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By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Tomoya Nihei, Hiroshi Hayashi

"A novel selenium removal process called Recycled Green rust/Ferrite Process is developed by MMC. In this process, a mixed Fe2+-Fe3+ hydroxide compound, green rust (GR), reduces selenate to elemental selenium, while GR is consequently oxidized to magnetite Fe3O4. Sequencing batch-mode experiment showed that the residual selenium concentration gradually decreased with the number of batch test increased. Stable selenium removal was achieved when the number of batch test exceed 15 times. Optimum selenium removal ratio reached 99.95% where initial Se concentration 2.1mg/L decreased to 0.001mg/L. Furthermore, the continuous feeding test carried out through a pilot-scale plant with a feeding capacity 600 L/hr. Approximately 860-hour-feeding test was carried out for the selenium-contaminated groundwater which had an averaged selenium concentration of 0.88 mg/L. Selenium concentration in the effluent from thickener maintained less than 0.01 mg/L (selenium removal rate of 99%) until a net operating time reached 800 hours.IntroductionJapan is one of the largest producers of selenium, and thus there are potential environmental impacts of selenium on soil and aquatic environments. The Mitsubishi Material Corporation (MMC) owns some real estate properties whose soil and groundwater was polluted by selenium and other heavy metals. These sites include former industrial plants: a smelter for nonferrous metal and a fabricating semiconductors and pigments. Selenium in aquatic environment commonly exists in four oxidation states, namely, VI, IV, 0 and -II. Selenate ion (SeO4 2-), the most oxidized form of selenium, and selenite ion (SeO3 2-) are highly soluble and mobile. Elemental selenium (Se0) is insoluble in water and therefore has much lower toxicity. Because selenium is carcinogenic and teratogenic at high concentration, the national effluent standard in Japan is fixed at 0.1 mg/L and the environmental standard at 0.01 mg/L. Although there are several selenium removal techniques, the most conventional process is coprecipitation with a ferric hydroxide because of its simplicity and low cost. It is known that selenite is adsorbed strongly on the surface of ferric hydroxide, but selenate is not. The low affinity of selenate on oxide mineral surfaces was demonstrated by the fact that selenate could be easily displaced by adding competing anions, particularly sulfate ion. Selenate removal from polluted water is one of the most difficult techniques, and more effective methods are desired. MMC developed a novel selenium removal process [1]. In this process, the concentrated slurry that contains Fe(II)-Fe(III) hydroxyl-salts known as Green Rusts (GRs) contributes to selenate removal. The main components of the iron precipitate in the reactor are GRs and their oxidation product, magnetite (Fe3O4)."

Jan 1, 2008

By Gordon Lewis

A complex mixture of hydrated reaction products is obtained from hydrothermally treated refractory cements and castable concretes. TGA can be used both to identify the product phases in the mixture and to determine a quantitative relationship among the phases. When reacted mixtures contain compounds that decompose simultaneously, or nearly so, additional assumptions must be introduced in order to develop a quantitative phase analysis. It is the purpose of this paper to examine some of these assumptions and to demonstrate their application, particularly to refractory cement systems.

Jan 1, 1982

By E. F. Vegman, Ndabezinhle Dube

"In the practice of conventional sintering, production is always afflicted with the problem of being unable to get a uniform quality of produced sinter in the bed. Invariably the top layer of the sinter cake is composed of weak but highly sinter, while the bottom layer is over-fused, forming a sinter that is very strong but less reducible. These symptoms point to a variable distribution of the heat balance in the process of sintering which results in a deficit of heat in the top layers of the sinter bed and an excess of heat in the bottom layers, due to an increasing input of regenerated heat in the heat balance down the bed. This causes losses in the productivities of the sinter machine and the blast furnace.The current work was designed to improve on the solution to the above problem through the establishment of a more accurate combustion zone heat balance of the sintering process. This development is mostly on the method of determining the regenerated heat input in the overall heat balance. Previous methods were based on the assumption that the width and the velocity of the combustion zone remain constant through out its whole life, which is not the case since tests have shown that both its width and velocity increase as the combustion zone moves down the bed. In this work, these factors have been taken into account. Tests and calculations using the model were carried out for haematite and limonitic ores. The high sensitivity of the model to changes in the sinter mix composition and sintering conditions was demonstrated.The results present the following prospects:• The minimum theoretically possible coke breeze consumption during the sintering of any type of iron ore fines, under any sintering conditions, can be established.• The model can be used to control the metallurgical quality of the sinter in any point in the sinter bed since calculation data includes desired basicity, combustion zone temperature and FeO content in the sinter produced."

Jan 1, 2001

By F. E. Brinckman, G. J. Olson, D. Johnsonbaugh, T. K. Trout

"Microbiological metal recovery is an emerging technology likely to play an increasing role in commercial ore leaching, metal removal from process and waste streams, and perhaps ultimately in processing to yield metal products in specified forms or oxidation states. We are studying the potential for using microorganisms for the recovery of elements important to emerging materials technologies and for which domestic supplies are limited and/or low grade. Examples to be discussed include the bioaccumulation of yttrium and gallium. These elements are important in the production of new superconductor and semiconductor materials. However, limited domestic reserves and technologies for their recovery may cause supply problems. Microbiological processes may offer new techniques for recovery of these and other strategic elements.IntroductionMicroorganisms in ore leachingMicroorganisms assist in the commercial leaching of copper and uranium from low grade ores (1,2) and recently have been shown to have immediate commercial potential for the pretreatment of refractory gold ores to increase the gold-cyanide recovery yield (3). Copper bioleaching is the best known example of biotechnology applied to metal recovery. Copper can be recovered by commercial leaching of huge piles or dumps of low grade sulfidic ores and waste materials, which are not otherwise processable. Microbial activity in the leach dump environment oxidizes metal sulfides to soluble metal sulfates:"

Jan 1, 1988

By S. Tandon

Equilibria studies of selenium distribution for sodium-borate slags were initiated at 1473k under reducing condition as a function of slag composition and alloy composition. The Se distribution coefficient (% Se in slag/% Se in metal) increased from 0.4 to 2.9 with increase in basicity (0.53 to 0.86) for Cu-0.446% Se alloy. However, the results are not very useful from industrial application viewpoint. Therefore, in order to improve the distribution of Se, CaO (10% to 50%) was added to the sodium-borate slag of basicity 0.864. On addition of 502 CaO, the distribution coefficient increased roughly by 100% for slag composition - 44.5% Borax, 22.2% Na2C03, 33.3% CaO and Cu-0.44677 Se alloy. Further, the value of this distribution coefficient has been found to increase by an additional 80% on addition of 20% CaF2 to the above slag for all Cu-Se alloy compositions. Also with increase in initial concentration of Se, the distribution coefficient has been noted to increase.

Jan 1, 1992

By Jorge Alberto Soares Tenório

Household zinc based batteries contain some heavy metals such as zinc, manganese and mercury. There is a large effort from manufacturers in order to eliminate the last one. As a municipal waste, the disposal of batteries has become an increasing worry. The aim of the present work was to characterize dry batteries scraps, and establish a flowsheet for their processing. This was done using unit operations of mineral processing and parameters and yields of each stage have been defined. Such procedures have been chosen due to their low cost. The operations were hammer mill grinding, size separation, magnetic separation and specific weight separation in water. The characterization step was done through chemical analysis and x-ray difiactometry. After size classification, it was verified that 76.6% of the total amount of zinc was over 1.70mm. This fiaction was constituted basically of zinc and some coarse pieces from the steel body, paper and plastics. This fraction was submitted to magnetic separation followed by specific weight separation in water. A visual examination showed that during the grinding process, graphite was concentrated in the finer fractions. Manganese concentration in the fractions over 6,35mm was less than 2%. This means that there was low contamination by the paste in this fraction. It was due to the entrapment of the paste by steel scraps (from the body) and zinc (from the cup) during grinding.

Jan 1, 1999

By Makoto Ohtsuka

The ternary Ni2MnGa intermetallic compound is an intelligent material which has both a ferromagnetic property and a shape memory effect (SMB), The use of the shape memory alloy films for an actuator of micro-machines is very attractive because of its large recovery force, The purpose of the present study is to investigate the effects of fabrication conditions and to clarify the relationships between these properties and fabrication conditions of the Ni-Mn-Ga films, The Ni-Mn-Ga films with a thickness of nearly 5 um were deposited with a radio-frequency magnetron sputtering apparatus using a NisoMn2sGa25 or Nis2Mn24Ga24 target. They were heat-treated at various temperatures between 873 and 1273 K for homogenization and ordering and then cooled in a furnace, The composition of the films depended on the sputtering power. The as-deposited films were crystalline and had columnar grains, After the heat treatment the grains widened and the grain boundary became indistinct with the increasing heat treatment temperature, The martcnsitie transformation temperature of the heat-treated films increased with increasing nickel content. Furthermore the effect of plastic deformation and constraint aging on SME is also investigated, After plastic deformation, the two-way SME was shown through the martensitie transformation and its reversion, The intensity of X-ray diffraction peaks from stress-induced martensitie phase was found, The constraint-aged films also showed the two-way 5MB by thermal cycling,

Jan 1, 2003

By Robert L. Opila

Negative electrodes for alkaline nickel-metal hydride batteries composed of MmNi3.5Al0.8Co0.7, where Mm is misch metal, have been characterized electrochermically and using x-ray photoelectron spectroscopy. The stability and rapid hydriding and dehydriding kinetics of the alloy in KOH are attibuted to a surface film. The protective surface film is shown to consist of an porous, outer hydrated layer and a dense, inner oxide layer. In addition, metallic nickel and cobalt are found throughout the film, and are presumed to form a conductive, percolative network that permits rapid electron transfer from the bulk to the solution, allowing rapid electrochemical formation of atomic hydrogen.

Jan 1, 1997

By A. A. Hejja

The effect of composition on electrical conductivity, viscosity and liquidus temperature of the slags was investigated in the temperature range of 1300" to 1450°C. The synthetic slags containing CaO, MgO, SiO,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Platinum Group Metals) from the Merensky Reef of South Africa. FeO and SiO, were found to affect the viscosity and conductivity the most while liquidus temperature depended on MgO content in addition to these. The activation energy for electrical conduction was found to vary from 67 to 159 kJ/mol and that for viscosity from 125 to 209 kJ/mol. Optimization of the slag composition was attempted on the basis of opposite trend of the viscosity-electrical conductivity relationship with slag composition.

Jan 1, 1994

By H. L. Ludtke

Microlaminate composites were fabricated by electron-beam physical vapor deposition. The microlaminates consisted of five layers, each 2 to 4 pm thick, and were composed of either pure metal layers (Cu-Ag), or alternated between metal and intermetallic layers (Nb(Al)- Nb3Al). The microlaminates were heat treated in an Ar atmosphere for 2 to 12 hours, at temperatures of 600°C for the Cu-Ag and 1000°C to 1200°C for the Nb(Al)-NbsAl. Microlaminates were examined after deposition and after heat treatment by scanning electron microscopy and energy dispersive x-ray spectrometry. The effects of heat treatment on the morphological stability of these composites will be described.

Jan 1, 1999

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By Lin Yang, Minjun Tang, Shuishi Liu, Jianfeng Zhou, Linjiang Qing, Xiaolei Song, Yufeng Guo, Tao Jiang

"The dynamics of oolitic hematite magnetic roasting was studied. The results show that oolitic hematite magnetic roasting was controlled by the internal diffusion, and the diffusion coefficient was 9.018x10-7 m2·s-1when the oolitic hematite was roasted at 650°C. Magnetic susceptibility improves when temperature increases and roasted time prolonges under the condition of roasting at 650°Cfor 50min, with the magnetic susceptibility is 39.88%. CaF2 and Na2C03 can significantly improve the magnetic susceptibility at the same roasting condition, and the magnetic susceptibility was 63.35% and 57.99% respectively, thus the reduction of oolimic hematite was promoted.IntroductionWith the continual depletion of free-milling iron ores and its rising price, developing the abundant resources of oolitic hematite has become one of the main research areas. The oolitic hematite accounts for 10% of China's iron ore reserve, and it also accounts for 30% of red ore reserve in China [1]. In order to exploit the oolitic hematite, there are many beneficiation research methods, including fine grinding/selective flocculation/high intensity magnetic separation or flotation, high-gradient magnetic separation, low intensity magnetic separation/high intensity magnetic separation/reverse flotation, chloridizing roasting/acid pickling, magnetic roasting/leaching process etc [2]. However, the oolitic hematite is easy to slim and the valuable mineral is covered by the slim, because of the tiny granule of value mineral, then the ooides are formed due to the state of layer morphology formed by iron ore and ganaue minerals [3, 4]. Fairly good separation indexes were hard to be obtained by traditional separation due to its structural features, so the magnetic property of the iron minerals will be changed with the use of the magnetic roasting [5, 6], which result in hematite variably altered to magnetite and simplified technological process so that a good separation indexes will be obtained by using the low intensity magnetic separation. Therefore, in order to provide theoretical direction of how to use the oolitic hematite effectively through the magnetic roasting, the oolitic hematite of GuiZhou province was studied, which emphasized on researching the dynamics of oolitic hematite magnetic roasting."

Jan 1, 2013

By Mikhail Mikhaylenko

Natural and technogenic sources of rare earth elements (REE) and other rare and scattered metals are remarkable for their chemical diversity. The pregnant solutions going to processing for the valuable metals have very complex compositions. Both targeted elements and competing impurities are present in the solutions in different chemical forms. Thus processing of such materials demands application of different technological tools addressing numerous specific tasks on the way to the final product. Screening work was undertaken to identify the best resins among developmental and commercial products addressing typical cases in the hydrometallurgy of scandium and REE. The cases outline typical sources of scandium and REE, such as streams of TiO2 production, extracted phosphoric acid, barren uranium solutions and others. Specially designed ion exchange resins can be effective tools.

By P. N. Anyalebechi

The effects of application of steady and pulsed electric current on the cast microstructures of ingots of a 7050 type aluminum alloy have been experimentally investigated over a solidification rate range of 0.1-10 K/s. This involved the application of an electric current of 465-930 mA/cm2 of melt surface area to laboratory-size ingots solidified in a unidirectional manner. Within the ranges of electric current density and solidification rate investigated, the applied electric current reduced the average dendrite, grain, and second-phase particle size. It also made the size distribution of the second-phase particles more uniform. The mechanism for the observed refinement of the cast microstructure by the applied electric current is not well understood. The potential effects of heat-induced local convections, shear stress-induced fragmentation of dendrites, increased temperature gradient due to Joule heating and the thermal and constitutional supercooling engendered by Peltier, Thompson, and Joule heating are discussed.

Jan 1, 2009

By Michael A. Lllga

Electrically Switched Ion Exchange (ESIX) is an approach for ion separation that combines Ion exchange (IX) and electrochemistry by utilizing electro active IX films to provide a selective, reversible, and economical separation method that greatly reduces secondary waste generation compared with conventional ion exchange. Studies on the development of films with improved stability and capacity and their use in continuous flow systems for ion separations will be. reported. Both technical and economic evaluations demonstrate ,the viability of once-through or batch recycle waste processing with ESIX.

Jan 1, 1999

By E. Oshima

The only one reverberatory furnace smelting in Japan has been alive in Onahama Smelter, Onahama Smelting and Refining Company. The fuel for the reverberatory furnaces had been changed from bunker C-oil to mainly coal and partially waste tires to reduce the energy cost. The steam, recovered by the waste heat boilers of the reverberatory furnaces, has been utilized fully for the power generation to save the purchase power. Copper concentrate has been smelted also by injection through tuyeres in the P.S. converters since 1983. The amount of concentrate, treated in the converters, was increased by the construction of small oxygen plant in December, 1990. In the paper, the current practice and improvements in the reverberatory and converter operations are described.

Jan 1, 1993

By M. Girgis

The behavior of arsenic III during electrolytic refining of copper in acidic copper ?sulphate electrolytes was studied by different electrochemical methods such as, linear potential sweep, cyclic voltammetry, chronoamperometry and chronopotentiometry. The study showed that arsenic behaves as a depolarizing ion and has a deleterious effect on copper deposit. Three substrates; Pb, Cu and Ag were used during the refining process and the electrode kinetics were found similar for both Cu and Pb electrodes while a little difference was found for the Ag electrode. A microscopic study by scanning electron microscope was undertaken to show the influence of arsenic on deposit's morphology. Surface analyses of the deposit were carried out by some electronspectroscopic techniques such as Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The results showed that arsenic coexists with copper deposit at potential?~ -0.25 V.

Jan 1, 1987

By J. L. Jambor

Sulfide-rich tailings accumulated in a 4l-hectare impoundment at the Waite Amulet minesite near Noranda, Quebec, have undergone partial oxidation and destruction of the principal sulfides (pyrite and pyrrhotite) in the vadose zone. Mineralogical studies and whole-rock chemical analyses of 18 samples from 3 boreholes along a cross-section of the tailings pile indicate that the principal chemical manifestations of the alteration are a pronounced depletion in sulfide-sulfur, and an enrichment in total Fe as Fe203' Other elements such as Al, Mn, Mg, Ca, Na, and K in the solids show erratic or inconsistent variations, but a trend to Si enrichment in the oxidation zone is clear. The trend is interpreted to be a relative enrichment whereby the proportion of the stable silicate minerals has increased as a consequence of the consumption of pyrite and pyrrhotite in the oxide zone.

Jan 1, 1989

By R. D. Irwin, W. M. Mullins, E. A. Medina

"Various stability criteria are introduced and thermo-kinetic models for metallurgical processes are used as concrete examples for evaluation. Kinetic criteria for the process of dynamic recrystallization are proposed. These criteria are compared to the non-equilibrium thermodynamic approaches discussed in the literature. The application of macroscopic stability criteria to materials processing is then discussed.IntroductionThe mechanical behavior of metals at elevated temperature is very well predicted by any of several empirical constitutive relations. Typical is the power-law (or Swift's) form,Equationwhere r-is the stress, y is the strain and m, n , t0, y0 and Q are material constants. This form has been used with some success in the metals processing area [1]. In general, though, all of the empirical constitutive equations are static, failing to account for any dynamical properties of the system they seek to describe.The physics of warm deformation is qualitatively well understood. An example is power-law creep, where the dominant mechanism is assumed to be lattice diffusion limited climb of dislocations, which allows the strain-rate to be determined by the applied stress through"

Jan 1, 1997