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By Itsuki Uehara, Hiroyuki T. Takeshita, Tetsuo Sakai, Nobuhiro Kuriyama, Hideaki Tanaka

"AB5 type hydrogen storage alloys (A: rare earths, B: transition metals) are extensively applied to a negative electrode of a nickel metal hydride (Ni-MH) rechargeable battery for portable electric equipments, electric vehicles, hybrid vehicles etc. Performance of a hydrogen storage alloy electrode is affected by various factors, microstructure and surface composition of the alloy and structure of the electrode as well as composition of the alloy. Control of those factors enables us to commercialize the Ni-MH battery in various field.IntroductionA Nickel-metal hydride (Ni-MH) battery has been extensively developed because of (1) good compatibility with a nickel cadmium (Ni-Cd) battery, (2) high energy density (1.5-2 times higher per unit volume than a Ni-Cd battery) and high dischargeability, and (3) low environmental pollution. The charge/ discharge reactions can be written as [l, 2,3]:(+) Ni(OH)2+OH- = NiOOH+H2O+e· (E=+0.490V NHE),(-) l/6LaNi5+H2O+e-· = 1/6LaNi5H6+OH- (E=-0.828V NHE),where E° is a standard potential of an electrode vs. normal hydrogen electrode (NHE). Because of the above advantages of a Ni-MH battery, the battery have been widely used as a power source of portable computers, cellular phones, electric vehicles (Toyota ""LAV4L EV"", Honda ""EV Plus"" etc.) etc. Some hybride vehicles (Toyota ""Prius"" and Honda ""INSIGHT"") and fuel cell vhehicles (Toyota ""FCEV"") are power-assisted by a high-power Ni-MH battery. In 1999, the production of Ni-MH batteries reached 870 million cells in Japan. Most of commercialized NiMH batteries are incorporated with rare-earth-based AB5-type hydrogen storage alloy as a negative_ electrode. The production of rare-earth-based alloy is estimated to be approximately 8000 tons.The battery performances of the Ni-MH battery, for example, capacity, durability (cycle life), dischargeability (kinetics) and selfdischarge, ate closely related to the metal hydride· (MH) electrode, especially, the hydrogen storage alloy in the electrode. Substitution of alloy components, heat treatment, and surface treatment in order to change surface and bulk structure of hydrogen storage alloys have been examined by us and many reseachers in order to improve the performances of MH electrodes. This paper is a review of our and their efforts to improve performances of MH electrodes."

Jan 1, 2000

By C. Lupi

The electrorefining of primary copper is a well known technology: in this work copper scrap was directly processed in the same way. he copper and copper alloy scrap was previously pressed by means of a 20 tons apparatus in order to avoid pyrometallurgical operations. The samples obtained in this manner showed a good compactness so that they were used as anodes in the electrorefining tests. The tests were carried out on anodes made by copper scrap, copper alloy scrap and a mixture of the two. The electrorefining tests were performed at both 303 and 333 K, in a perspex cell having a volume of 500 ml using a current density of 250 A/m2. The cathode used was always a sheet of pure copper and the electrolyte composition was 40-50 g/l Cu as CuS04 and 150-200 g/l H2SO4. Current efficiency in the range of 92-97% and specific energy consumption ranging from 0.14- 0.20 kWg of copper were reached in all the tests. The refined copper deposits were analyzed by AAS to verify their purity and observed by SEM to highlight their morphology.

Jan 1, 1998

By P. S. Seryogin

R & D works supported by industrial-scale tests, which were carried out by joint efforts of the OAO Gipronickel Institute and MMC ?Kola? engineers, have accomplished with the production of 90?95% metallized nickel powder in tube furnaces (NPTF), with its ?active fraction? (AF) to be further used for decopperization of nickel electrolyte by cementation. Consistently positive results obtained in the course of the lab and industrial experiments have allowed the Severonickel Combine management to effectively replace all activated nickel powder (ANP), which was then employed for cementation, with the AF, having activity over 80%, and eventually shut down the entire operation of gaseous reduction. Ever since the developed technology has been implemented, its annual economic effect exceeds 2 ml. dollars.

Jan 1, 2006

By Shunsuke Yagi

A surface alloying technique was investigated using alternating pulsed electrolysis in an aqueous solution containing a single metal component for the formation of an Fe-Cr layer on an iron substrate. In the process, the iron substrate was dissolved during each anodic polarization of the pulsed electrolysis, providing iron ions in the vicinity of the substrate, while the Fe-Cr alloy was electrodeposited during subsequent cathodic polarizations. A bright, flat, and crack-free Fe-Cr layer with a composition gradient was obtained using a solution containing a trivalent chromium component and a complex forming agent together with some supporting or buffering salts.

Jan 1, 2006

By Hee Dong Jang

Crystalline metal oxide nanoparticles such as lithium cobalt oxide (LiCoO2) and indium tin oxide (ITO) were synthesized from sprayed droplets of aqueous precursor solution by flame spray pyrolysis. Complete thermal decomposition of the aerosol precursors was obtained at high flame temperature. Molar concentrations of the precursor solution, and the flow rate of combustion gas such as hydrogen, oxygen and air were varied to control particle size, size distribution and crystal structure. The crystalline nanoparticles synthesized were nearly spherical, and their average primary particle diameters ranged from 11 to 35 nm for LiCoO2 and from 8 to 15 nm for ITO.

Jan 1, 2006

By Ju Shao-hua

Although nowadays gold extraction methods are very abundant, none of them is satisfying, especially, in the field of heap leaching of low grade gold ore. The traditional heap leaching method of cyanide method plays an inglorious role of badly environmental pollution. In this paper, a bran-new and innoxious method of gold extraction system, metal-ammonium-chloride-ammonia (MACA), was proposed, and also analyzed both thermodynamically and practically. Thermodynamically, according to the principles of simultaneous chemical equilibrium and electronic charge neutrality, the thermodynamics of Au-NH4Cl-NH3-H2O system was studied by using the exponential computation method and through MATLAB programming, and the solid figure of its potential - c(NH4Cl) - c(NH4OH) was drawn. The results showed when the concentrate of ammonia is higher than 0.6 mol?L-1, fAu+/Au is only about -0.2 v. Practically, the leaching results of a cuprous gold ore showed that the extraction of gold can reach to 80% in this system. The preliminary results of reduction of the rich solution with copper and zinc powders showed that with deoxygenizing, the reduction effects were relatively good. These new findings and results have established a theoretical and practical base for developing a new process for heap leaching of low grade gold ores in this system. And the new process owns a series of merits such as, non-cyanogens, nontoxic, broader applicability.

Jan 1, 2006

By David R. Sadedin

The highly negative Gibbs free energies of hydrogen atom reactions suggest that refractory oxides such as titanium dioxide should be easily reduced by hydrogen atoms. These reactions appear to be most favourable at low temperatures; oxides should be reducible even at room temperature. Since hydrogen atoms are produced in plasmas containing hydrogen a number of investigators have used hydrogen plasmas of various sorts to test these possibilities for reducing refractory oxides, in particular TiO2. None of these attempts has succeeded, a small degree of reduction being achieved in only a thin layer near the surface. A deeper consideration shows that several factors complicate the reactions expected on the basis of the negative Gibbs free energy. One factor is that the back reaction by water molecules produces molecular hydrogen, not hydrogen atoms, and the metal atoms that have been reduced may be immediately re-oxidised. In plasmas there are complications due to diffusion, thermal and charge boundary layers and charged particle reactions. Interpreting the results of hydrogen atom reactions is difficult. Hydrogen is not detectable by electron dispersive spectroscopy and amorphous products are not determinable by x-ray diffraction. Another consideration is economics. The cost of producing hydrogen atoms has a large bearing on the metals for which hydrogen atom reduction may be competitive. In this paper these factors are discussed, some necessary basic studies are highlighted and the general principles of a laboratory reactor are given, together with the results of tests using ZnFe2O4, ZnO and TiO2 as test oxides.

Jan 1, 2006

By G. A. Brooks

The problem of treating concentrates with increasingly higher levels of arsenic and antimony is compounded by the trend to stricter environmental guidelines regarding the disposal of smelter wastes. Much of the arsenic and antimony from non-ferrous processes is recovered as oxide fume. The options for handling these fumes include recycling them to the smelter, stabilising and disposing of them, and recovering values from them. Whilst arsenic oxide has little value, there is a market for antimony oxide and this provides an incentive for devising techniques for separating antimony oxide from arsenic oxide before disposal of the arsenic oxide. Arsenic can be separated from antimony oxide by selectively volatilising the more volatile arsenic trioxide from a mixed oxide sample or by selectively condensing the less volatile antimony tetroxide at high temperatures, leaving arsenic trioxide to condense out at lower temperatures. The results of selective volatilisation experiments at 379 to 587 °C indicate that it is difficult to achieve an arsenic content below 5.0 wt.% using air or nitrogen as carrier gas due to the formation of solid solutions between the two oxides. Injection of oxygen into a mixed vapor stream improved separation by selective condensation and antimony tetroxide containing as low as 0.23 wt.% was obtained in laboratory experiments.

Jan 1, 1994

By Melinda Channel, Alan W. Weimer, Jonathan R. Scheffe

"There is a need to develop cost effective renewable energy processes for the production of clean fuels that can simultaneously mitigate the U.S. energy/global environmental security issue. If H2 can be obtained cost effectively via the splitting of water using concentrated sunlight, then it’s possible to operate a fuel cell using renewable H2 or to synthesize other fuels based on renewable H2 for generating electricity or for running internal combustion engines. For example, H2 can be reacted with sequestered carbon dioxide (CO2) to produce syngas (H2/CO) via reverse water gas shift (RWGS), i.e. H2 + CO2 ? CO + H2O. The syngas can be catalytically methanated to form synthetic natural gas (SNG) or it can be catalytically reformed to produce liquid fuels such as “green” gasoline via the MTG process (syngas? methanol ? gasoline). The desert SW United States is home to world class sunlight. Fundamental ferrite thermodynamics will be reviewed, an example of the beneficial effect of ferrite surface area on reaction kinetics will shown, and process economics will be investigated for a 100,000 kg/day facility to produce H2.Introduction and Background ThermodynamicsSpinel ferrites of the form MxFe3-xO4, where M generally represents Ni, Zn, Co, Mn, or other transition metals, have been shown to be capable of splitting water according to the two step cycle shown below:MxFe3-xO4 + solar thermal energy ? xMO + (3-x)FeO + 0.5 O2 (1)xMO + (3-x)FeO + H2O ? MxFe3-xO4 + 2H2 (2)This is an inherently clean and sustainable process, as the only net inputs are solar energy and water, and the net outputs are hydrogen and oxygen. Ferrite water splitting cycles are advantages compared to other high temperature water splitting cycles, such as the ZnO/Zn and Mn2O3/MnO cycles, because thermal reduction has been demonstrated at significantly lower temperatures[1, 2]. As a result, overall efficiency may be increased due to the fact that radiation losses increase as the fourth power of temperature, and material considerations for reactor design should be more flexible. Additionally, cycle repeatability has been demonstrated with relative ease as compared to other thermochemical cycles [3-6]. However, the amount of hydrogen per mole that is generated is significantly less than for other high temperature thermochemical cycles due to the fact that only Fe3+ is capable of being reduced at the temperatures of interest[6]. In addition, water oxidation kinetics appear to be very slow, likely due to diffusion or surface area limitations created by near surface oxidation [6, 7]."

Jan 1, 2010

By Jianhua Xin, Min Chen, Cuihuan Huang, Shan Yu, Xiaoao Li, Nan Wang, Guanghao Chen

Copper enrichment behavior in continuously cast slab induced by scale formation after continuous cooling in H2O vapor atmosphere and consecutively in air has been experimentally investigated by combining with SEM-EDS analysis, for the purpose to examine the effects of initial slab surface temperature and contents of copper and nickel. For Slab 1 with copper content of 0.1 percent, no visible copper enrichment is found at scale-substrate interface irrespective of the various scale microstructures formed at different initial slab surface temperatures. For Slab 2 with higher contents of copper and nickel, copper-rich phase accumulates and stays at scalesubstrate interface under the condition of lower initial slab surface temperature; while Cu-rich phase in the porous scale formed at higher initial slab surface temperature is noted with simultaneous Ni-enrichment appearing in front of the steel-scale interface. Both a porous scale and high nickel content work together to provide pores for copper-rich phase migration away from interface and occlude within the scale layer.

Jan 1, 2016

By Jan Yaozhong

The composition and the possible utilization of Ti bearing blast furnace from a titanomagnetite blast furnace smelter were studied. The slag contained about 20% Ti02 and trace Sc. The mineralogical analysis indicated that Ti in the slag is mainly as perovskite. By means of magnetite separation, the Ti containing phase could not be enriched. An effective hydrometallurgical approach was proposed with sulphuric acid leaching. The method proposed for processing the studied slag renders product Ti02 and SC203. Besides the recovery ofTiO2 and SC2O3' the leaching process yields fine grained residues which can used as additives for making cement.

Jan 1, 1996

By Darryl Lovato, Ramiro Pereyra, Daniel S. Schwartz

"During an annual inventory of nuclear material, a plated steel container which contained plutonium oxide failed. The container had been packaged for temporary storage but had been overlooked and remained in storage for more than 23 years. Although it was determined that the failure occurred through the slip-top rim, a metallurgical evaluation was requested to help to determine the integrity of the container.Optical metallography and scanning electron microscopy were used to analyze the character and degree of corrosion in the container. The depth of corrosion, measured at approximately 10 µm, did not pose a threat to the integrity of the container. However, the corrosion morphology and chemistry did suggest that a galvanic cell had developed between the tin and steel from the condensation of water. The morphology also suggests that the attack of the steel took place over a series of cycles due to changes of the environment.IntroductionMetallographic analysis was requested as part of the investigation into the mechanism of the failure of a slip-top container (#38621) containing plutonium oxide (PuO2) powder. The container had leaked during a special nuclear material (SNM) annual inventory causing contamination and closure of the vault. A photograph of the container and interior container is shown on the right in Figure 1. An initial investigation established that the source of contamination was the consequence of the failure of multiple layers of containment. Initially by the deterioration of the interior plastic bottle and polyvinyl chloride (PVC) bagout bag, and finally through the lid and steel container interface at a location where tape had not adhered properly [1]. Although the source of the breach was established, it was determined that metallographic analysis was important to establish the extent of deterioration of the steel container."

Jan 1, 2008

By James B. Pfeiffer

TETRA Technologies, Inc., has applied its HDSIM metals precipitation system to treat a waste stream containing scrubber blowdown and process water from a smelter operation. The combined stream contained cadmium, lead, selenium, arsenic and zinc, plus some iron and copper. Treatment requirements included meeting stringent mass flow limitations for specific heavy metals. The HDS ? system can reduce the arsenic from 600 ppm to less than one ppm. The process generates a dense sludge that can be reprocessed in a smelter, eliminating the liability associated with landfilling. Flow diagrams and process details are discussed.

Jan 1, 1994

By W. G. Davenport

A survey of world copper refining tankhouse .practices has been carried out. This paper compiles the results and examines changes in operating practices .since the similar 1987, 1991 and 1995 surveys. Continuing trends are the installation of ISA Process and Kidd Process stainless steel cathode technology, polymer concrete cells, anode preparation machines and automatic cranes. Instrumentation and automatic control are increasing, particularly for addition agent optimization; solvent extraction .and ion exchange techniques are being increasingly applied for electrolyte purification. The overall consequences of these changes have been 'improved cathode purities and enhanced tankhouse productivities.

Jan 1, 1999

By K. Sanjay

Factorial optimisation technique has been used to develop regression equations at different time intervals for extraction of manganese from precipitated manganese oxide/hydroxide in sulphuric acid using charcoal as the reductant. The three parameters chosen for a 23 full factorial design were : acid concentration, amount of carbon and temperature. The regression equations were used to predict >> 90% extractions as well as kinetic data.

Jan 1, 1996

By Staia. Mariana H.

Thermochemical equilibria of the heterogeneous system Ti-N-H-CI-Fe-Cr-Mo-Ni-Mn-C were calculated by using a commercial software based on the minimization of the free energy. Equilibrium calculations were done for temperatures varying between 800" and l 100°C and an initial molar relationship between reactants, a=NJTiCI,, of 0.1 to 2. The deposition process was considered to occur at atmospheric pressure. The activities of the alloying elements of the stainless steel were considered equal to their molar fractions. It was shown that for the conditions studied the substrate is no inert with respect to the gaseous phase. The existence of liquid chlorides was predicted for temperatures between 800" and 850°C and a ratio between 0.3 and 0.9. The most important metallic chlorides which appears to be present from the calculations in appreciable quantities in the gaseous phase are iron dichloride and manganese dichloride. In the low-temperatures zone and for low initial nitrogen contents, it result that the appearance of the liquid chlorides seems that partially inhibits the production of gaseous HCI. The highest deposition process efficiency calculated is obtained at a temperature 2 900°C and a N2/TiCI, ratios 2 0.7.

Jan 1, 1995

By Kim Verbeken, Evelien Van de Steene, Marc Verhaege, Jeriffa De Clercq

"AbstractThe industry is confronted with stricter discharge levels and an increasing awareness to avoid toxic waste (such as heavy metal containing sludge obtained in physicochemical water treatment) and recover valuable metals. This can be realized by ion exchange or by electrodeposition. Both techniques however show an optimum concentration range to efficiently remove and/or recover metals: electrolysis can recover the metal in its metallic form but suffers from low efficiency when applied to diluted solutions, whereas ion exchange can only be applied economically in the low ppm range.A combination of ion exchange followed by electrodeposition was applied to an industrial wastewater. The strong acidic ion exchange resin was stripped with H2SO4 giving a solution of 9g/L nickel. From this solution, nickel was electrodeposited in an ammonia buffer on a Ti-mesh cathode with high current efficiency. It is shown that organic compounds (surfactants, brighteners, …) present in the industrial wastewater do not influence the recovery process.IntroductionAlmost all rinse waters emerging from metal plating plants are generated during the washing operation of plated materials. These solutions with low metal content must either be recycled within the process or be discarded to the surface water after decreasing their metal content to acceptable levels determined by the local environmental regulations, which become more and more stringent. Today, the most commonly used practice is a physico-chemical treatment (precipitation) and a resin post treatment to meet the standards. A more sustainable approach should use a technology to recover efficiently the metal or metal salt without the production of sludge and the effluent should be consistent with environmental regulations."

Jan 1, 2008

By I. A. H. Schneiderl

Eichhornia crassipes approaches being a scourge in many parts of the world, .choking waterways and hindering transport upon them. At the same time it is known to readily abstract heavy metal ions from water and, thus, aids in the removal of heavy metals found in such waters. This paper considers the possibility of using specific parts of the plant as an inexpensive adsorbent for the removal of heavy metals from contaminated chemical and mining industry waste waters. In particular the root of the plant was found to be an excellent accumulator of 'heavy metal ions including uranium from solution. It is. also suggested that dried roots of the plant ?might be placed in simple bags and used in a very low cost metal ion removal system.

Jan 1, 1995

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 J. R. Parga

A shortage of landfill space and growing environmental concerns in Mexico are renewing interest in the recyclability of scrap from automobiles. This work describes a pyroumetallurgical process for the recovery of metallic lead from waste lead paste. Argentopyrite concentrate is commingled with lead paste residue and smelted in a fuming process thereby transferring the precious metals into lead bullion. The process consists of smelting lead paste and argentopyrite, sodium carbonate, and metallic iron at smelting temperatures of about 1100 T. The reaction products are slag and molten lead bullion enriched with precious metals. A major feature of this process is the removal of precious metals from the bullion by means of zinc, whereby a silver-zinc intermetallic compound is formed and floats out of the lead. The recoveries of precious metals are about 98%.

Jan 1, 1996