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By Junhong Noh, Kug Sun Hong, Jung-Kun Lee, Bo Ding

"The photocatalytic splitting of water into H2 and O2 by oxide nanoparticles has received much attention. However, the full potential of photo-catalysts for efficient hydrogen generation out of water has not been fully realized yet due to unresolved limitations including the low electrical conductivity and ineffective carrier extraction. Here, we report composite oxide materials consisting of 1-dimensional (1-D) transparent conducting oxide (TCO) core and TiO2 shell. Highly conductive ITO nanowires were grown on a flexible SUS mesh as a core component. The photoelectrodes consisting of these 1-D nanocomposites have increased carrier mobility due to the TCO core, while the TiO2 shell provides the photocatalytic functionalities. In addition, the built-in-potential at the interface between TCO core and the TiO2 shell improves the collection of charge carriers from TiO2 to TCO. These factors altogether contribute to increasing the photocurrent of the device under light.I. IntroductionPhotocatalytic behavior of semicondcutors has been extensively explored since it was discovered in TiO2 in 197Os. When TiO2 is exposed to UV light, the light is absorbed and electron/hole pairs are generated in the conduction and valeence bands. Holes in valence band will oxide/mineralize pollutant target directly or indirectly (via mediator hydroxyl radical). If the adsorbed A is O 2, O 2 will react with electron from conduction band to generate hydroxyl radical as described in the second set ofreactions. The photocatalytic reaction is schematically explained in Figure 1.Photoelectrochemical (PEC) cells using the photocatalytic reaction have attracted emerging interest as a potential route to convert solar radiation into useful forms of energy by reaction such as water splitting to generate hydrogen1 or the reduction of carbon dioxide.2 Another application ofphotocatalysis is water splitting and CO2 reduction, both of which utilize the electrons that are optically excited to the conduction band. 3•4 For this purpose, the conduction level of the semiconductor should be higher than hydrogen production level (EHZ1HZO) while the valence band should be lower than water oxidation level (Eo21112O). Electrons and holes will be generated on the semiconductor site, and holes generate O 2 at semiconductor site, while electrons will migrate to counter electrode to execute reduction forming H2. In addition to that, materials should be chemically stable to resist photocorrosion and have long lifetime of electron/hole pairs. TiO2 is a suitable material from the viewpoint of band arrangement and chemical stability requirement"

Jan 1, 2012

By J. Chen Kuriyama

One method to store hydrogen effectively involves the use of metal complexes such as the alkali-element aluminum hydrides. The hydriding/dehydriding properties of these materials depend on how to prepare them with different structures and microstructures. The present work focused on a high-energy ball milling technique to produce Ti-doped lithium tetrahydridoaluminate (LiA1H4) and lithium hexahydroalanate (Li3AIH6) powders with nanocrystallites. The phase structures and dehydriding/rehydriding characteristics were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller measurement, thermogravimetry, and differential scanning calorimetry. The mechanism of dehydrogenation and rehydrogenation was also examined by means of X-ray photoelectron spectroscopy (XPS). The results on the relation between the reversible hydrogen storage and catalysis function of the Ti-doped complex hydride indicate that both the homogenous distribution of Ti+AI nanoclusters and the Ti¬catalyst with Ti e> Ti3+ (Ti0/Ti2+/Ti3+) defect sites play important roles in optimizing the reversible hydrogen storage.

Jan 1, 2002

By Jeffrey Shepherd, Scott R. Smith, Eduard Guerra

"Electrochemical and spectroscopic evidence for the dissolution of a Au electrode by meso-2,3- dimercaptosuccinic acid (DMSA) from an acidic LiCl04 electrolyte is presented. Near the potential of zero charge, DMSA was determined to form a stable layer on the metal surface but at more anodic polarizations, DMSA was displaced from the metal through an oxidative process. The anodic displacement of the layer from the electrode resulted in a small amount of Au that was detected in the electrolyte using atomic absorption analysis. The extent of Au dissolution, was monitored while holding the potential of the electrode for 24 hours at the thermodynamic Eo/H,O in LiCl04 electrolytes containing 10 mM DMSA. This routine resulted in detectable quantities of a soluble Au-DMSA complex in the electrolyte and the greatest leaching was observed at a pH = 2.0. At room temperature, the leaching rate was stable at 10.9 µg cm·2 hr·' however, upon increasing the temperature to 50.0°C, the rate of Au dissolution increased yielding an average rate of extraction of 40.1 µg cm·2 hr- 1. Interestingly, after the first 12 hours of leaching at 50.0°C, the leaching current decreased dramatically suggesting surface passivation which prevented further Au extraction. The implications of this process in the industrial leaching of Au will be discussed.IntroductionThe use of cyanide in the industrial process of leaching Au from ores has raised concerns regarding both operational safety and environmental issues surrounding the disposal of spent leaching eftluents in tailings ponds. Depending on the chemical nature of the processed ore, the spent solutions that are released into the tailings ponds can contain toxic cyanide, either dissolved or complexed with different metals and may pose serious risk to wildlife as well as freshwater contamination to nearby water systems. Because of these issues, some recent studies have focused on the exploration of more environmentally-friendly molecules to selectively leach Au with appropriate kinetics. However, to effectively leach Au into an aqueous solution, a suitable ligand that reacts to form a stable chemical bond with Au is needed to form soluble Au complexes that can be later recovered [I]. Recently several sulfur bearing alternatives have been shown to leach significant quantities of Au in aqueous solutions. These include thiourea [2], thiocyanate [3], and thiosulphate [4]. However, alkylthiols are also known to quickly form a stable covalent Au-S bond [5], but have been relatively understudied in term of their ability to leach Au in solution, even though some short chain thiols are water soluble and relatively nontoxic."

Jan 1, 2012

By Yoshihiko Maeda

It is said that the 21st century will be an era of the remedy of the global environment. In order to reserve natural resources for the future and to avoid the dispersion of heavy metals after usage and to avoid pollution problems, it is extremely important to recycle heavy metals as much as possible by reasonable recovery procedures. The nonferrous metal industry is expected to play a important role in the recycling of heavy metals that are originally their products. From the depressed metal price experienced in Japan in 1980'h due to the sudden change in current exchange rate between US dollar and Japanese yen, one of major nonferrous metal company, Dowa Mining, has diversified its business area not only to the so-called down stream, but also to the environmental business including metal recycling, industrial waste treatment and soil remediation by utilizing technologis and facilities once used or still used for mining and smelting of copper, zinc, lead and precious metals. In this paper some of these applications will be presented.

Jan 1, 2003

By Norihiko Fukatsu

In order to use effectively the previously reported new sensing system for hydrogen and oxygen potentials in molten copper, the criteria of the potentials for getting sound castings have been determined in the laboratory experiment. The copper melt equilibrated with a given hydrogen and an oxygen potential was rapidly quenched in the crucible. The relations between the holding potentials and the gas porosity in the solidified sample were investigated by measuring the density of the sample and microscopic observations. It was found that the defects of the gas porosity became the maximum at the potentials where the dissolved amount of hydrogen and oxygen was in the mole ratio 2: I. The samples having the density more than 99% of the theoretical value were obtained in the higher oxygen and lower hydrogen potential region or in the lower oxygen and higher hydrogen potential region. The criteria thus determined were examined by comparing with the measured potentials in the practical easting machine. In tough-pitch copper casting, the problem due to gas porosity was found to be serious when the hydrogen potential increased. In the oxygen-free copper casting, the evolution of hydrogen was found not avoided. The gas porosity in the casting, however, was found eliminated when the oxygen potential was kept at a low value.

Jan 1, 2003

By X. K. Lan

The greater demand for high-quality large-diameter crystals has led to the robust idea of a free- flying solar-powered furnace satellite, whereby the buoyancy-driven convection effects are almost nonexistent, and diffusion-controlled crystal growth with minimal radial segregation is promoted. In the proposed solar furnace, a paraboloid of revolution imaging concentrator is used to focus the sun's radiation onto an-ampoule which holds the solid charge to be processed. The charge will start melting in the vicinity of the focal point, after which it is translated in order for the melt to resolidify as a single crystal. A ray-trace method has been developed to determine the incident concentrated solar heat flux on the ampoule surface for a perfectly-aligned configuration with an incoming columnated beam. A transient 2- dimensional conduction problem with phase change is formulated, which is solved using the commercial code FIDAP. Results highlighting the feasibility of growing GaAs, Ge and Si crystals with diameters of the order of 20 cm using the solar furnace satellite concept are presented. The transient temperature fields within various charge materials are quantified.

Jan 1, 1994

By M. Tokumasu, T. Mutoh, Y. Sugawara

"In October 1986, a process computer was introduced in order to achieve an optimum combustion of pulverized coal at the reverberatory furnaces. The secondary combustion air volume is controlled based on the nitrogen oxide concentration of the off-gas from the reverberatory furnaces. The carbon monoxide concentration has strong relation with the concentration of nitrogen oxide under the situation of using alternative fuels, such as chipped tires and p,ulverized coal. Using this computer aided combustion control system, both nitrogen oxide and carbon monoxide concentrations were stabilized and conventional monitoring and controlling apparatuses were absorbed into this computer system. Due to this easily operated system, labor cost was reduced and the operation of the reverberatory furnaces and the off-gas treatment plant became stable.IntroductionOnahama Smelter and Refinery started its operation in April 1965 as a large scale copper smelter and refinery in Japan. The green charged reverberatory furnaces were introduced and bunker C oil was chosen as the fuel for the reverberatory furnaces. After the oil crises, Onahama was forced to use cheaper fuels such as coal and waste tires, i.e., alternative fuels instead of the expensive oil. As the amount of the alternative fuels fed to the reverberatory furnaces increased, the concentrations of nitrogen oxide and carbon monoxide in the off-gas became unstable. Consequently, the fluctuation of the combustion condition became not to be negligible in view point of a combustion efficiency and pollution regulations. A process computer has been introduced to overcome these off-gas troubles and to reduce the operating cost of the smelter.Outline of Operation HistoryInitially, the operation started by one reverberatory furnace and then the capacity was expanded almost twice by additional furnace in December 1972. As shown in Figure I, the smelting throughput was depressed after oil crises in 1973 and 1978. From 1983 to 1985, some copper mines stopped their operations because of low price of copper metal. During this period, Onahama suffered from the shortage of concentrate production levels were depressed."

Jan 1, 1989

By Sridhar Seetharuman

Sulfur and oxygen dissolved in nickel and cupronickel melts can be removed as gaseous oxides of sulfur by a vacuum treatment. Presented in this paper is a new matched thermochemical diagram that permits direct evaluation of the equilibrium partial pressure of SO, as a function of temperature over an alloy of specified composition. The matched thermochemical diagram consists of a central plot which shows the integral Gibbs' energy of mixing for the binary system S-O2, at different temperatures. The central plot is flanked on either side by terminal plots of the chemical potentials of oxygen and sulfur, as functions of temperature, for different alloy compositions. By projecting the chemical potentials of oxygen and sulfur from the terminal plots on to the central diagram, the equilibrium pressure of SO2,can be directly read on the nomograms on the central plot at different temperatures. The matched thermochemical diaerams are - useful in assuring the efficiency of vacuum refining.

Jan 1, 1993

By Richard Jack De Klerk

The standard industrial method of arsenic removal from acidic aqueous processing effluents involves coprecipitation of arsenic with ferric iron (Fe/As>3) by lime neutralization in continuous circuits. To better understand current industrial practice, continuous circuit coprecipitation experiments were performed to identify industrially relevant process parameters and co-ion solutes that contribute to improved arsenic removal and retention. The coprecipitated solids were subjected to accelerated ageing at 20°, 40° & 70°C and arsenic behavior was monitored and modeled. Staging and the presence of calcium ions were found to have the most significant impact on arsenic retention. In this paper the techniques used and major results obtained are discussed.

Jan 1, 2008

By A. Korbel

The progress in understanding the nature of strain localization in metallic materials and in particular the understanding of the role of external (deformation conditions) and internal (material substructure) factors in the development of the tendency toward concentration of plastic flow within transgranular shear bands was the background of the concept given in the title. Following this idea, the practical possibility of replacing the homogeneous in a micro scale mode of deformation by transgrasnular shear bands gives a chance to change the arrangement of the dislocation substructure in the material from that typical for homogeneous deformation into long wavelength (transgranular), pseudo-periodic dislocation walls. The presence or formation of such a substructure in a thermodynamically unstable matrix may result in the formation of the products of phase transformation along shear bands, giving rise to a composite-like structure. This work is aimed to provide a coherent justification to the concept of Natural-Metal-Matrix Composite and summarizes the results of experimental works in this area.

Jan 1, 1997

By Bo Zhou

During secondary aluminum recovery, complex aluminum scraps are melted and refined often in a rotary melting furnace and the aluminum metal has to pass through a molten salt layer and melt down in a bottom aluminum bath. Previous experimental study and industrial observations have indicated that salt shell formation and re-melting on the metal solids in the early stage plays a critical role in the overall melting process of the scrap. In the present paper, mathematical models are developed to simulate the process of salt shell formation and its re melting, as well as aluminum melting in the molten melt. Influence of the salt layer properties, the residence time of the metal particles in the salt layer, the particle size, the temperature of bulk melt were investigated. Reasonable agreement with the measurement data was reached. The developed melting model will be used to construct a population balance model of the scrap melting behavior for a rotary melting furnace, taking into account the distributed characteristics of the scrap. Finally, an overall process model based on Computational Fluid Dynamics (CFD) for the rotary furnace will be constructed, coupling with the population balance model for the scrap melting.

Jan 1, 2003

By T. Manlyama

The Tamano Smelter of Hibi Kyodo Smelting CO., Ltd. went into operation in 1972. The Flash Smelting Furnace that was originally adapted was equipped with electrodes that were attached to the settler substitute of the slag cleaning furnace. Later the development of our own original coke combustion technology was promoted and a new Tamano Type Flash Smelting Furnace (T-FSF), without electrodes, was put into operation in 1988, T he technology of coke combustion and combustion the burner have continued to improve. As a result the copper losses in the Wag have been reduced as well as a stable operation has been achieved, Furthermore; this has been accomplished while increasing the concentration feed and the matte grade. The current objective is to continue to strive for high matte grade operation and to raise production efficiency while paying attention to the important subject of copper losses in the slag. In this report, the data related to the copper loss in the slag reduction are presented along with the influence of the thickness, settling time and coke. The recent operation conditions of the T-FSF are also presented.

Jan 1, 2003

By C. H. Quan

Solvent extraction tests were carried out on a rare earth chloride solution derived from monazite processing to determine the effect of extractant and diluent on the distribution coefficients between organic and aqueous phases, and the separation factor between rare earths. The extractants were 20% by volume di-2-ethyl-hexyl phosphoric acid (DZEHPA) or 2-ethyl-hexyl phosphonic acid (Ionquest® 801). Four Shellsol diluents were tested ranging from nil to 100% aromatic content. D2EHPA gave the highest rare earth extraction for a given pH but was less selective than Ionquest. The geometric mean separation factor between adjacent rare earths varied from 2.41-2.56 for D2EHPA to 2.62-3.01 for Ionquest. The nil-aromatic diluents (Shellsol 2037 and 2358) gave better separation factors in Ionquest but, in D2EHPA, were slightly inferior to the 100% aromatic diluent Shellsol AB. Yttrium behaved as a pseudo-heavy rare earth with a distribution coefficient lying between Ho and Er, as expected from its ionic radius.

Jan 1, 1992

By Min Xiaobo

As for treatment of zinc-containing wastewater, traditional SRB (Sulfate Reducing Bacteria) process was used, however, there exist two defects, like toxicity of heavy metal ions and high effluent COD (Chemical Oxygen Demand) value. In this study, a new technique, called ISIS process (Immobilized SRB sludge beads with Inner cohesive carbon Source), in which SRB sludge is embedded in carrier of PVA (Polyvinyl Alcohol) with carbon source that adsorbed on certain material, is put forward for the first time to overcome the two defects existing in traditional SRB process. Furthermore, it has been shown that compared to traditional SRB process, ISIS process increases average zinc removal rate up 30%, average sulfate reduction rate up20%, and decrease average effluent COD value to meet discharge standards. If activated carbon is selected for carbon source adsorption and fixing material, and PVA for immobilization material, the zinc removal rate can reach above 98% under the conditions of 35 and pH 6. Meanwhile, the mechanism of zinc removal has been determinated according to the results from SEM (Scanning Electronic Microscope) and XRD (X-Ray Diffraction).

Jan 1, 2006

By Y. W. Miao

Along the south-west coast of Taiwan is about 550,000 metric tons of heavy sand deposit containing about 10 % black monazite. The Institute has developed a separation process to recover the individual rare earths and the developed process has been commercialized by a local private company. The decomposition of the local black monazite by sodium hydroxide through hydrothermal and fusion methods has been investigated. In the hydrothermal process 4.5 wt. % of aqueous alkali solution was used in an autoclave. In the fusion process, caustic soda (9.8% NaOH) was employed in am open cylindrical reactor. The same product of hydrous rare earth oxides were obtained and then dissolved by hydrochloric acid and the p-H adjusted in order to separate the thorium from the rare earths. After filtration, the filtrate contained rare earth chloride and the cake contained mainly the silica and thorium hydroxide. Both methods give a yield of 90 % with respect to the rare earths recovery. A detailed description of operation and comparison of the two methods are given.

Jan 1, 1989

By S. Bagchi

The LaNi5-xMnx-hydrides have potential applications in cryocooling devices for non-mechanical method to compress hydrogen gas. Thermal aging behavior of LaNi5-xMnx-hydrides of compositions x=0.4 and x=1.5 has been investigated. The hydriding properties of the La1.02Ni4.6Mno.4 alloy do not change significantly after thermal aging at 453K for 260 hours. X-ray diffraction analyses of this aged alloy do not reveal the presence of any new phases but the Bragg peaks become broader. Line profile analyses show anisotropic microstrains with an average <e2>1/2 value of -5x103. Thermal aging of the other hydride, LaNi3.5Mn1.5 hydride, at 623K for 280 hours, showed significant disproportionation; the hydrogen capacity reduced significantly from an H/M value of 0.75 in the activated condition to -0.15 after aging. X-ray diffraction analyses showed disproportionated lanthanum dihydride, metallic Ni, and Mn phases. The Bragg peaks were very broad indicative of microstrains or small crystalline domains.

Jan 1, 1997

By Animesh Jha

Univariant diagrams are constructed for the reduction of nickel and cobalt oxide and sulphide minerals. The results from the carbothermic and hydrogen reduction of sulphide minerals are compared. The importance role of lime and calcium sulphate in controlling the emission of sulphurous- gases during reduction reaction is also explained. The mechanism of carbothermic reduction of nickel sulphide is explained by examining the sulphur exchange and reduction reactions. The phase equilibrium relationships that determine the formation of multicomponent liquid are characterised. Also the governing equilibria for inert atmosphere calcination- roasting of nickel and cobalt sulphide minerals are also described for the metallization of nickel and cobalt.

Jan 1, 1993

By Yu. A. Grinin, Yu. A. Sannikov, M. A. Lyamina, V. A. Shumskij, L. V. Slobodkin, N. N. Ushakov

This manuscript describes the Kivcet treatment of lead-bearing materials having high contents of copper and zinc. The tests were carried out on bulk concentrates from the Zyrianovsk Mining and Concentrating complex, "Kazzinc" JSC (Kazakhstan) with the following composition: Pb 37.6%, Cu 10.4% and Zn 6.8%. Two properties of the concentrate were under investigation: their calorific value and their desulphurization rate. By adding flux, the charge properties were brought close to the properties of high-grade lead sulphide concentrate. The charge was melted with high productivity. To ensure high copper recovery, Waelz residue was added to the charge. The residue contained more than 20% carbon and about 30% iron metal. The residue was partially replaced by coke that facilitates high copper recovery into the matte. The smelting achieved a production rate of 20 t/h with one burner. Lead recovery into the lead bullion was 88.8%; copper recovery into matte was 92.3%; zinc recovery into slag was 75.5%; and zinc recovery into the fume was 5.1%.

Jan 1, 2000

By Chen Yongming

In order to eliminate the serious environmental pollution caused by low concentration of sulfur dioxide smoke in antimony smelters, a new smelting process, named as reducing-matting smelting, is proposed in this paper. The effects of technical conditions such as smelting temperature, smelting time, Pyrite cinder addition and the amount of additive on the smelting of stibnite concentrate have been investigated by the method of single-factor experiment. The results show that the optimum conditions are as follow: The amount of pyrite cinder is 1.2 times of its theoretical amount. The addition of soda and sodium sulfate is 15% and 72.6%, respectively, to the amount of stibnite concentrate when the total amount of sodium is 30%. The reducing-matting smelting is conducted at 1100°C for 2h then the smelting temperature is raised to 1200°C for 50min. Under the optimum conditions, the direct and total recovery ratio of antimony can gain 90.99% and 98.87%, respectively, and the fixed ratio of sulfur is higher than 99%.

Jan 1, 2006

By Daojin Cao

Aiming at many controversial reports on Raman spectral pattern of octamolybdate ion in aqueous solution appearing in the literature, a new method for the establishment of corresponding relation between Raman spectral pattern and chemical components of aqueous molybdate solution was put forward using spectroscopy measure and component analyses of saturated solution of ammonium octamolybdate hydrate known structure. It was found that the main characteristic of Raman spectral pattern of the saturated solution was described as the same ?double-peaks, hereinto a weak peak at the boundary? as some literature, but chemical components of the saturated solution were affirmed to be octamolybdate ion (Mo8O264-) and double protonated heptamolybdate ion (H2Mo7O244-), which were in equilibrium in aqueous solution each other. The authors propose that the pattern of the saturated solution can be regarded as the standard pattern of primiparous octamolybdate ion during acidified molybdate solution. It is satisfying that the standard pattern is applied to the identification of primiparous octamolybdate ion during acidified molybdate solution.

Jan 1, 2006