authors to analyze the slope of Fcurves after dividing them into three different time zones and the effect of these time zones on intermixing."

Jan 1, 2012

By Payal Bakshi, Sangeeta Tiwari, Mohini Saxena, Anusha Sharma

"Recycling and reuse is perhaps the most favorable and beneficial way to solve the problem of industrial waste disposal. However, the use of industrial wastes like fly ash, tailings etc is in practice for brick manufacturing, land filling, embankments filling etc. These existing practices do not add enough value to the wastes. Moreover, some wastes may have very good potential to be incorporated in valuable products like paints. This study reveals about the value addition of industrial wastes like fly ash, copper tailing and blue dust as an extender in paints. Comparative properties and characteristics of these three wastes for application in paints are discussed. Fly ash, copper tailing and blue dust were characterized for physical, chemical and mineralogical properties and used in different paint formulation based on their potential to the particular application. Fly ash has been found very useful in enamel, primers and flat paints while copper tailing was found suitable in oil based paint formulations. The performance of fly ash and copper tailing paints were evaluated by comparing with those of conventional whiting extender. Blue dust was compared with conventional iron oxide for use in priming coats. The extender properties of these new material and paints prepared out of blue dust, fly ash, copper tailing, were found better than the existing related materials.IntroductionIndustrial development and environmental reforms should run parallel to benefit each other. This is the best policy, which must be adopted by industries for the sustainability of the current modern life. The high degree of industrialization and urbanization adds scads of waste resulting problem of pollution and challenges of their safe disposal. The nature of waste depends on the process that produces waste as its by-product. Therefore, policies/plans are prepared by keeping the view of possible potential hazards. Among the different wastes some are generated in the industries, which have great importance in the country’s economy, like fly ash waste from thermal power industry and mining waste. In India the total contribution of thermal power in the total electricity generation is more than 70% and it produces about 123 million ton of the fly ash annually [1]. On the other hand mining plus extraction of ferrous and nonferrous metals also produce waste in million tonnes of categories [2]. Since the generation of this waste is very high they cover large land area for their disposal and dumping [3]. The storage of this waste in the dumping sites for long time duration may cause problem of land, surface water, ground water and fertile soil contamination [4]. As far as Indian fly ash is concerned it does not contain toxic element over the limits of hazardous waste [5]. However, in general most of the metals deposits are found in the form of pyrite based ores. Mining wastes contain toxic elements e.g. heavy metals in varying amount, which get mobilized when pyrite get oxidized to sulphate producing sulphuric acid [6,7]. These ores contain very less amount of targeted metals in themselves thus they require extensive preprocesses for concentration of the metals [8]."

Jan 1, 2008

By H. Kung, T. R. Jervis, M. Nastasi, T. E. Mitchell

"A systematic study of the structure-mechanical properties relationship is reported for nanolayered composites of MoSh-SiC, Mo-MoSh, Mo-MoShNx, MoSi2-MoSi2Nx, and Mo-MoShMoSi2Nx (x=3-4) synthesised by sputtering techniques. These composites have been studied by nano-indentation and cross-sectional TEM as a function of annealing temperature. As-deposited layers are amorphous except for Mo. With increasing annealing temperature, first MoSh and then SiC crystallize, while the hardness progressively increases until the layers start to spheroidize and grain growth sets in at 900ºC. For the case of Mo-MoSi2, the layers react and the composite deteriorates rapidly. However, MoSi2Nx remains amorphous up to 1000ºC, suggesting that it could act as a diffusion barrier between Mo and MoSi2. In fact the Mo. MoSi2Nx, MoSi2-MoSi2Nx and Mo-MoSi2-MoSi2Nx nanolayers are found to remain stable up to such temperatures. IntroductionMolybdenum dislicide, MoSh, is a potential matrix material for high temperature structural composites due to its high melting point and good oxidation resistance at elevated temperature [1]. The two major drawbacks for structural applications are inadequate high temperature strength and poor low temperature ductility. Silicon Carbide (SiC) being hard and thermally compatible with most ceramics and intermetallic compounds, has been found to be suitable for second phase reinforcement in various structural applications and, in particular, the addition of SiC whiskers improves the high temperature yield strength of MoSi2 [2]. While most of the research in MoSb-SiC composites has been on the particulate form of SiC, laminated composites may offer unique properties. It has been shown that synthetic multilayers with alternating layers of metal and/or compounds may exhibit interesting mechanical properties [3]. Enhancement in mechanical properties by decreasing the wavelength of multilayer spacing has been studied extensively. In general, two types of strengthening have been proposed: (1) Hall-Petch strengthening [4,5], where the strength increase is inversely proportional to the square root of the layer thickness; (2) Koehler modulus strengthening [6], which increases with modulus difference and decreasing layer thickness. In the present study, we have performed a systematic study of the relationship between strength and structure in a number of different nanolayered systems based on MoSh. Layer thicknesses have been varied and their nanostructures have been varied by heat treatment. Previous work on MoSi2-SiC is summarized [7]. In an attempt to improve fracture toughness, MoSh-Mo nanolayered materials have been prepared but are found to react and deteriorate. Previous work has shown that nitrided MoSi2 (MoSi2Nx with x=3-4) is highly stable [8] and so nanolayered composites of MoSi2-MoSi2Nx and Mo-MoSi2-MoSi2Nx have been prepared to assess the' stability and mechanical properties of these composites. Preliminary results are presented."

Jan 1, 1994

By K. S. Han, M. Yoshimuura, H. Fujita, Y. Sato, S. W. Song

"Film of LlCoO2 as cathode material for rechargeable lithium microbatteries has been fabricated on the platinum metal substrate by electrochemical-hydrothermal method in concentrated LiOH solution at 200 °C as Soft Solution-Processing. The film fabrication has been understood in terms of dissolution of cobalt metal powders and subsequent oxidative deposition on the substrate. The film structure was characterized using scanning electron microscope, X-ray diffraction analysis; X-ray photoelectron spectroscopy and micro-Raman spectroscopy.IntroductionRapid growth of wireless communications and emerging integrated optoelectronic circuits caused the miniaturization· cif electronic devices, thus the demand for high energy density microbatteries as a power source for the microelectronics increases. In this regard, all solid-state lithium microbatteries including LiCoO2 and LlMn2O 4 [l-4], the most promising intercalation cathode material, have been developed. However, major difficulty of .fabrication of a lithium microbattery arose from the preparation of cathode film, according to a· recent report on Rare Metal News [5]. Although many attempts have been made to deposit the cathode films, all those methods are mostly chemical vapor deposiiton (CVD), various evaporation, sputtering techniques and spray pyrolysis. These methods require preparation of bulk cathode materials cir its precursor, then deposition with complicated instruments including high· vacuum system, and even postsynthesis annealing to obtain desire electrochemical 'properties. It is clear that all of these techniques are neither economic nor environmentally friendly. Compared to those methods, film form.ation from an aqueous solution is thought to be simpler and more economical, and requires much· less energy consumption. Our .group has demonstrated the utility of Soft SolutionProcessing [6,7], which is defined as environmentally friendly processing using (aqueous) solutions, to produce films of a variety of functional solid materials. According to the Pourvaix's diagram [8], some metal can be dissolved in an alkaline solution and consequently combined with hydroxyl group or oxygen anion forming metalate or metalite. Cobalt also seemed to form cobaltite, HCoOi in strong alkaline solution in the Pourvaix's pH-potential diagram. Based on this information, it was expected that LiCoO2 could be prepared using the cobalt metal in Li OH solution by Soft Solution-Processing. Recently, we reported the successful single step fabrication of electrochemically active LlCoO2 films on the cobalt metal substrate by hydrothermal methods without any post-synthesis annealing as Soft SolutionProcessing [9,10]. Film formation mechanism could be elucidated by the following evidences. . As expected from Pourvaix's diagram, cobalt metal was dissolved in concentrated LiOH solution forming dissolved cobalt species which was detected by an observation of absorption band in UV-VIS absorption spectrum [10]. Thus the reaction was assumed to be started from dissolution. Time dependent potential of Co electrode exhibited only one-step evolution with 0.6 eV from Co metal to LiCoO2 [10]. Another strong evidence was the finding of LiCoO2 powder precipitates at the bottom of tetlon beaker after the reaction [11]. Based on those experimental findings, it was understood that film is formed by dissolution-precipitation mechanism [9-11]."

Jan 1, 2000

By Greg Dowling, Jun Ge, George Shannon, Shufeng Yang, Yongfeng Chen, Lifeng Zhang

"Inclusions in 316L stainless steel ingots poured using two different upgate designs – a traditional upgate and a swirl upgate - were investigated using SEM and ASPEX automated inclusion analysis. The main inclusions were high SiO2 inclusions, MnS inclusions and SiO2-Al2O3-CaO inclusions. More inclusions were detected at the top of the ingot than other places in vertical direction, and more inclusions were at the edge of the ingot than other place in the radial direction. With swirling upgate there were more K- and Na- bearing inclusions than that with the traditional upgate indicating possible more serious flux entrainment with the swirl upgate.IntroductionIngot casting still is very important for production of special steel grades including high carbon chromium bearing steel, thick plate, seamless tube, forgings, bars, and wire rods [1] . During the bottom teeming process, molten steel enters the trumpet and passes through the spider into the runners. Molten steel then enters the ingot mold through an upgate near the end of the runner. In the early stages of filling a mold, a mold flux bag hung in the mold were burnt and the mold flux will cover the top of the rising steel to protect the steel from being reoxidized, acting as well as act as a thermal insulator. So far, some efforts on studying inclusions characteristics in the ingot have been reported. A review paper on the control of inclusions during steel ingot casting was published by Zhang et al. [2] Zhang also studied Inclusions in bottom-teemed ingots of plain carbon steel and found that the >20µm inclusions originated from either the entrainment of mold flux of the reoxidation during teeming process. [3] The results of Nagendra and Du showed that there were more inclusions in the centre part of the ingot [4]. Eriksson et al reported that the composition of inclusions was more complex in the mold samples in comparison to the ladle samples, and more inclusions in the mold were found than in ladle because of the reaction between the mold flux and the molten steel [5]. It was reported that SiO2-CaO-Al2O3 inclusions originating from mold powder with reoxidation product Al2O3 as a part, and there were more inclusions close to the side wall than the center of the ingot in the radial direction. [6]. A more recent investigation showed that four main types of inclusions in runner samples were classified: oxides, sulfides, complex and carbon-nitrides. [7] The flow pattern in the mold during filling has been found to be an important factor regarding inclusions in the ingot. In the early stages offilling a mold, steel enters the mold through the entry nozzle at a high velocity. The effect of the resulting turbulence on the meniscus can lead to the entrainment of mold flux. Efforts have been paid over the years to find methods to reduce the velocity of the molten steel entering the mold, such as using opening angle of the inlet nozzle [8], using swirl blade at the runner [9], using a divergent nozzle combined with a swirling flow generated in the nozzle [10-11]."

Jan 1, 2012

By Srinath Viswanathan, Adrian Sabau

"In general, the occurrence of microporosity during metal casting is due to the combined effects of solidification shrinkage and gas precipitation. The governing equations for fluid flow and hydrogen evolution indicate that porosity formation and fluid flow are strongly coupled. However, in most studies on microporosity, it is considered that the porosity formation does not influence the fluid flow in the mushy zone. In this study, a computational methodology is presented for the numerical simulation of interdendritic fluid flow and microporosity evolution. The solution algorithm presented includes a fully coupled, implicit treatment of microporosity and local pressure in the mushy zone. The effects of microporosity evolution due to the local pressure drop in the mushy zone, and pore expansion in casting regions where liquid feeding alone cannot compensate for the solidification shrinkage are also considered. It is shown that neglecting the effect of porosity formation on the pressure in the mushy zone yields higher pressure drops. By its growth, microporosity partially compensates for the solidification shrinkage, reducing the feeding demand. A reduced feeding demand requires less fluid flow to compensate for solidification shrinkage, and results in smaller pressure drops in the mushy zone. Therefore, in order to accurately describe casting defects, comprehensive models of fluid flow, heat transfer, and solidification must include the effect of microporosity as well.IntroductionIn the terminology commonly used by foundrymen, porosity is usually considered to be either ""hydrogen"" or ""shrinkage"" porosity. Hydrogen porosity is the term given to porosity that is generally rounded, isolated, and well distributed. Porosity that is interconnected or clustered, and of an irregular shape corresponding to the shape of the interdendritic region, is usually termed shrinkage. In general, the occurrence of microporosity in aluminum alloys is due to the combined effects of solidification shrinkage and gas precipitation [1]. Continuum models [1, 2- 7] have been used to predict the level of porosity in castings. A number of other studies have also attempted to understand the phenomena of porosity formation and pore growth [8-10] and pore morphology [11].The governing equations for fluid flow and hydrogen evolution indicate that porosity formation and fluid flow are strongly coupled. However, in most studies [4, 9, 10], it is considered that the porosity formation does not influence the fluid flow in the mushy zone. Kubo and Pehlke [3] presented a methodology for the prediction of microporosity distribution in shaped castings by considering the effects of both the hydrogen precipitation during solidification and the pressure drop in the mushy zone. In their approach, the local pressure and porosity were computed in an uncoupled manner based on a ""flux of interdendritic liquid"" criterion, i.e., either pressure or porosity was first computed using the other variable at the previous time step. Their approach has been used with little change in numerous studies [6, 12, 13]. Recently, Kuznetsov and Vafai [14] presented a fully coupled, one-dimensional model for the computation of pressure and porosity. They showed that neglecting the effect of porosity formation on the pressure in the mushy zone yields higher pressure drops and an over-prediction of final porosity. They also showed that the influence of porosity formation on the pressure is larger at lower pressures in the mushy zone."

Jan 1, 2001

By T. C. Goel, A. Venna, R. G. Mendiratta

"Processing of ferrites has gained tremendous importance in recent times to meet the high performance demands on ferrites in keeping with the fast emerging· technologies. The quality of ferrite powders has strong influence on ·the performance of final device. Fabrication· of high performing ferrite components requires starting ferrite powders of precise stoichiometry, purity and microstructure. It is difficult to obtain these attributes by the conventional ceramic method. The key to obtaining quality powders lies in the· solution techniques. With this in view soft ferrites have been prepared by a wet chemical process, known as the citrate precursor method, which involves the formation of citrate complexes of the constituent cations. The advantages of this process are the ease of preparation and close control of composition, homogeneity, purity and particle size. Electrical and magnetic measurements on lithium ferrites have shown resistivity higher by more than two orders of magnitude compared to that observed for samples prepared by the conventional ceramic method, and low magnetic losses, making the ferrites specially suitable for high frequency applications.IntroductionProperties of ferrites are known to be sensitive to .their processing technique. A small deviation in the compositional stoichiometry of the ferrite affects its properties greatly. Soft ferrites such as Ni-Zn, Mn-Zn and Mg-Mn. are well known ferrites covering wide-ranging applications [1,2]. Lithiiim ferrites have also assumed technological importance for microwave applications and are potential substitutes for the expensive garnets [3]. Lithium ferrites are often doped with zinc to tailor the saturation magnetization required at high frequencies. Lithium and lithium-zinc ferrites, however, present difficulty to processing due to the volatile nature of both the cation components, namely Li and Zn. These ions are volatile at temperatures > 1000°C which makes their processing difficult. One of the main considerations of high frequency performance of ferrites is the high eddy current losses which prevent the interaction of the magnetic field with the ferrite component and hence impair device performance. These losses can be reduced by having a material of high resistivity. Electrical conductivity in lithium ferrite has been attributed to electron hopping [4] between the two vaience states of iron, Fe2+ <=> Fe3+, on octahedral sites. Maintaining the + 3 valence state of otahedral- Fe ions is thus a prerequisite for achieving high resistivity. The resistivity of ferrites is normally found to be low when processed by the conventional solid-state or the ceramic method [5]. This is attributed to (a) extensive ball-milling employed in the method to mix the component oxides results in non-stoichiometric compositions due to introduction of additional Fe ions on abrasion of steel balls during milling, (b) high processing temperatures involved which result in significant volatilization of Li and Zn ions creating thereby oxygen non-stoichiometry which results in reduction of Fe3 + to Fe2 +, (c) large and non-uniform grain sizes. In the present work, preparation of Li and Li-Zn ferrites by a non-conventional method known as a citrate precursor method [6, 7] which requires lower processing temperatures and duration is reported. The method gives stoichiometric compositions on account of homogeneous atomic-scale mixing of the constituent cations via the formation of metal-citrate complexes mixed in solution state. The method is also capable of giving small grain size which aids the oxidation ofFe2+ ions."

Jan 1, 2000

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