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By Defeng Zhou, N. Trubaki, Jian Meng, Fanzhi Menga, Xiaojuan Liu, Yanjie Xia

"The microstructure and the electric conductivity of (Ce0.9Nd0.1)1 xMxO2 d (M=Mo, W) solid solutions were investigated. It has been found that their conductivity containing the grain (s gi ), the grain boundary (s gb) and the total conductivity (s t ) at 300°C- 700°C can be ranked as: (Ce 0. 9Nd 0. 1 ) 0.99 W 0.01 02- d (s gi = 0.065 S.cm·1, (s gb = 0.265 S.cm·1, s t = 0.039 S.cm-1) > (Ce0.9Nd0.1)0.99Mo0.01O2- d (s gi = 0.053 S.cm·1, s gb = 0.142 S.cm·1, s t = 0.029 S.cm-1) > Ce0.9Nd0.1 s 2- d (s gi 0.045 S.cm-1, s gb = 0.091 S.cm-1, s t = 0.018 S.cm-1) measured at 700°C. The highest conductivity is obtained in (Ceo.9Ndo.1)0.99W0.01O2 d. These results indicate that (Ceo.9Nd0.1)0.99W0.01O2- d is the most promising electrolyte materials of intermediate-temperature solid oxide fuel cells among (Ce0.9Nd0.1)1-xMxO2- d. IntroductionRare-earth (e.g. La3+, Nd3+, Gd3+ and Sm3l doped ceria-based ceramic materials have been acknowledged to be attractive electrolytes for solid oxide fuel cells operating below 600°C due to their high ionic conductivity [1, 2]. In order to improve ionic conductivity of these electrolytes further, in recent reports [3-6], some aids such as Mo03 [3] etc. in a limited amount can be used which causes extremely high conductivity. For example, Zhou et al. found that with MoO3 doping, the grain boundary conductivity of Nd3+ doped CeO2- d increased notably especially at lower temperatures due to the effect of severely undersized do pants [3]. It is well known that the size of W6+ (rw6+ = 0.60 Å) is close to Mo6+ (rMo6+ = 0.62A) because of lanthanide shrinkage. Thus, rare-earth doped ceria e.g. Nd3+ doped CeO2g with WO3 in a limited amount will be probably good and even better electrolytes. However, much less information is available about these materials. Therefore, in our paper, (Ce0.9Nd0.1)0.99 1-xMxO2- d (M=Mo, W) solid solutions have been prepared and characterized. Much higher conductive electrolytes are found in the series of (Ce0.9Nd0.1)0.99 M0.01O02- d particularly (Ce0.9Nd0.1)0.99W0.01O2- d"

Jan 1, 2012

By M. Okido, O. Takai, Z. Zhao, M. Ishikawa, R. Ichino, K. Kuroda

"Electrolytic method was applied to calcium phosphate coating on titanium plates as an excellent technique for high density and intensive contact of coated films on biomaterials. The effect of H2O 2 as oxidation reagent on coating characteristics was examined to obtain biomineral films. Solution was containing 7.0 X 10·3 mol/dm3 ofCaC12 and 3.0 X 10·2 of Ca(H2PO4)z, kept at 55 ""C. All deposits were hydroxyapatite (HAp) in this study, independent of H2O 2 concentration, applied cathodic potential and solution pH. In the case of H2O 2 addition, an increase in cathode current started at the low potential, namely, ca. -0.2 V (vs. SCE). In contrast, the current increased at more than ca. -1.4 V in the solution without H2O 2 addition. H2O 2 appeared to be an effective reagent for increasing nucleation density and improving adhesion of deposits on titanium plates.IntroductionIn recent years, many researches have been undertaken to develop the techniques of calcium phosphate coating on titanium or bioglass for medical implantation. High density and intensive adhesion of coating are necessary for adding bioaffinity to these materials and for inducing bone morphogenesis on them when implanted in human body.1) Electrolytic deposition has been a newly developed method as high-speed deposition process. By this method, the supersaturation of calcium phosphate can be increased just in the vicinity of metal substrates and the heterogeneous nucleation is promoted on them. In this process, H2O is reduced according to eq. (1) on the cathodically polarized electrode"

Jan 1, 2000

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 Alexander V. Suvorin, Vladyslav M. Sokolov

"The traditional technologies for production of the coprecipitated and deposited catalysts are analyzed from the standpoint of diversion of application of the feedstock and increase of efficiency for its usage. The options for return of the metals of spent catalysts to the catalysts production are described. The novel environmentally friendly and cost efficient approach for reutilization of the spent catalysts is realized in practice. It anticipates application along with spent catalysts of the waste generated in the catalytic productions. Reutilization of the Ni-containing catalysts is referred as an illustration. Introduction The recent development of large catalytic manufacturing for organic and inorganic synthesis, and petroleum refinery as well as for applied environmental catalysis has brought about increase and diversification of catalysts production. The generation of spent catalysts has been increased correspondently. The feedstock for production of catalysts is mostly metals in a form of nitrates, carbonates, hydroxides, hydroxydcarbonates. Sometimes salts of organic acids, of ammoniates, of chlorides and of sulphates occur. All these materials are scarce and expensive. So their repeated use by reutilization of spent catalysts is very actual issue. The traditional recycling the Fe-, Cr-, Ni-, Cu- or Zn-containing spent catalysts are carried out by pyrometallurgical reclamation of pure metals or alloys. They can not be used directly in production of catalysts [1, 2]. The hydrometallurgical approach is used for recycling spent catalysts with PGM, W, Mo, Co, Ni or Cu. It provides production of salts of these metals in a form of sulphates, chlorides, carbonates, hydroxydcarbonates and sometimes nitrates or ammoniates. Only a limited number of these salts can be used directly in production of catalysts. Material losses during catalysts production The basic feedstock for manufacturing coprecipitated and deposited catalysts that may be produced from the spent catalysts is aqueous solutions of metals nitrates. Their production is based on application of nitric acid as a dissolvent. About half of it is lost with the flue gases in a form of nitrates vapor and nitrogen oxides (II, IV). The last compound is generated by reaction:"

Jan 1, 2008

By Xuling Chen, Yi Wang, Xiaohui Fan

"The current control method of grate-kiln iron ore oxide pellet production is lack of accuracy and normalization due to the limited detection conditions. Therefore, mathematical models of grate-kiln temperature field are presented. With calculation of gas-particle heat transfer as well as enthalpy changes of moisture evaporation and magnetite oxidation, the thermal history of pellets throughout grate-kiln process can be acquired and used for production status estimation. Taking the calculated results as well as detected data in production as inputs, process parameters such as running speed, fan opening and coal injection rate as adjusting objects, expert system for grate-kiln pellet production is outlined. And the preheating section dominated control strategy is explained. Results of production application show that the stability rate of gas temperature in gas hood of preheating section is increased from 91.0% to 94.2%, compressive strength and first grade rate of pellet are increased by 3.62% and 2.36%, respectively, while FeO content is 18.18% lower. Control guidance of this expert system can solve production anomalies effectively, stabilize grate-kiln iron ore oxide pellet production and improve pellet quality.IntroductionSteel industry in China has developed rapidly in recent years. China’s crude steel production in 2010 is nearly 627 million, which is 44.2% of the world total production. Burden with higher quality is demanded by enlargement and modernization of blast furnaces. And oxide pellet production has become a growing concern. In 2010, the total production of pellet in China is 110 million, and about 60% is produced by grate-kiln process."

Jan 1, 2012

By Kiyoshi Takai

The Para-Eco Incinerator Ash Processing System for cleaning slag has been developed after a seven-year pilot plant study. The major part of the system is an electric furnace heated to 1773 K. The feed material consists of a municipal solid waste incinerator ash mixture containing a reducing agent of a coke and an inorganic flux of calcium and magnesium. With this furnace system, three kinds of products are produced. They are an inorganic molten salt that is slag, molten iron alloy absorbing non-ferrous metals, and fly ash. Due to the reducing atmosphere in the furnace, the slag does not contain any metal components as well as chlorine components just like natural rock and/or aggregate. A retreatment plant modifies this slag into a practically useful aggregate. The plant consists of a slow cooling step for crystallizing the slag as well as a water granulation step. The iron components in the ash are reduced to molten iron droplets, which concentrate at the furnace bottom. The non-ferrous metal components such as copper, chromium, and others are absorbed into the molten iron but not into the molten slag. Volatile metals such as lead, zinc, cadmium and others as well as sodium, potassium, and chlorine go back into the fly ash. A solvent extraction method and/or other appropriate procedures can be used to extract the metal components from this fly ash.

Jan 1, 2003

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 Toshiaki Tsuru, Takeshi Ohgai, Hisaaki Fukushima, Shigeo Kobayashi, Tetsuya Akiyama

"Electrodeposition behavior of Zn-Cr alloys from the methanol baths was investigated. In the methanol baths of low Cr3+ concentration, Cr (III) compound was incorporated in the deposits and no lusfrous Zn-Cr alloys was deposited. However, Cr was existed as metallic state in the deposits obtained from the baths of higher Cr3+ concentration. With an increase in water content in the baths, the chemical state of Cr in the deposits changed from metallic to trivalent state. Under the condition that metallic Cr can be electrodeposited, Zn deposition was significantly polarized to the potential of Cr deposition.INTRODUCTIONAn attention has been paid to Zn-Cr alloy plated steel sheet because of its excellent properties for body panels of automobile and electrical appliances [1]-[4]. This plating process can be operated using the sulfate solutions containing Cr3+ ion [1] - [6].In decorative single Cr plating, on the other hand, many attempts have been made to electroplate Cr from trivalent electrolytes, which is motived by environmental deficiencies of the presently used hexavalent process [7]. [8]. However, it has been reported that in the aqueous solutions the behavior of the electroreduction of 0 3+ is atypical due to the complicated nature of the chemistry and electrochemistry of cr3+ species [9]-[11]. Even in Zn-Cr alloy plating, it is difficult to codeposit metallic Cr with Zn in simple sulfate electrolytes [l]-[4], [12]. Therefore, it can be expected that the electrodeposition behaviors of Zn-Cr alloys as well as Cr are significantly changed when the electrodeposition is conducted in non-aqueous plating solutions.In this study, the electrodeposition of Zn-Cr alloy was conducted from methanol solutions to clarify the electroreduction mechanism of Cr3·-Cr0 in the alloy deposition process."

Jan 1, 2000

By Yuanbo Zhang, Zhixiong You, Guanghui Li, Peidan Wen, Tao Jiang

Sn-bearing iron ore containing small amount of Zn, Pb and As is one of the typical complex polymetallic ores in China. This kind of ore is not extensively utilized due to the complicated relationships between iron and other associated nonferrous metal minerals. Excessive contents of these elements would adversely affect the metallurgical operation as well as the quality of steel products. In this study, reduction behavior of Sn was detailedly investigated using H2 or mixed H2/CO as reductant. The results revealed Sn volatilization was improved in the presence of H2 than individual CO/CO2 atmosphere. Simultaneous volatilization of these elements was realized by roasting under weak H2/CO reducing potential, and metallization reduction was advantageous for further Zn volitilization. A metallic pellet (DRI) with Fe metallization greater than 90%, residual Sn, Zn, Pb and As content of 0.054%, 0.012%, 0.0045% and 0.09% was prepared via a simulated reducing gas of coal gasification.

Jan 1, 2015

By Susumu Nagae, Hajime Ikeda

Recently, a number of mine development projects have been setback by social, economic and, environmental circumstances that had not been seen before. Many of these problems do not always originate from direct mine pollution. Typical examples of these are· conflicts between the exploration company and the local residents, sudden objections just before the development is to begin, and unexpected tightening of environmental regulations. The common background to these problems is expanding global environmental awareness. This includes complex factors ·such as the expansion of exploration to remote regions, the brisk activities of environmental NGOs, the increase of international environmental laws and, governmental policy changes. Today, the range of issues concerning mine development is widening significantly. The participation of local residents arid NGOs in the development planning, together with the company and government, has become essential for smoothly carrying out mine projects and making them more beneficial for stakeholders. Introduction The common image of the environmental problem with respect to mining is direct mine pollution, such as the collapse of tailings dams, pollution from refineries, and acid mine drainage. All over the world, the mining industry has made large investments in capital and technology to solve and prevent mine pollution, and these efforts have been making steady achievements. However in recent years, new cypes of environmental problems which are not originating directly from mine pollution are emerging frequently. Most of the problems are concentrated at the exploration stage to early stage of development, which have less impact on the environment. In the worst case, mining project may be forced to cancel and could cause serious damage to the industry because they could not collect their investment. I would like to take a general view of the examples of new types of trouble, their characters, background, and strategies against these problems.

Jan 1, 2000

By Wenjie Zhu

Chromite ore processing residue (COPR) is a hazardous waste containing high concentration of chromium. We describe here a pioneer trial of detoxification of COPR in column reactor with an indigenous chromate reducing bacterium Leucobacter sp. Ch1, which showed high chromate reducing ability at high pH. Under the optimum conditions, at 30°C and pH 10.0, pH of leachate decreased from 10.3 to 8.3, and Cr(VI) concentration in solution decreased to zero mg L-1, and 76.4% of Cr(VI) was removed from COPR samples. The leaching toxicity of detoxified residue was 1.1 mg L-1 that was lower than national standard of China.

Jan 1, 2008

By Barry J. Welch

The production of primary aluminium can potentially lead to metal that, with minimum treatment, meets a high purity standard. Smelters that can achieve a significant proportion of their production in this manner have a competitive edge which is of growing importance as the use grows for such items as compact discs and the like. Superimposed on the desire to produce high quality metal are stringent environmental requirements that the industry must adhere to. The environmental 'legislation focuses on fluoride emissions and the approach adopted is towards a zero waste management philosophy. The fluoride recycling process does, however, result in volatile impurities being captured and recycled to the cell. Aluminium has an extremely high reduction potential and this results in a significant proportion of the recycled impurities being reduced at the electrolyte metal interface and thus contaminating the metal. This paper reviews sources of impurities and the impact of the operating procedures adopted on metal treatment.

Jan 1, 1996

By Suzzann Nordwick

Over the past decade, significant advances have been made in the development of sulfate-reducing bacteria (SRB) technology to treat acid mine drainage (AMD). Bench-scale testing, field demonstrations, and engineered applications of SRBs for the treatment of AMD will be presented. Designs include an in situ bioreactor installed in the subsurface workings of the Lilly Orphan Boy Mine in 1994, the SRB bioreactors installed at the Calliope Mine from 1998 to 2001, the integrated biological reactors built at the Surething Mine in 2001, and the ongoing development of a replaceable cartridge system. SRB technology benefits include the reduction of dissolved metal ions to insoluble metal sulfides and the neutralization of the AMD resulting from the production of bicarbonate from the oxidation of organic nutrients. This paper will address engineering design criteria including the selection of organic media and system permeability and complete mitigation of AMD. Research was funded under Interagency Agreement No. DW899388-70-01-1 between the US EPA and the US DOE and was conducted by MSE Technology Applications, Inc., through the National Environmental Technology Laboratory (DOE Contract No. DE-AC22-96EW96405) at the Western Environmental Technology Office located in Butte, Montana.

Jan 1, 2003

By Animesh Jha

The carbothermic reduction of chalcopyrite has been studied in the temperature range 1073 to 1273K in presence of lime. The role of lime during the reduction process is explained and the phase equilibria leading to the metallisation of copper and iron are discussed. The effect of coal and carbon monoxide on the reduction process have been studied and the rate governing steps are identified. This investigation also cites examples of possible mechanisms of physical separation of metallic Cu from iron during the reduction process.

Jan 1, 1992

By C. M. Dentan

Conventional testing of crude kaolin ores emphasizes physical properties as they relate to end uses of kaolin products. This approach to evaluating crude ores does not reveal the basis of behavioral differences between typical coarse and fine kaolins from central Georgia. Optical and scanning electron microscopy in combination with XEDS have been employed to characterize both coarse Cretaceous and fine Tertiary kaolin in order to shed light on the reasons for the gross differences in their properties. Routine evaluation of various parameters was also carried out. Bulk densities were 1.48 g cc-l for the coarse clays and 1.53 g cc-1 for the fine clays. Surface areas were 15 m2 9-1 and 25 m2 9-1, respectively. Brookfield viscosities were low for the coarse clays at 70% solids, and high for the fine clays. The situation was reversed for Hercules viscosities. Sixty percent of the coarse clays had particles of less than 2 um and the fine clays had 90% less than 2 cm. Micrographs of thin sections prepared from blue-dyed epoxy-impregnated crude ores and of SEM fabric samples demonstrated vivid differences in texture. Cretaceous kaolins appeared to be completely recrystallized residual products of former aluminous sediments, while Tertiary kaolins retained their essentially sedimentary character. Differentiation of the coarse and fine kaolins is rapidly accomplished by both optical and scanning electron microscopy, and should be considered a valuable analytical technique in evaluating kaolin ores.

Jan 1, 1981

By Jaeheon Lee

Gold-copper alloys are shown to form during the cementation of gold on copper in a solution containing 0.25M [S2O32-] at 25oC. The alloy composition is strongly dependent on the initial Cu:Au ratio in solution and ranges from Au3Cu to AuCu3. XPS results for Au, Cu, S, and O are reported as a function of depth through an entire deposited film with an initial solution containing 20 ppm [Au] and 30 ppm [Cu]. The deposit contained about 20 atomic % gold and was predominantly Cu3Au. Underpotential deposition (UPD) theory is discussed as a mechanism for explaining the formation of these alloys. Several other systems that produce alloys during contact reduction/cementation are also discussed.

Jan 1, 2003

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 Chidchai Loyprasert, R. A. Stoehr

"A computer model has been developed to predict grain structures in alloys solidified under unidirectional flow using a combination of three techniques -- solution of the equations for flow of an incompressible fluid bounded by curved surfaces by the SOLA-SURF algorithm, calculation of heat flow by a finite difference method, and simulation of grain formation by a two-dimensional cellular automaton (CA) model. The changing rigid surface has been taken into account. Heterogeneous and homogeneous nucleation are considered, and the growth kinetics of a dendrite tip are evaluated by the Kurz-Giovanola-Trivedi (KGT) model. These calculations were applied to solidification of an Al-4.5% Cu alloy flowing over a chill on the bottom of a channel, a system for which experimental results were available. Using a variety of flow rates and superheats, agreement between the computed and experimental results were very good including transitions between columnar and equiaxed grains, the aspect ratio of the grains, and the inclination of the grains to the flow.IntroductionModeling of casting and solidification processes has developed over the years along two distinct tracks: (1.) modeling of macroscopic heat transfer and fluid flow for design purposes, and (2.) modeling of microscopic processes such as nucleation and growth in order to improve the scientific understanding of the phenomena involved. The present work is an attempt to combine the macroscopic and microscopic approaches for the solidification of an alloy flowing over a chill. The specific case chosen is that of an aluminum-4.5 % copper alloy flowing linearly over a water-cooled copper chill for which experimental results were available over a range of flow rates and superheats. For the macroscopic calculations, the SOLA-SURF algorithm for solution of the twodimensional fluid flow equations was combined with the finite difference method (FDM) for calculating heat transfer. For the microscopic calculations, heterogeneous and homogeneous nucleation were considered, and the growth kinetics at the dendrite tips were evaluated. The cellular automaton (CA) technique was used to apply the microscopic kinetics to the temperature and .flow conditions."

Jan 1, 1999

By Hua-qing Li

Electromagnetic stirring process effectively improves the casting quality of metals. In this paper, the physical simulation experiment, in which the molten copper is displaced by mercury, was designed. The factory test parameters were determined according the simulated data. The flow behavior of the mercury to be stirred as well as the relations between the microstructure of plate blanks and the current parameters were analyzed. With an appropriate electromagnetic stirring, the inverse segregation of tin for C51900 alloy plant blank reduces from 15 % ~ 30 % to about 5 %, and the proportion of equiaxed grain rises to larger than 30%.

Jan 1, 2009

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