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By Lv Guozhi, Niu Liping, Liu Yan, Zhang Zhiqi, He Jicheng, Zhang Ting’an, Dou Zhihe

"CuCr alloy can be extensively used as contact materials in integrated circuit, electrodes, electric contact and high strength conductor. We proposed thermit reduction-electroslag remelting method of preparing the large scale CuCr alloy. But there are pores and oxide inclusions in CuCr alloy prepared by thermit reduction process. This paper studied mainly the effects of ratio of reactant and additive on the inclusion type and their occurrences in CuCr alloy. The slags and CuCr alloy were characterized respectively by XRD and SEM. The results show that when the additive is Na3AlF6, the slag consist of Al2O3 and Cr. When the additive is CaF2, the slag consist of Al2O3, Cr, CaF2 and CaAl4O7. The inclusions in CuCr alloy are mainly Al2O3 and pores which disperse in Cu-rich zone and Cu-Cr phase interface. When 5% CaF2 and 5% KClO3 are added, there are fewer pores and inclusions, and the more better microstructure.1 IntroduceCuCr alloy is the contact terminal material with an eximious properties[1,2], which gradually replaces CuBi alloy becoming the first choice for contact terminal material in the medium and high power vacuum switch after the 1970s. The traditional preparation methods of CuCr alloy mainly contain powder metallurgy, infiltration process and vacuum electric arc melting methods. But the above methods exist some shortcomings, such as poor product quality, high cost of production, processes complex ect[3-9]. CuCr alloy is made by the thermit reduction self-propagating method, which uses CuO, Cr2O3 and Al as raw material to get the high-temperature melt, and then casts to manufacture CuCr alloy ingot, which response equation follows as:"

Jan 1, 2012

By Larry M. Southwick, Phillip J. Mackey, A. E. (Bert) Wraith, Albert Pelletier

In 1881, the first commercial pneumatic Bessemer-type converter treating copper matte was successfully introduced by Pierre Manhes at the Eguilles copper plant near Vedène in France. This development followed over a year of testing on a smaller scale at a foundry in Vedène, during which the vertical tuyeres of the conventional Bessemer converter had been successfully replaced by horizontal tuyeres in an effort to avoid the freezing of copper which had occurred in the bottom of the vessel having vertical tuyeres. The Manhes Converter, as it became known, was the first successful large-scale adaptation of the Bessemer concept of using compressed air blown into a melt for metal refining and treatment. Within a few years, Manhes Converters utilizing horizontal tuyeres in either the original type of vertical converter, or a later and more enduring horizontal barrel converter, were in operation at over a dozen copper smelters around the world. It was this process that Messrs Peirce and Smith essentially improved with the introduction of the larger converter which bears their name and the development celebrated at this Symposium. The present paper briefly traces the original development by Pierre Manhes in the early 1880s and which set the stage for the later Peirce-Smith adaptation. The paper observes that the original development by Manhes was in part driven by the need to reduce coal (energy) consumption and hence the production cost in order for Eguilles to remain competitive with the larger plants in Swansea, Wales, where a ready supply of cheap coal helped keep smelter treatment terms of the day low. These themes are eerily resonant of today where booming copper production in China has impacted the industry, and also where energy consumption, closely linked to today’s more familiar theme of ‘climate change’ remains an important challenge currently confronting the entire industry. The paper concludes with comments on these seemingly parallel situations today and offers some thoughts for the future.

Jan 1, 2009

By Jan Dabrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures at each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 2D graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mu, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By Jonkion M. Font, Ramana G. Reddy

A thermodynamic model for a priori predictions of arsenic and antimony impurity capacity in Ni-Cu mattes and slags was developed based on the Reddy-Blander (RB) capacity model. The As and Sb capacities were calculated a-priori considering the RB capacity model in Ni-Cu mattes and FeO-FeO1.5-MgO-CuO0.5-NiO-SiO2 slag at 1573 K and 0.1 to 1 atm partial pressure of SO2. The results showed an excellent agreement between the model calculated and experimental data of arsenic and antimony capacities between the mattes and slag. The impurity capacity model developed here, can be extended for prediction of impurity capacities in multi-component base metal slags and base metal mattes. Such a priori predictions of impurity capacities can lead to develop or improve the efficiency of impurity removal from the base metal smelting, converting and refining processes.

Jan 1, 2014

By Hongbo Yang, Tongbo Zhang, Ting Huang, Jingshe Li, Fangfang Song

"Liquid core length is a very important parameter of the process of continuous casting, which directly reflects the cooling status in secondary cooling zone and solidification rate of the slab. In this paper, the billet caster in some steel plant in China was chosen as the prototype of simulating. A numerical simulating model for calculating the liquid core length of continuous casting billet was built by ProCAST software, which was verified reasonable and accurate by pin-shooting technique. Based on the model, the relationships between casting speed, casting temperature and liquid core length of casting billet were found, which was very practically useful for the workers on sit to improve casting billet quality. IntroductionContinuous casting process developed very rapidly because of the high metal yield, energy saving, and low-cost 111• And the quality requirements of continuous casting billet for customers became higher and higher with the fast development of economic121• Internal defect usually is the major quality problem for continuous casting billet[3•61 , which is influenced by the solidification process of casting billet, especially the solidification process of liquid core17•81 • So it is very important to study on the relationship between casting parameters and the liquid core length which means the distance between the crystallizer meniscus and the casting billet solidification end-point. In practical production process, the workers usually control the quality of casting billet according to the liquid core length."

Jan 1, 2013

By Mariana H. Staia

The present communication reports the results obtained by applying different concentration methods, at laboratory level, to the black sands from Estado Bolivar, Venezuela, with the aim of obtaining an adequate ilmenitic concentrate for the subsequent chlorination process. Sizing analysis was performed and plasma emission spectroscopy method was used to determine the chemical composition. It was found that from the two hydrogravimetric methods used, the Humphrey spirals is much more effective than Wilfley tables, leading to a 85% recovery. The most convenient particle size group for these concentration methods was the one corresponding to ASTM 40-140 mesh. When magnetic concentration was applied to the concentrate, obtained as a product from Humphrey spiral, a recovery of ilmenite more than 90% was obtained in the first step. It has been shown that the ore would respond to the separation techniques employed, giving individual minerals: ilmenite, zircon and silica as concentration products.

Jan 1, 1995

By Jana Dobrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures al each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 20 graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mn, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By Marietta Canty

A paper is presented in which an innovative biological process is described for the treatment of cyanide-, metals-, and nitrate-contaminated mine process water. The technology was tested for its ability to detoxify cyanide and nitrate and immobilize metals in wastewater from agitation cyanide leaching. A pilot-scale demonstration is described in which a pilot plant was constructed to demonstrate the technology on a mine process waste stream at a mine in Nevada. The demonstration was performed Jointly under the Mine Waste Technology Program (MWTP), which is funded by the U.S. Environmental Protection Agency (EPA) and is jointly administered by the U.S. Department of Energy's (DOE) Western Environmental Technology Office (WETO) and the Superfund Innovative Technology Evaluation (SITE) Demonstration Program under Interagency Agreement Number DW89938513-0 I-0. MSE Technology Applications, Inc. (MSE) located in Butte. Montana, was the contractor responsible for conducting the project, and Pintail Systems, Inc., of Aurora. Colorado, was the technology provider. The pilot-scale unit was field-tested at the Echo Bay McCoy/Cove Mine southwest of Battle Mountain, Nevada. The biotreatment process was considered to be successful in destroying cyanide in the mine process water. The process was also determined to be effective in removing metals. The pH was consistently neutralized, and nitrates were successfully removed from the mine process water. As a result of conducting these pilot-scale tests, the biotreatment process was concluded to be an innovative, cost-effective alternative for the treatment of mining wastewaters.

Jan 1, 1998

By Guoqiang Lv, Xi Yang, Wenhui Ma

Cast multicrystalline silicon ingots are widely used in photovoltaic manufacturing. A key issue to achieve high solar cell efficiencies is to attain an optimized temperature field during directional solidification (DS) process. This paper reports numerical investigation of multicrystalline silicon (mc-Si) ingot production using two major types of DS furnace. Specific examination is made on thermal distribution, interface shape and stress field. Evaluation is performed for the applicability of thermal system design to reduce thermal stress, improve crystal quality and enhance energy efficiency. The effects of procedure parameters and geometric configuration on temperature distribution are discussed as well to provide the viable solutions for systems optimization.

Jan 1, 2015

Al2O3,-WC Composite powder for cutting tools was synthesized by self-propagating high-temperature synthesis using A1 powder as a reducing agent. WC, W2C and Al2O3 were concurrently formed in WO3Al-C system. It was found that the complete reaction was achieved with excessive addition of carbon and appropriate processing parameters such as degree of dilution, particle size of aluminum, compaction pressures of green pellets and carbon source. The final product which was leached by 50% HN03+HF diluted solution was consisted of Al2O3-55wt% WC having 2-3um of mean particle size.

Jan 1, 1999

By Wenxian Zhu, Xuema Li, Patrick R. Taylor

"Experiments were performed in a non-transferred arc, thermal plasma flow reactor to investigate the synthesis of ultra fine boron nitride (BN) powder from the reaction system of boron oxide (Bz03), methane (CH4), ammonia (NH3) and hydrogen (H2). Argon (Ar) and nitrogen (N2) were used as plasma gases. The thermodynamics and kinetics of the synthesis reactions were examined and a chemical reaction mechanism was proposed. The powders produced under certain operating conditions had high purity and good conversions. All the products were extremely fine powders (< 30nm) and were uniform in size distribution. The powder products were analyzed by chemical and physical characterization. The effects of the reaction variables on the conversions from B203 to BN and the purity of the products were investigated.IntroductionIn the past few decades, boron nitride (BN) has attracted a great deal of interest because of its excellent thermal, chemical and electrical properties (1-4) It has a high thermal stability and thermal conductivity. Chemically, it is very stable and is not wetted by most molten metals and slag. It is also an excellent low loss insulator. Since hexagonal boron nitride (h-BN) is light in weight, strong and easily fabricated, it has applications in a variety of specialized high temperature areas, such as a high temperature lubricant, crucibles for molten metals, thermocouple protection tubes, break rings for horizontal continuous casting of steel, and friction reducing coatings. In cubic form, boron nitride is one of the hardest materials known, second only to diamond, and it is an excellent material for tools in which the use of carbon based materials is limited by oxidation or reaction with metals."

Jan 1, 1998

By Pekka Taskinen

The converter-less nickel matte smelting technology (DON) adopted more than 20 years ago in Boliden Harjavalta smelter has been since that applied successfully to the processing of large number of nickel sulphide concentrates of various Ni-to-Cu ratios and MgO contents. The operational point of the technology is far from the conventional primary nickel smelting in the smelting-converting route. Therefore, a careful scouting of distribution equilibria of the base and trace elements in the smelting conditions of DON process has been conducted, in order to obtain quantitative information about the equilibria and thermodynamic properties of the nickel mattes at low iron concentrations, less than 10 wt% [Fe] in matte. The series of investigations has included novel experimental and analytical techniques for increasing the reliability and sensitivity of the phase equilibria as well as the element distribution observations carried out in typical high-grade nickel matte smelting conditions.

By G. J. Abbaschian, A. B. Gokhale, M. M. Kunjapur

"A laboratory scale model furnace was constructed for obtaining radially inward oriented columnar grains in disc shaped castings. The furnace consisted of eleven circular, concentric, equispaced resistance heaters on each half of a split graphite mold. Water or air flowing through a copper pipe along the periphery of the disc constituted the heat sink. After filling the mold, the heaters were turned off consecutively in top and bottom pairs from the rim towards the center, causing the temperature gradients to move inward. Equiaxed structure was obtained at the center by turning off the inner coils together when desired. Sn:15%Pb alloy was used to cast integral blade disc castings using the above technique to obtain dual-property discs with a central equiaxed structure and an outer columnar grain structure projecting inwards from the blades to the rim. A numerical technique was used to predict the temperature profile in the disc during solidification, and good correlation was obtained with the experimentally measured temperature profiles. The corresponding heat transfer coefficient values obtained were h = 544 Wm- 2k-1 (0.013 cal/cm2- ° C-sec) for cooling between metal and chill and h' = 71 Wm- 2k-1 (0.0017 cal/cm2- ° C-sec) for the heat input from the hot mold to the liquid metal. BackgroundHigh temperature alloys used in the current generation of gas turbine engines have evolved through two main stages of development: in 1950's, the increase in the efficiency of gas turbines was paced by improvements in alloy design, which led to the development of Ni and Co-based superalloys (1). By mid-1960's, it was realized that improved alloy chemistry alone was inadequate in meeting the increasingly stringent service requirements. The focus of research then shifted from alloy development to process development, and resulted in the introduction of directional solidification (DS) techniques for the production of turbine blades and vanes (1,2).Under typical operating conditions, the blades and vanes are subjected to aerodynamic loading, while the blades are additionally subjected to high centrifugal loading and vibratory stresses. The primary material requirements for blades may be summarized as follows (1,3):•,High creep resistance•,Good high temperature tensile strength (typically in the range of•,275 to 550 MPa at temperatures in excess of 750°C)•,Resistance to both low cycle and high cycle fatigue (LCF and HCF)•,Resistance to erosion, corrosion, and oxidation•,Resistance to thermal fatigue"

Jan 1, 1986

By F. Elgersma

Hydrometallurgical zinc winning processes ?are frequently based on iron containing concentrates which yield a goethite, jarosite or hematite residue. Jarosite or goethite are mostly stored in waste ponds which ,are lined with foil. Water percolating through the pond is withdrawn from the deposit ,and decontaminated before discharge. Despite these measures, more and more pressure is put upon zinc companies to treat their (historical) residues and to produce environmentally acceptable residues. The criterion which determines this acceptability is the potentiality of leaching out hazardous elements by natural processes. This paper provides the comparison of five different process designs for integrated jarosite treatment in a hydrometallurgical zinc winning plant leading to environmentally acceptable residues. The processes are esigned for producing 200 ktons/yr zinc and for treating 80 ktonslyr historical jarosite. Mass and energy balances are used to determme parameters such as: the energy use per ton waste treated and the amount and composition of final residues. The conclusion of the work is that. pyrometallurgical jarosite treatment integrated in hydrometallurgical zinc winning is preferable to hydrometallurgical jarosite treatment. Integrated pyrometallurgical processes lead to a ?smaller quantity of remaining hazardous residues and require less energy.

Jan 1, 1992

By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process, The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

By Liangying Wen, Feng Xia, Chenguang Bai

"The situation of the Ti-V-Magnetite samples reduced with microwave has been investigated in laboratory. Firstly, the paper focuses on the heating behaviors of vanadium-titanium magnetite and characteristics of carbothermic reduction of V-Ti-magnetite in the microwave field. The effect of concentrate's size, quality on heating behaviors and reduction processes were researched. Results show that microwave heating may be a new heating resource replace of carbonic combustion reaction in reducing reaction. When the allocation of carbon is (16.7-30)%, carbothermic reduction of V-Ti-magnetite in the microwave field can proceed; with the increasing of carbon mixed, the metallization rate increases; and Fe, V can be reduced from their oxides in the microwave field; Titanic low oxide can be reduced from TiO2.1. IntroductionThe resource of Ti-V-Magnetite is abundant in the western area of Panzhihua in China, so far a mineral deposit of 4.64 billion tons have been proved up, it contains 14.75 million tons of V2O S which accounted for 87% of the vanadium and 5.93 hundred million tons of TiO2 accounted for 94% of the titanium resource respectively in China. The previous study proved that the major composition of mineral of the Ti-V-magnetite are Ti-magnetite, limonite, iron spinel, magnesium spinel etc, and the main elements of the Ti-V-magnetite in this area are Fe, Ti, V, Cr, Co, Ni, Ga, Sc etc[1] Due to the restrict of the BF-BOF process technical, during the smelting of the iron, the level of extracting the vanadium, titanium as well as other metal elements is limited. This results serious wasting of resources. To develop a new reduction process of Ti-V-magnetite is on the agenda, the microwave assistant reduction could meets this need, based on its characteristic of easy controlling of heating rate. To make use of the microwave energy to substitute the released heat sources of carbon combustion with air, use the solid phase state reduction at a relative lower temperature, make the beneficial element in Ti-V-magnetite transferred into the metal phase, then separated from the impurity. It is well worth to point out that once the microwave based reduction method has its industrial scale, it will take an outstanding position by its less release of carbon dioxide. This new environment-friendly process will play a vital role in the development of social industry and economy."

Jan 1, 2008

By Jose Bengoa

Low metal prices and environmental restrictions are always a challenge for copper smelters operation and its productivity. Thus, in order to reduce production costs and control gas emissions, improvements of the Teniente Converter (CT) operation were made at 110 Smelter Plant of Southern Peru Copper Co., 110, Peru, and the main objective was to increase its capacity for smelting copper concentrates without affecting normal operation. The present work corresponds to a recent study conducted during the normal industrial operation of the Teniente Converter in this plant and, it shows the effect of increasing air oxygen enrichment from 28 to 34% on its productivity. The results show an increasing of concentrate smelting rate from 800 to 1370 tpd and hence a notorious improving in copper production, and practically no effect on the refractory consumption. The increment of the concentrate throughput, increases also the SO2 concentration and the sulfuric acid production, showing the effort done by this operation in order to accomplish the environmental Peruvian regulation.

Jan 1, 2003

By R. L. Player

"The Copper Isasmelt process has been developed over the past 15 years by Mount Isa Mines Limited (MIM) and the Commonwealth Scientific and Industrial Research Organisation (CSIRO). The first two commercial plants were commissioned in mid 1992.The results of four heat balances on the Mount Isa plant are presented. At a smelting rate of 98 t/hr of chalcopyrite concentrate plus 14 t/hr reverts, the total heat generated was -91MW. Approximately 39% of this energy came from coal, while 50% of the energy reported to the process waste gas. To a first approximation the furnace is near chemical equilibrium.The impurity distribution in the Mount Isa plant was presented. Approximately 91 % As, 85% Cd, 75% Bi, 68% Zn, 60% Sb and Tl, 45% Pb and 30% Te in concentrate was eliminated from the matte.The ""bubble"" frequency of the gas cavity below the foot of the lance was measured at -2. 1Hz. Side bands displaced by -l.lHz modulated the bubble frequency. This was consistent with radial gravity wave motion in the slag bath. The two processes, gas bubbling and wave motion appeared to be coupled together; the bubble frequency was twice the slop wave frequency. IntroductionCopper Isasmelt has been developed over the past 15 years by Mount Isa Mines Limited and the Commonwealth Scientific and Industrial Research Organisation. The process is based on the Sirosmelt lance, invented by researchers at the then Division of Mineral"" and ProcessEngineering ofCSIRO in 1973.The first two commercial scale copper furnaces were commissioned at Mount Isa and the Cyprus Miami Mining Corporation smelter at Miami, Arizona in August and June 1992 respectively.The process concept, the history of the development, and the Mount Isa plant have been described (1, 2, 3).This paper sununarises heat balances obtained on the furnace, the impurity distribution among the output streams and lance injection characteristics."

Jan 1, 1996

By Chen Wen, Li Zhao-jia, Zhao Qiang, Ning Shun-ming, Tang Sanchuan, Wang Hong-qiang

"The carbon-burdened and cold-bonded pelletizing-electrosmelting process is used to dispose low-grade manganese, and the qualified rich-manganese slag is obtained. On the condition that reduction roasting temperature was 1000?, reduction time was 45min, particle-size was -1mm, reductant dosage was 1.6%, basicity was 0.3, smelting temperature was 1410?, smelting time was 60min, it had a good effect on the melting between slag and metallographic phase, the manganese content was 32.58%, manganese recovery was 92.16% in the slag; while the iron content was 94.40%, iron recovery was 95.32% in the metallographic phase. It was proved by the demonstration tests.IntroductionManganese is an important raw material for steelmaking, which is extensively utilized in modern industry, the consumption of manganese for iron and steel industry accounts for 90% to 95%. After mining over 30 years, the high-grade manganese resources drop markedly, especially with the hypergrowth of steel industry, the domestic manganese is far from the requirement, as a result, we have to buy significant quantities of manganese overseas. Besides, the property of imported manganese is more and more complex, and the high-grade and lump manganese decrease year by year, while the fines and high-crystal water manganese are on the increase. Therefore, how to make effective use of domestic low-grade manganese and intensify the manganese’s smelting is an effective approach to reduce the cost of manganese series ferroalloy and improves market competitiveness[1-4]. It has important practical meaning."

Jan 1, 2012

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