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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 Martin E. Nelson

Several heavy metal separation techniques are currently being developed for soil remediation at various Department of Defense and Department of Energy (DOE) Facilities. The majority of these techniques involve a wet process using water, PH modifiers or other compounds. The United States Naval Academy (USNA) has developed a dry process for heavy metal separation. The process uses air classification technology to concentrate the metal contaminant into a fraction of the soil. The advantages of this dry process are that it creates no contaminated by product and uses commercially available technology. The USNA process is based on using a Gayco-Reliance air classifier. Tests have been conducted with the system at the Naval Academy and the University of Nevada-Reno (UNR). The USNA tests used soil from the Nevada Test Site mixed with bismuth at a concentration of 500-1000 ppm. The UNR tests used soil from four DOE sites mixed with uranium oxides and plutonium at an activity level of 100-700 pCi per gram. Concentration of activities and volume reduction percentages are presented for the various soils and contaminants tested.

Jan 1, 1995

By W. K. Tolley

The U.S. Bureau of Mines (USBM) is currently investigating improved technology for mineral flotation. A variable often neglected in flotation control is redox potential. The use of redox control is illustrated by the separation of molybdenite from chalcopyrite. Laboratory testing showed that redox potential had a greater effect on product quality than collector addition. A significant need in froth flotation is greater reliability of the sensors used in measuring and controlling redox potential in mineral slurries. The USBM has developed an automated method for removing scale and reconditioning gold redox-sensing electrodes. Fouled electrodes are anodically polarized to 1.2 V versus the AglAgCI reference potential to remove scale. The electrodes then are conditioned by a brief potentiodynamic treatment to re-establish electrochemical equilibrium. In laboratory tests, this technique removed calcarious deposits from gold electrodes and reconditioned them for useful service in approximately 10 min. In plant practice, this technique would obviate the need for plant operators to manually polish electrodes, and also should result in greater reliability in redox measurements. Inexpensive, automated equipment to condition electrodes in a plant setting is described.

Jan 1, 1995

By Keith Cramer

As a leader in the development of metal extraction technology, Avecia continues to pioneer advancements for the processing of copper through leach, solvent extraction, and electrowinning of copper. From the initial patent of the second generation of oxime 5- nonylsalicylaldoxime in the 1970's; to the effective use of modifier technology; and development of computer assisted modeling programs, Avecia is driving SX technology to maximize extraction productivity. Keys to consider when advancing productivity are: 1) high quality, high performance products; 2) a responsive, partnering approach to technical service; and 3) tools to aid in the education of industry wide technical personnel with a view on continuous improvement. The focus of this paper is on the advancement of tools to aid in the education for optimization of processing copper through solvent extraction. One such tool is Avecia's own customized solvent extraction modeling program called MEUM. MEUM is currently used world wide to analyze plant operations, test ideas for improving operations, assist engineering companies in design, and to teach basic solvent extraction concepts. Recently MEUM has also been incorporated into a University setting. In the spring of 2000 Avecia worked with the University of Melbourne to integrate MEUM into their Mass Transport tutorial class. Students completed exercises to evaluate how operational changes affected a solvent extraction plant's performance. This paper introduces the basic functions of the program and discusses the successful implementation of MEUM into the University of Melbourne curriculum.

Jan 1, 2002

By Masahiro Yoshimura, Sergiy Korablov

"Hydi-othermal corrosion ofTiN, TlAlN and CrN PVD films (3 µm thick) deposited on SUS-304 substrate was studied in 100MPa water in 20-950°C temperature range up , to 750h. The beginning temperature of their reaction was determined as 200°c for TiN and TiAlN and 500°C for CrN films, which are quite low in comparison with that of air oxidation of those powders. Very thin oxide scales. of TinO; n-I homologous series phases were formed above 300°C. TiO2 anatare. is observed for TIN and TiAlN films at 400°C. The· feature of hydrothermal corrosion of CrN films seems to be CrNxOy phase formation.Distinguishable weight changes were observed at higher temperature than 700°C for TiN, 750°C for· TiAlN and 800°C for CrN respectively. Hydrothermal corrosion kinetics .was constructed to calculate the activation energy of hydrothermal corrosions. On the base of obtained data, hydrothermal corrosion resistance was as follows: TiN – TiAlN - CrN. Facetted oxide crystals were formed at higher temperature than 500°C for TiN, TiAlN and 850°C forCrN.IntroductionThe metallic nitride (TiN; TiAlN, CrN) PVD films have high hardness, strength and wear resistance. Therefore these films are widely used in industry for wear resistij.nce application such as cutting tools and die molds. Their performances depend on not only the mechanical properties but also corrosion resistance of coated films. High temperature oxidation of metalliq nitride and nitride films was well studied [1-5]. However there are no reliable data concerning the .corrosion resistance of coated nitride materials. In high-temperature and high-pressure water. There are a few reports on hydrothermal corrosion of nitride films [6,7]. The increase of corrosion resistance of CVD films was observed in following succession TiC - TiCNO - TiCN - TiN at 300-680°C temperature interval and I 00 MPa pressure water according to data of the first report. Kawana et al. [7] have reported about excellent corrosion resistance of CrN films under 290°C and 8, 6 MPa water during I 000 h in the circulating type experimental loop. The films thickness was about 7-10 µm in both cases. However it remains unclear the chemical state of the surface species and especially in-depth distribution, oxide scale thickness and its growth, and defects formation in the oxide film."

Jan 1, 2000

By Yoshio Waseda, Tetsuya Uda, Tom H. Okabe

"Halide salt has been tested as a reductant for producing titanium powder directly from TiCl4. From the results of thermodynamic investigation for several rare earth chloride systems, DyCl2 was found to be used for the reduction of TiCl4 instead of the conventional metallic reductant. When TiCl4 was fed into molten salts containing DyCl2 at 1073K, titanium powder of several ten micron meters in diameter was obtained. In contrast to the sponge titanium produced by the conventional Kroll process, the present new process using a halidothermic reduction in a reactive molten salt appears to be suitable for producing metal powder. From the thermodynamic point of view, the resultant DyCl3 can be reduced to DyCl2 by magnesium. By utilizing the multivalent halide redox couple, some possible ways of titanium powder production directly from TiCl4 by magnesiothermic reduction are shown to be feasible. This can also be applied to the development of a new continuous titanium reduction process.1 IntroductionTitanium and its alloys show attractive mechanical properties such as strength-to-weight, rigidity-to-weight ratios and excellent corrosion resistance. Nevertheless, the application of titanium alloys is limited compared to other structural materials (e.g. steels, aluminum alloys) because of its high cost of production. Currently, almost all of titanium is produced by metallothermic reduction of TiCl4 by magnesium (Kroll process)[1] in an airtight metallic reactor. This process is batch type and labor intensive. Therefore, many attempts to develop new process for producing titanium are investigated so far."

Jan 1, 2000

By David Norval

Ni, Co, Cu and Pt, mattes are common materials that require granulating and milling of the resultant granules for further processing. This route is acceptable if the material is brittle (friable) which is a property associated with the higher sulphur mattes. For lower sulphur levels, where the matte is less amenable to milling, the costs of the milling increases. This paper will compare water granulation with certain dry granulation processes and the downstream processes required for Hydrometallurgy. It will further introduce and expand on atomisation which offers a further safety benefit in the control of the metal flow into the 'wet zone' with the use of a tundish flow control also reducing the conversion from the matte to powder in one fairly straightforward operation.

Jan 1, 2006

By Richard W. Lawrence

Leaching of copper from sulfide minerals using biooxidation offers a potential route for copper recovery. Oxidation of . sulfide sulfur can proceed either; to sulfate or to elemental sulfur depending on mineralogy and process conditions. The advances in commercial application of biooxidation for sulfidic gold ores has made available operating and cost data which allow the derivation of conceptual costs for copper ore processing for comparison with conventional processing routes. Although costs for copper biooxidation generally remain high relative to conventional smelting, application might be competitive in specific cases. Biooxidation becomes more competitive in the general case if the cost ofS02 emissions in pyrometallurgical processing were to be internalized to a greater degree than currently required. This paper describes the technical aspects of biological processing of copper sulfide ores and concentrates, specifically with respect to the fate of sulfur. The environmental and economic implications of the biooxidation route are discussed in relation to conventional processing.

Jan 1, 1996

By Hani Henein, J. Barry Wiskel

"The easy accessibility and power of the PC, as well as the education of our engineering students in the use of these tools, are compelling reasons for developing computer aided instructional (CAI) tools. There are a wide range of areas in the engineering curriculum where students must learn the steps and the process of applying judgement in problem solving. In the typical course instruction, · an instructor introduces theory to students; the application of the theory to solving problems is often demonstrated in the abstract. Students therefore spend a significant amount of time learning how to apply the theory to problem solving. Additional time and effort must then be spent to get students to the point of learning concepts and integrating this knowledge. A number of computer aided packages have therefore been developed for use in several courses in the materials science and engineering curriculum that encompass both calculational and instructional capabilities. This paper presents an overview of some of these packages which include the solution of a non-linear equation, the instruction of binary diffusion couples, an introduction of crystallography, an introduction to heat transfer and the solution of thermodynamic stability diagrams. The context in which these CAI Tutorials were developed and are being used will be discussed. The pitfalls in the development of these packages will also be discussed. The use of the tutorials has important implications on the expectations from an engineering education of both instructor and student.IntroductionTraditionally, it is quite routine to teach engineering students how to use a computer (the PC today for undergraduates) as a tool in performing engineering calculations or in simulating a process or a unit operation. This often takes the form of one course in computer programming, whether it is Fortran, Visual basic or a spreadsheet, and another course in numerical computation. However, the materials and electronic revolution have brought about considerable advances in computer power and speed, and accessibility. Today, the manipulation of digital images, movies, and speech are commonplace on a desktop PC.' Many mathematical models that were executed only on workstations can now be readily handled on a PC. Concurrently, more of our students own a PC even if their curriculum does not require them to purchase one. Today, virtually every university student has been introduced to the PC in either their elementary or high school education. Hence, the increased capabilities and accessibility of the PC and the familiarity of students with this tool make it compelling to explore its use as an educational tool for our engineering students. This is not a traditional role of a computer in our engineering curriculum."

Jan 1, 2000

By Zhang Chuanfu

The fibrous nickel oxide powder was prepared by the method of chemical precipitation and pyrolysis, that is, the NiO precursor was firstly precipitated from nickel ions solution with addition of oxalate salt and then the final NiO powder was obtained by pyrolysis of the prucursor. The effects of the pH, reaction temperature, reactant concentration, addition of surfactant on the morphology of the precursor particles were investigated. The influences of the various conditions, including the temperature and time, the air flow and the speed of the temperature increase on the morphology, average size and specific surface area of the NiO particles were also addressed. The fibrous NiO particles with IOO~ 120 in axis/diameter ratio and 5.5 m2/g of the specific surface area may be produced under certain operation conditions by this process.

Jan 1, 2003

By Ramana. G. Reddy, Haoxing Yang

The electrodeposition of zinc from zinc oxide using urea and choline chloride mixture in a molar ratio 2:1 is investigated in different experimental variables, namely, the concentration of added [BMIM]HSO4, temperature, and applied cell voltage. The additive, [BMIM]HSO4, was determined to have beneficial effect on the current efficiency, energy consumed in the process and surface morphology of the deposits. The highest current efficiency (92.6%) and lowest energy consumption (2.92kWh/kg) was obtained for solution with 20mg/mL [BMIM]HSO4. The morphology showed the formation of absorbed additive layer on the cathode at higher concentration of additives. Experiments were conducted at different temperatures between 343K and 388K and at various applied cell voltages between 2.7V to 3.6V to determine the best experimental conditions. By varying temperature, highest current efficiency (91.3%) and lowest energy consumption (2.69 kWh/kg) was obtained at 373K. The electrodeposition process is enhanced between the applied voltage 3.0-3.3V by achieving lower energy consumption (2.75~3.06kWh/kg) and higher current efficiency (88.4~89.7%). SEM images showed grain size is significantly increased in higher applied voltages. While at higher temperatures, it seemed to generate particle growth as clusters at the outer deposit layer.

Jan 1, 2014

By Nicole de Jager, Michael J. Nicol

"In order to liberate gold from refractory gold ores and concentrates it is generally necessary to oxidise the surrounding sulphide minerals, typically pyrite and arsenopyrite. Traditional methods of oxidation include pressure leaching, roasting and bacterial oxidation. In recent years, bacterial and pressure oxidation have found increasing favour, although these methods are by no means completely satisfactory and each is subject to particular disadvantages.A novel process has been developed as an alternative to the traditional methods whereby electro-generated ferrate(VI) ions in alkaline solution are used to oxidise a pyrite concentrate. This process has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. As an added benefit, operating in an alkaline environment is advantageous for downstream cyanidation processes.Ferrate(VI) is a relatively unknown species, due mainly to its instability in acidic solutions. However, in alkaline solution it has been observed to be sufficiently stable for use as an oxidant when used under favourable conditions. Ferrate(VI) is most conveniently manufactured electrolytically via the dissolution of high-carbon anodes in strongly alkaline solutions. Some literature has been published on the electrolytic generation of ferrate(VI) and relatively high efficiencies have been observed by both the authors and other researchers.This study utilises both electrochemical techniques and leaching experiments to examine the kinetics of the oxidation of pyrite by ferrate(VI), which is produced electrolytically. Cyclic voltammetry, rotating disk voltammetry and potential step experiments have been used to investigate the kinetics and mechanism of the oxidation process."

Jan 1, 1997

By Zhijing Zhang

Sodium borosilicate is the basic composition of coating materials, Vycor and Pyrex glasses. In the present study, viscosities of Na2O-Si02-B2O3 ternary melts were measured under various compositions and temperatures. Experiments were carried out using rotary viscometer and graphite components. Our experimental results were compared with those in literature. Based on present experimental results, the previous structure based viscosity model was modified. The predicted viscosity results are in excellent agreement with the present experimental data in the temperature range with molten state samples. The fitting ranges of the model cover the composition of XB2O3 from 0.1 to 0.6 combined with xSio2 / xNa2O = 0.5, 1,2 and 5 respectively.

Jan 1, 1998

By Behrouz Abedian, Livia M. Racz

"We address dynamic interactions between high-energy, reactive surfaces of polymer-matrix composites and solid surfaces. A common characteristic of these interfaces is that bonding occurs readily upon contact. In many industrial and biomedical applications, it is desirable to suppress this bonding phenomenon. This interfacial effect is discussed in light of the development of our new method of handling polymer-matrix composites in dental applications. This method involves vibration of the solid-polymer interface at different frequencies. For each material, there is a critical frequency at which the sum of the viscoelastic and inertial energies of the fluid at the surface exceeds the energy available for bonding. When the polymer is vibrated at or beyond this frequency, it does not adhere to solid surfaces. An important aspect of the developed process is that it can be used to characterize surface and interfacial properties of polymers under dynamic conditions, whereas existing techniques are restricted to the study of bulk dynamic properties.IntroductionThe purpose of this paper is to report on the development of a new method for manipulating polymer-matrix composite materials used in dental applications, and the potential of this process for use in materials characterization. The materials under discussion have polymer matrices of a combination of bisphenol A-glycidyl methacrylate (BIS-GMA) and triethylene glycol dimethacrylate (TEGDMA), and contain filler particles of silica and/or zirconia glasses. These materials are called direct aesthetic restorative materials, and are used for filling of cavities, repairing chipped teeth, and for other restorations in which appearance is of importance. They have the appearance of natural tooth material, and are therefore in great demand for use in the anterior portion of the mouth(l,2)."

Jan 1, 1998

By F. D. S. Marquis

An investigation of the mechanisms of formation of two types of porosity-primary and secondary-their characterization, evolution during processing, and effects on the mechanical behavior (fracture, fatigue, and failure) of 7X50 and 2X24 alloys has been conducted. The mechanisms of formation of three forms of primary or cast porosity were investigated, and each form was characterized: (a) macroscopic shrinkage porosity-MSP); (b) microscopic interdendritic porosity (MIP); and (c) hydrogen gas porosity (HGP) or primary hydrogen porosity (PHP). The mechanisms of formation of four forms of secondary or thermal/thermomechanical porosity were investigated, and each form of porosity was characterized: (a) high temperature oxidation (HTO). internal hydrogen precipitation (IHP), or secondary hydrogen precipitation (SHP); (b) preheating blistering porosity (PBP); (c) eutectic melting porosity (EMP);and, (d) dissolution micro void formation (DMF). The evolution and interactions of the primary and secondary types of porosity (w.ith special emphasis on PHP and SHP) during industrial and laboratory processing and their effects on the fracture and failure behavior of both types of alloys (with special focus on fatigue crack initiation and propagation) were investigated.

Jan 1, 1996

By Sarel Johannes Francois Gates, Ida Kero, Yan Ma, Gabriella Tranell

During the tapping and casting of manganese ferroalloys, fumes are generated and released to the working environment. The fumes are mostly composed of metallic oxides generated due to reaction between high temperature molten metal and ambient oxygen in the air. From an environment perspective, it is important to limit these emissions. However, to do so, it is important to understand fuming mechanisms and kinetics as well as fume compositions, i.e. element behavior during the oxidation process of liquid manganese ferroalloys. Silicomanganese alloys are composed of aminimum of 65 wt% Mn and 17 wt% Si, 2 wt% C as well as minor and trace elements. These elements include Fe, Mg, Al and other elements originating from ores and reductants. Trace elements behavior in fume from liquid silicomanganese generated under an impinging air jet in the temperature range of 1450–1700 °C has been investigated in this work. The thermodynamic and kinetic conditions governing the generation mechanisms are discussed.

Mar 1, 2017

By J. N. Hryn

This paper describes some of the work done in Phase 1 of a multi-year, five-phase program aimed at demonstrating the economic feasibility of producing commercial-scale quantities of commodity materials derived from salt cake residue-oxide. The amount of salt cake generated annually in the U. S. is estimated to be 510,000 tons, including 340,000 tons of residue-oxide. Used beverage can (UBC) processing accounts for the majority of residue-oxiae that could be made available for further processing into commercial products. To characterize the composition of residue-oxide. eight residue-oxide samples from various secondary processors were obtained and analyzed. Surprisingly, the composition of residue-oxide was found to be independent of source or alloy family being processed, with? the exception of slightly elevated silicon levels in 3XXand UBC residue-oxide samples. Major phases detected in the residue- oxide were? alumina, spinel, and aluminum hydroxides. Preliminary economic analyses indicated that the refractory market appears to be the best choice for high value-added products produced from residue-oxide with minimum processing. Bench-scale tests indicated that low silicon containing residue-oxide is ready to enter this market, but the elevated silicon content of UBC and 3XX residue-oxide preclude this possibility. A separation technology should 'be developed to remove silicon-containing . species from the alumina and spinel values Present in residue-oxide. This technology would then allow UBC and 3XX residue-oxides to be converted to significantly higher value-added products.

Jan 1, 1995

By Zhuo Sheng

We have designed a high-temperature Raman micro-furnace and cell that is suited for the electrochemical process study of the NO3 − in molten NaNO3– KNO3 (fraction of NaNO3 50 wt%) salt. During the cycle voltammetry and constant potential electrolysis process, the Raman laser beam was focused near the electrode; subsequently, the Raman spectra are obtained and the reduction process of NO3 − is analyzed. In the CV cathodic scan process, the new peak attributed to the ν1 mode of NO2 − emerges, and the peaks assigned to superoxide ions (O2 −) and peroxide ions (O2 2−) are not found. In the constant electrolysis process, the peaks at 1130 and 800 cm−1 appear when the potentials are between −2.0 V and −3.2 V (vs. Pt). The results show that when the NO3 − is reduced in molten the NaNO3–KNO3 mixtures, the reduction product O2− cannot stably exist, and O2− will react with NO3 − to form of superoxide ions (O2 −) and peroxide ions (O2 2−).

By G. Lindkvist

Roasting of concentrates with high impurity levels is normally done in multiple- hearth furnaces where the concentrates are heated with oilfired burners in order to remove As, Sb and Bi before the final sulfide oxidation. Although it is a countercurrent heat exchange process it uses a lot of oil. In order to develop an energy saving, and from a working environmental point of view a less harmful process than the multiplehearth process, pilot-plant tests have been done in a two-stage fluidized bed for partial roasting. The test materials have been As-rich concentrates with 8-25 % As some 5b and Bi. The Cu-content was 0-28 %. The tests have been successful with <0.3 % As,in the calcine and with an elimination of 5b between 80 and 90 %. In order to achieve the proper conditions for good impurity removal, 1.e. right temperature,residence time and sulphur potential, the tests were performed in a special designed roaster. The roaster consists of two beds with the facilities for recirculation of calcine, preheating of the blast, and possibility to use oxygen enrichment. The construction makes it easy to control the reactions that generate the heat in the bed and reduce the amount of dust that passes through the cyclones. As two roasting steps are used, the possibility to obtain optimal conditions for impurity removal is improved and the calcine can either be smelted to a normal matte, or after being dead-roasted in the second stage, be leached in the normal way for gold extraction. The calcine was smelted with slag. The matte and the slag obtained had low quantities of impurities in the matte and a favourable distribution of impurities to the slag.

Jan 1, 1983

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.