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By Henrik Gudbrandsen, Anne Støre, Ana Maria Martinez, Karen Sende Osen, Ole Kjos

The light rare earth metals Nd, Pr, La, Ce as well as some alloys with Fe, are today produced in China by electrolysis in molten fluorides using oxide raw materials. A major challenge is to obtain a good cell operation without de-composing the electrolyte leading to emissions of per fluorinated carbon (PFC) green-house gases to the atmosphere. This work is focused on understanding the fundamental requirements to run the electrolysis cells for DyFe alloy production in an ef ficient and environmental friendly way. Electrolysis experiments was carried out in DyF 3-LiF melts at 1050 °C. A Fe rod was used as consumable cathode and the (consumable) anode was made of graphite. To establish at which anode potential PFC occurred and thus enabling optimisation of the oxide batch feed rate, analysis of the anode gases was performed with Fourier Transform Infrared Spectrometer (FTIR). The produced DyFe alloy was characterised by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS).

Mar 1, 2017

By Derek Fray

Molten salts have been used for the extraction of metals since the 19th century but, recently, many interesting processes have been investigated using mixtures of molten salts and different cathodic materials. In several existing processes, the cation is simply discharged from melt but, in some cases, complications arise when the electrode potentials of the cations are relatively close. For example, the co-deposition of sodium with aluminium in the Hall-Heroult process is discussed in terms of electrode potentials of the components in the molten electrolyte. Similar considerations will also be given to the anodic reactions with respect to chlorine, oxygen, carbon dioxide or monoxide evolution from chloride-oxide melts. In some cases, the cathodic product interacts with the cathode to produce new and exciting products such as nanotubes from carbon or titanates and reduced titanium oxides from titanium dioxide. Depending on the electrode potentials, it is also possible to completely change the cathodic reaction from discharge of the cation in the salt to ionisation of the anions in the cathode. Examples are given of the reduction of metal oxides to produce metals, high technology alloys and nanomaterials and the cathodic refining of liquid metals.

Jan 1, 2006

By Alicia Esther Ares, Carlos Enrique Schvezov, Alejandra Silvina Roman, Claudia Marcela Méndez

In this paper the structure of aluminum based alloys and their corrosion behavior by using different electrochemical techniques as characterization methods are considered. Currently, it becomes imperative to know the role of the Al2Cu against the susceptibility to corrosion of these alloys. The present work aims to studying the electrochemical behavior of aluminum base alloys with the following compositions: Al-1wt.%Cu, Al-4.5wt.%Cu and Al-15wt.%Cu (with different grain structures), in 1M NaCl solutions, at room temperature. Cyclic potentiodynamic polarization tests were performed and were found that the alloys with more than 1wt.%Cu in the matrix have an unstable behavior and without tendency to reach passivity. The equivalent circuits derived from electrochemical impedance spectroscopy technique (EIS) generally showed two capacitive contributions. The susceptibility to corrosion becomes a complex function, not only of copper concentration and structure, but also with interdendritic spacings and distribution of phases in the alloys.

Jan 1, 2015

By A. Dell’Era, M. Pasquali, C. Lupi

"An electrochemical cell has been designed to treat very diluted cobalt solutions, i.e. those deriving from recycling processes of lithium-ion batteries. A reticulated vitreous carbon sponge was used as cathode and a Pt-coated Ti net as anode. A controlled potential electrolysis has been carried out in a solution flowing in the cell and maintained at a constant pH of 6.5. Considering the cathode dimensions (10.0 cm * 10.0 cm * 1.25 cm), rather high volumes of solution (>1 litre) can be treated with flow rates up to 1.6 l/min. The process yield is obviously related to the solution concentration; it has been observed that, starting with a solution containing 200 ppm of Co2+, the yield is initially ~35-40%, but it decreases to ~20% when 80% of the initial cobalt content has been electrowon. The yield increases up to ~50% if the carbon electrode is coated by cobalt. The conditions allowing a fast and complete removal of cobalt are outlined. Introduction Industrial liquid effluents containing heavy metal ions arise not only during hydrometallurgical processing, but also in many sector of chemical industries utilizing metal catalysts and process reagents. These waste solutions containing low quantities of metallic ions can be treated by chemical precipitation, solvent extraction, ion exchange, etc. before final discharge. All these techniques could be efficient for complying the aqueous effluents with the severe rules related to the environmental impact, but they can not directly produce metals. Particularly the chemical precipitation presents two main drawbacks, huge amount of sludge prodction and reagent costs to produce this useless and sometime dangerous sludge that have to be considered. Electrochemical technologies can be used for the treatment of effluents polluted by metal ions, showing the following advantages in comparison with other processes: 1. recovering of the polluting substances in metallic forms, with subsequent reusing; 2. absence of process slag, which should be subsequently disposed of. In this work an electrochemical reactor with a reticulated vitreous carbon cathode and a platinated titanium net anode has been designed and utilized for removal Co from waste aqueous solutions. Porous materials have been used as electrodes for this cell, as their high specific surface area favours the treatment of these low metal content solutions (1-7). This kind of electrodic material presents very interesting chemical-physical characteristics such as: low density, low thermal expansion and high electrical and thermal conductivities; particularly the reticulated vitreous carbon (RVC) presents a very elevated void volume, rigid structure, good resistance to temperatures in non-oxidizing environments and very low resistance to fluid flow."

Jan 1, 2008

By Melvin H. Miles

"Considerable research has been conducted on the anodic oxidation of methanol in fuel cells. The electrochemical reduction of carbon dioxide in aqueous solutions to form methanol is the same reaction in reverse, i.e. CO2 + 6 H+ + 6 e- ? CH3OH + H2O. The same catalysts and conditions may operate for both reaction directions. This carbon dioxide reduction reaction, however, must be able to compete with the electrochemical reduction of water to form hydrogen gas. Thermodynamically, the reduction of CO2 to form CH3OH is slightly more favorable than the reduction of water. The use of nearly neutral electrolytes rather than acidic electrolytes makes the reduction of CO2 kinetically more favorable. The thermodynamics of various reaction steps are presented. Similarities exist with the electrochemical reduction of CO2 and the green-plant photosynthesis process that converts CO2 to carbohydrates.IntroductionVirtually all of the oxygen in the earth’s atmosphere is of biological origin having been generated by green-plant photosynthesis from water and carbon dioxide [1]. The net reaction can be represented byCO2 + H2O ? O2 + [CH2O] (carbohydrates, etc.) (1)Chlorophyll and enzymes promote this reaction, and the energy required comes from sunlight. The actual photosynthesis process is a complex multistage reaction and requires 469 kJ mol-1 of energy supplied by the sun. Isotope tracer experiments using 18O have shown that both the oxygen atoms in the O2 molecule originate from H2O, whereas oxygen atoms in the carbohydrates come from CO2 [1]. The total amount of water on the earth is split by photosynthesis and reconstituted by respiration and combustion once every 2 million years or so. The photosynthetically generated oxygen gas temporarily enters the atmosphere and is recycled about once every 2000 years [1]. The carbon dioxide is partly recycled in the atmosphere and oceans after an average residence time of 300 years and is partly fixed by precipitation of CaCO3 and other carbonate minerals [1]."

Jan 1, 2008

By Zhongning Shi, Ramana G. Reddy, Min Li, Zhaowen Wang

Electrodeposition of cobalt from cobalt tetrafluoroborate (Co(BF4)2) was investigated using 1- butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) ionic liquid. The experiments were conducted at 353 K. Chronoamperometry experiments confirm that the electrodeposition of cobalt on tungsten electrode proceeds via three-dimensional instantaneous nucleation with diffusion-controlled growth process. The average diffusion coefficient of Co(II) was found to be 7.5 × 10-8 cm2s-1 at 353 K, which is in good agreement with the estimated value from cyclic voltammetry. The electrochemical deposit was characterized using SEM-EDS and XRD methods. The SEM image shows formation of a dense and compact deposit at - 0.75 V. The EDS and XRD analysis confirm that the obtained deposit is pure cobalt metal.

Jan 1, 2015

By H. J. Sohn, S. G. Doo

A systematic study was carried out to investigate the reduction reaction mechanism of oxygen on pyrite surface using electrochemical techniques. The polarization curves showed two distinct regions, the Tafel region for superoxide formation and limiting current region for diffusion of dissolved oxygen to form hydrogen peroxide. These results were confirmed with a-c impedance measurements.

Jan 1, 1990

By J. Howarth

Two electrochemical processing methodologies have been used to electrogenerate bromine-laden solutions for gold-leaching purposes. In the first process, a laboratory-scale cell in which the anode and cathode compartments were separated by a cation-exchange membrane was employed. The bromine produced by electrolysis of a 4% bromide solution was used to leach gold from a low-grade ore. The pregnant leach solution was then returned to the cell to recommence the cycle. High current efficiencies (90-93%) were maintained over six cycles. In the second process, an undivided hypochlorite generating cell (Chloropac"') was used to generate bromine from a simulated leach solution. Electrolyses were performed on a pilot-scale (100-150 gallons) with solutions containing different levels of bromide ion. The current efficiencies were also high (80-90%) and unaffected by the bromide concentration (over the range 2.5-5%) provided the electrolysis was run to low conversion « 15%). The Chloropac module was capable of delivering 0.6 kg bromine per hour at a power cost of $0.09 per kg. Using these figures, a detailed economic assessment for a 1000 metric tonnes (MT) per day gold ore processing plant was made. Electrolytic regeneration of bromine in a gold leach/recovery circuit dramatically improves the process economics over cyanidation.

Jan 1, 1991

By K. Enns, J. J. Byerley

"While thiocyanate (SCN-) is used in a number of industrial processes (production of polyacrylonitrile filaments, synthesis of agricultural chemicals and certain metallurgical solvent extraction and flotation circuits) it is recognized more as an undesirable by-product associated with ' the metallurgical industry. Thiocyanate is present at low concentrations in some waste streams from the iron and steel industry. Of particular significance is the formation of thiocyanate during cyanidation of gold and silver ores, concentrates, tailing s and residues. The thiocyanate levels present in the resulting effluents may range from a few mg/I to several thousand mg/I.At present, thiocyanate does not appear to be as hazardous in the environment as cyanide (CN-) at the same concentration although its interaction with other species and resulting decomposition of products may be unacceptable. Of course the presence of thiocyanate in the leaching circuit and ultimately in the effluent streams may add considerably to the oxidative requirments of any non-selective treatment process for cyanidation wastes.With respect to the thiocyanate as it relates to the cyanidation process, two aspects are evident. Thiocyanate forms and persists in the cyanidation circuit resulting in a ""fouling"" condition with subsequent loss of leaching activity. In order to reduce or control this problem, it is common practice for some mills to discharge daily as much as 20% of the barren leach liquor. Besides contributing to fouling of the leach liquor the formation of thiocyanate represents an irreversible loss of reagent cyanide. It is noteworthy that in some present or proposed mill practice reagent cyanide loss through thiocyanate formation may reach 50%(1). The purpose of this paper is to discus s the application of controlled electrooxidation of thiocyanate with the view of suggesting a process for regenerating cyanide from waste thiocyanate(2). The paper describes the important theoretical aspects and presents experimental data obtained for thiocyanate electrooxidation using both small and large scale electrochemical reactors. Some economic conclusions are presented."

Jan 1, 1984

By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By F. Tailoka, G. Zhao

Pb is an unwanted impurity in Al for which there is no established method of removal. As it interacts strongly with alkali metals, separation was achieved by adding Na or K to molten Al at 953-1 003 K. Direct Na addition led to considerable evaporative loss but in-situ addition by electrochemical titration from a eutectic NaCl-KCl or KCl-BaCl2 mixture was found far more effective, in some cases reducing Pb content below detection levels within 2 h of titration. K appeared more effective than Na at low Pb concentrations but the use of Na was preferred as it is less toxic and explosive. Na removal from Al-Na and Na-Pb alloys was also carried out electrochemically, the use of these two alloys rather than the eutectic salt as a source of Na avoiding liberation of Cl2 at the anode

Apr 1, 1995

By G. R. Doughty

It is shown that sodium can be removed very readily from molten aluminium by the use of a beta"-alumina, the more highly conducting form of beta-alumina, provided that the surface of the tube is wetted by a layer of salt. From current/time plots the theoretical amount of sodium removed has been calculated and excellent agreement obtained. The beta"-alumina tubes can be immersed directly in the Al without fracturing if they are pre-heated for a few minutes prior to immersion. According to its stability beta"-alumina should be attacked by molten Al at low Na contents, but in these experiments the salt acted as a protective layer. Magnesium chloride is a relatively cheap salt, whose Mg product can be used within a foundry. The only other product is NaCl, which can be used in-house as a flux or sent for disposal. No polluting gases are used or produced and no drosses created. The time for removal of sodium was quite short, comparable to that for chlorination

Jun 21, 1905

By Q. G. Liu

New solid-state electrochemical sensors 1;.1sing Li2SO4-Ag2SO4 electrolytes have been developed to measure SO2 and/or SO3 in gas mixtures. Silver embedded in part of the electrolyte is used as the reference electrode. Although single-phase electrolyte sensors yield accurate results for one to two days, a two-phase electrolyte cell exhibits excellent long-term chemical stability. For example, stable and accurate potent iometric responses have been obtained over a six mo.nth period. The. advantages of the two-phase electrolyte ( 23 mol% Ay 2SO4 ) cell include excellent mechanical strength on temperature cycling and an insensitivity to compositional variations in the electrolyte and to temperature fluctuations. Experimental tests have shown excell.ent results in SO2-air. mixtures with the SO2 concentration ranging from 3 to 10,000 ppm (vol). However, the SO2 concentration range was limited by a lack of standard gas mixtures, and our sensor cells can be used to measure S02 concentrations significantly less than or larger than our experimental range. Results also indicate that the presence of significant concentrations of CO2 and H2O in the gas mixture has no effect on the sensor response. Thus the two-phase electrolyte ( 23 mol% Ag2S04) sensor has exceptional selectivity, reliability and long-term chemical and mechanical stability.

Jan 1, 1985

By O. A. Olaseinde

The 2101 lean duplex stainless steel has wide potential application in storage, heat exchangers, and in the oil and gas industries. This work investigates the electrochemical behaviour of 2101 duplex stainless steel with an addition of 0.15 wt% ruthenium, using potentiodynamic techniques in 1M H2SO4 at 25º, 40º, 60º, and 80ºC. The microstructures of samples were characterized using optical metallography and scanning electron microscopy. The results showed that the ruthenium addition moved the corrosion potential of alloy 2101 to a more positive potential. All samples containing ruthenium displayed longer passive regions at 25°C and 80°C compared to those without ruthenium. Alloys without ruthenium had higher critical current density (icrit) values when compared to the alloys with ruthenium. Ruthenium additions decreased the passive current densities and inhibited anodic dissolution. At room temperature the corrosion rate of alloys with ruthenium was lower than these without ruthenium.

Jan 1, 2012

By O. A. Olaseinde

The 2101 lean duplex stainless steel has wide potential application in storage, heat exchangers, and in the oil and gas industries. This work investigates the electrochemical behaviour of 2101 duplex stainless steel with an addition of 0.15 wt% ruthenium, using potentiodynamic techniques in 1M H2SO4 at 25º, 40º, 60º, and 80ºC. The microstructures of samples were characterized using optical metallography and scanning electron microscopy. The results showed that the ruthenium addition moved the corrosion potential of alloy 2101 to a more positive potential. All samples containing ruthenium displayed longer passive regions at 25°C and 80°C compared to those without ruthenium. Alloys without ruthenium had higher critical current density (icrit) values when compared to the alloys with ruthenium. Ruthenium additions decreased the passive current densities and inhibited anodic dissolution. At room temperature the corrosion rate of alloys with ruthenium was lower than these without ruthenium.

Jan 1, 2012

By J. A. Venter, M. K. G. Vermaak

There are practical indications that flotation recovery of palladium bismuth tellurides is poor. This work tested whether this can be caused by a lack of interaction of the collector with the telluride. Impedance measurements, voltammetry and Raman spectroscopy were performed to determine the interaction of dithiocarbonate collectors (KEX) with Pd-Bi-Te. Impedance measurements showed lower capacitance values in solutions containing KEX indicating the formation of a continuous surface layer. Anodic and cathodic polarization diagrams show the mixed potential tobe higher than the reversible potential of the xanthate-dixanthogen equilibrium reaction; hence the formation of dixanthogen on the surface is possible. Electrochemically controlled in situ Raman spectroscopy did indicate the presence of bulk diethyl dixanthogen on the surface. Raman spectroscopy has confirmed the co-presence of xanthate with dixanthogen, indicating that xanthate retains its molecular integrity when it adsorbs on the surface of the Pd-Bi-Te. As a result, the mineral surface is expected to be hydrophobic and a lack of collector interaction with the mineral is not the reason for low PGM recoveries experienced. Keywords: Raman spectroscopy; Pd-Bi-Te; ethyl xanthate; platinum flotation; Great Dyke; Pd-bearing bismutho-tellurides and moncheite.

Jan 1, 2004

By M. K. G. Vermaak

There are practical indications that flotation recovery of palladium bismuth tellurides is poor. This work tested whether this can be caused by a lack of interaction of the collector with the telluride. Impedance measurements, voltammetry and Raman spectroscopy were performed to determine the interaction of dithiocarbonate collectors (KEX) with Pd-Bi-Te. Impedance measurements showed lower capacitance values in solutions containing KEX, indicating the formation of a continuous surface layer. Anodic and cathodic polarization diagrams show the mixed potential to be higher than the reversible potential of the xanthate-dixanthogen equilibrium reaction; hence the formation of dixanthogen on the surface is possible. Electrochemically controlled in situ Raman spectroscopy did indicate the presence of bulk diethyl dixanthogen on the surface. Raman spectroscopy has confirmed the co-presence of xanthate with dixanthogen, indicating that xanthate retains its molecular integrity when it adsorbs on the surface of the Pd-Bi-Te. As a result, the mineral surface is expected to be hydrophobic and alack of collector interaction with the mineral is not the reason for the low PGM recoveries experienced. Keywords: Raman spectroscopy; Pd-Bi-Te; ethyl xanthate; platinum flotation; Great Dyke; Pd-bearing bismutho-tellurides and moncheite.

Jan 1, 2004

The present work is mainly focused on developing intermetallic inert anodes for aluminum electrolysis. The anode alloy based on Al-Ti-Cu system was prepared by casting, followed by the application of a protective coating. Behaviour of corrosion and the passivation under anodic condition was characterized using the electrochemical and microscopic techniques. The results obtained clearly demonstrate that the oxide coating can provide good corrosion resistance via surface passivation of alloy anodes, rendering them inert in cryolite melt.

Jan 1, 2006

By Tomás Vargas

The catalytic influence of a pure strain of Thiobacillus ferrooxidans (ATCC 19859) on the dissolution of natural pyrite crystals was studied using electrochemical techniques. The results showed that this microorganism catalyze the leaching of pyrite by both, oxidizing ferrous iron in solution and depolarizing the reduction of ferric ion on this sulfide. In addition, studies of bacterial corrosion under applied potential showed that pitting on the pyrite surface centers on weak sites of the sulfide structure in which bacteria has attached, but occurs only when the ferric iron in solution induces an adequate level of anodic polarization on the mineral.

Jan 1, 1992

By E. Ghali, A. D. Bas

"Treatment of oxide, e.g. roasted gold ores has received relatively less attention than sulphidic ones and recently, handling of oxide gold ores is becoming essential. In this study, the influence of roasted gold ore (RGO) slurry (at 35% solid ratio) on the electrochemical dissolution of gold has been examined using pure gold and iron oxide minerals (hematite, maghemite, and magnetite) as disc electrodes by zeroresistance ammeter mode either in one or two separate containers. The presence of slurry decreased galvanic currents, i.e. corrosion rates due to the release and increase in the amount of soluble and/or insoluble species that could retard further the anodic behaviour of gold. Higher galvanic currents were observed in two separate containers than that in one container indicating the primary importance of galvanic interactions. SEM-EDS results observed iron hydro/oxide coatings on gold surface in case of magnetite test. However, in case of RGO electrode it is not a perfect passivation, although somewhat decreasing trend was observed on gold dissolution. These findings have revealed that passivation is not only a laboratory phenomenon, but also it could be responsible for the slowdown of gold dissolution in industrial practice.INTRODUCTIONThe cyanidation of gold is an electrochemical corrosion process thus; the dissolution of gold can readily be studied by electrochemical techniques. The outcome/summary of previous electrochemical studies of gold leaching can partially be summarized as follows: Filmer (1982) and Lorenzen and van Deventer (1992) reported the negative effect of pyrite and pyrrhotite on gold leaching due to the galvanic interactions; Aghamirian and Yen (2005) studied gold galvanic corrosion in presence of sulphide mineral electrodes only in one cell using zero-resistance ammeter (ZRA) mode; Dai and Jeffrey (2006) discussed, individually, the anodic and cathodic behaviours between gold and sulphide minerals, and Azizi et al. (2010, 2011) used a bed reactor to examine the influence of sulphide minerals on gold dissolution in one and two separate cells. Accordingly, a slowdown in gold leaching has generally been attributed to the passivation phenomenon, although the indication of this phenomenon is still an undergoing debate. For instance, Mrkusic and Paynter (1970) identified the passivation as the film formation of dissolved species from calcine, Crundwell (2014) explained passivation, in the case of corrosion of metals, as the formation of a layer which is composed of a new chemical species on the mineral surface and this layer inhibits or blocks further reactions. He suggested that passivation is related to the oxidation of the metal, and the formation of a passive layer that retards the rate of dissolution by several orders of magnitude. Consequently, galvanic interactions, passivation phenomena, or combinations of them are considered significant electrochemical factors affecting gold dissolution (van Deventer, Reuter, Lorenzen, & Hoff, 1990; Azizi, Petre, & Larachi, 2012). It is important to note that generalizing the influence of a mineral/metal on gold dissolution may not be correct in all cases, since contrary behaviours/results (for pyrite) have been observed (Aghamirian & Yen, 2005). Therefore, electrochemical study of gold is still a subject of research and need to be examined further in detail."

Jan 1, 2016