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By F. Rashchi, A. Ghahreman, J. Moghaddam, S. Karimi

"In this work, the kinetics of ferric-ferrous redox reaction on a passivated sphalerite electrode is studied by the application of chronoamperometry method in 0.5 mol L-1 H2SO4 solution. The electrochemical behaviour of ferric and ferrous couple was investigated on two sphalerite minerals acquired from two different geological regions (Iran and Canada). The carbon paste electrode (CPE) of sphalerite was initially prepared and passivated in 0.5 mol L-1 H2SO4 solution and after reaching the steady-state condition, ferric and ferrous sulfate solution was added. The registered current density differences between the current density of the passivated electrode and that of the electrode in the iron salts added solution were interpreted for kinetics of ferric-ferrous reduction-oxidation reaction. The equilibrium potential for ferric-ferrous couple on sphalerites surface was about 500 mV vs. Ag/AgCl. The exchange current density (i0) for ferric-ferrous redox reactions on the sphalerite samples had the same magnitude of 10–6 A cm–2. The electrochemical impedance spectroscopy (EIS) measurements at 550 mV vs. Ag/AgCl illustrated that sphalerite oxidation was controlled by two charge transfer process in both of Fe-free and Fe-containing solutions. The charge transfer resistance remarkably decreased when Fe salts added to the 0.5 mol L-1 H2SO4 solution, owing to the ferric-ferrous redox reactions being the predominant reactions on sphalerite surface.INTRODUCTION Direct atmospheric leaching processes for sphalerite concentrates are performed by reduction of an oxidant (e.g. ferric ion and oxygen) and oxidation of sphalerite to zinc ions. Oxygen could be an oxidizing agent as well, but the concentration of oxygen is very low in the solution. The role of ferric ions is predominate in this oxidation (Babu, Sahu, & Pandey, 2002). The oxidation reaction for sphalerite in the presence of ferric in can be presented as follows (Lampinen, Laari, & Turunen, 2015):"

Jan 1, 2017

By M. G. Mena, M. S. Mena-Junio

Silver (Ag) filler is the most attractive choice among all the conductive fillers of die attach materials for the attachment of silicon devices because of its balanced properties and relatively low cost. However, a major problem of silver is that it electrochemically migrates in the presence of moisture and applied bias. In microelectronic devices, silver migration can occur between adjacent conductors/electrodes, which leads to the formation of dendrites and eventually results in short-circuit failure. In order to assess the reliability of these conductive fillers, an investigation for two types of Agfilled die attach materials was done using the water drop test at room temperature and using a 1000 hour temperature-humidity-bias (THB) test under 85 ºC and 85% RH conditions. Four different bias/voltages and six different electrode distance spacing were used. Both dendrite and cloud/lace-like growths were observed as a result of the electrochemical migration of silver, Water drop test results revealed that increasing the applied bias/voltage and decreasing electrode spacing causes migration to occur faster, thus resulting into shorter time to fail (TTF). It was also observed that the growth rate of the dendrites from the cathode increased linearly as the dendrite approached the anode, probably due to a combination of increased ion availability and electric field. A minimum applied bias of 3 volts was required for migration to occur in Epoxy A as compared to 2 volts for Epoxy C. The higher migration voltage requirement for Epoxy A was attributed to the higher volume resistivity of the said epoxy. In addition to the minimum voltage requirement, it was observed that a minimum electric field of about 1 volt/mm is required for migration to occur. The 1000 hour THB testing did not result into any failures. It is surmised that the presence of condensed moisture is another requirement for migration. Such condition is not present during the THB testing.

Jan 1, 2012

By H. C. E. Regidor, M. G. Mena, H. D. Mendoza

Cyanidation leaching has always been the most widely used method of extraction of gold in the world. Its low cost and high selectivity has made it the prevalent choice for mining companies, and even for the small scale miners. The use of cyanidation in small scale mining has been an issue for the longest time, mainly due to the operation’s lack of safety measures, health care or environmental protection regulations. In pursuit of more environmentally friendly methods of extraction of gold, several alternative extraction processes have been explored, one of which is chlorination. The chlorination process is advantageous when recovering refractory gold locked in sulfides, as it simultaneously oxidizes the surrounding sulfides as well as dissolve any gold exposed to the lixiviant. This research was conducted to study and develop a safer alternative way of extraction of gold from small scale mining operations, without compromising the recovery of gold. In this study, a variation of the chlorination process has been employed for a refractory flotation concentrate wherein the majority of the gold is locked in sulfides. Hypochlorite-bearing reagents were used as the leaching reagents, and the method developed was a 2-stage leaching process in differing pH conditions. The solution pH and Eh was monitored all throughout the runs, and aliquot samples were taken at time intervals for analysis. SEM-EDS imaging was used to determine the mode of oxidation of the chlorination process, and the image obtained showed that the oxidized layer followed the shape of the particle, suggesting a diffusion controlled process. XRD analysis of the sample before and halfway through leaching further confirmed the oxidation of the sulfides. The amount of gold dissolved in the aqueous solution and in the solid residue were used as the basis for the determination of the recovery of gold. An average gold recovery of up to 84.38% was obtained using the developed method in just 7 hours of leaching. This method was then employed for a pilot-plant scale test and a gold recovery of 79.2% was obtained.

Jan 1, 2018

By Shangshu Li, Xin Li, Xionggang Lu, Xingli Zou, Kai Zheng, Yinshuai Wang

Ti5Si3/TiC composite has been successfully prepared from the titanium-rich slag/SiO2/C mixtures precursors by an electrochemical process. The electrochemical production process was carried out in molten CaCl2 salt at 1000 °C and 3.8 V. A pressed cylindrical pellet of titanium-rich slag/SiO2/C mixtures served as a cathode, and a solid oxide oxygen-ion-conducting membrane (SOM) tube filled with carbon-saturated liquid tin acted as an anode. The phase transformation of the cathode pellets during electrolysis process was investigated, the microstructure of the obtained products was characterized. It is found that the reaction pathways can be divided into three main stages during the electro-reduction process. The first stage is the generation of calcium compound, the second stage is the electrochemical reduction of the compound, and the third stage is the formation of Ti5Si3/TiC composite. The prepared Ti5Si3/TiC composite exhibits homogenous and nodular particle morphology.

Mar 1, 2018

By G. P. Dvoichenkova, E. A. Trofimova, M. V. Zaskevich, V. A. Chanturiya

The paper presents theoretical and practical aspects of directed adjustment of physicochemical properties (pH,Eh) and ion composition of recycle and mine water by electrochemical treatment. Treatment is run in the conditioners of diaphragm-type with production of alkaline catholyte of pH value up to 12 and acidic anolyte of pH up to 2. In process of water electrolysis the directed motion of Mg2+ and Ca2+ ions is observed from anode volume to cathode one, were they precipitate as hydroxides and carbonates; it leads to decrease of salt content in anolyte and catholyte. The anolyte has been concentrating anions, it is being saturated with oxygen, which reaches 20-35 mg/L. The results of experimental and industrial testing of electrochemical technique for mine and recycle water in flotation of diamond-containing and sulphide-scheelite, hematite, phosporite, apatite-nephelite, bauxite ores indicated the increase of recovery up to 2-1 5% and grade up to 0,5-2%, concurrent with decrease of reagent consumption from 15 to 50 %. Modules of industrial conditioners of different type capacity have been developed.

Jan 1, 1995

By George Nekoksa

The biofilm activity monitoring probes measure applied current during intermittent short-term polarization of the probe electrodes and current or potential between the electrodes after removal of the polarization. The probe polarization mimics conditions at crevices, welds and inclusions where the biofilm activity and microbially influenced corrosion usually concentrate. Monitoring of AC resistance between the probe electrodes can provide infornation about the thickness of deposits.

Jan 1, 1994

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 H. Moslemi

Metal sulphides are usually semiconductor and their electrical conductivity is low; therefore they are sources of electrons and promote electrochemical reactions. This phenomenon is of significant importance in sulphide flotation. The formation of a hydrophobic surface on the sulphide minerals is the result of various electrochemical reactions. Potential difference in the mineral-liquid interface plays an important role in the kinetics of the reactions, and consequently, on the flotation behaviour of sulphides. The value of the potential difference is influenced by different oxidation-reduction reactions at the interface area, and is measured by a two-electrode system in which an electrode is applied as reference electrode. In this study, we attempted to measure open-circuit potentials of pyrite, pyrrhotite, and steel electrodes with respect to the reference electrode. To verify the results, two reference electrodes, saturated calomel and gold, were used. Time-potential relations with respect to both reference electrodes show that the potential of both pyrite and pyrrhotite increases with time; however, this trend decreases for steel except when at pH 12. The results show a potential drop by an increase in pH value, except for steel, for which the opposite holds. This paper discusses galvanic interactions between minerals and grinding media in the grinding circuits, as well as among other minerals in the flotation processes.

Jan 1, 2012

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 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 Bing Li, Miao Shen, Qiang Wang, Yuqi Chen

Electrochemical methods including cyclic voltammograms, square wave voltammograms, chronopotentiometry are applied to characterize the reduction potentials of Na+ and Li+ ions in LiCl-KCl melts. According to theoretical calculation, the reduction potential for Na+ is slightly more negative than Li+ in NaCl-LiCl-KCl melts at 450℃. However, by electrochemical measurements, the reduction potential of Na+ is slightly more positive than Li+ in the above melt and the potential difference between Na+ and Li+ reaches 0.16-0.2V on an inert W electrode in 1.0-2.0 wt% NaCl-LiCl-KCl melts. An active Pb electrode is used to improve the removal rate of Na+ from LiCl-KCl melts. The reduction potentials for both Na+ ions and Li+ ions on a Pb electrode shift to more positive values and the reduction currents become larger. After 6h electrolysis on a Pb electrode at -3.0V, the practical removal efficiency of Na+ ions reaches 90.12% and the reduced products contain metallic Na and Li with a Na/Li mass ratio of 4.25/1.

Jan 1, 2015

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 Kazuya Koyama

We are studying the hydrometallurgical recycling process of indium from an Indium-Tin-Oxide(ITO) target. For this process, it is necessary to remove Sn(IV) ions from the aqueous hydrochloric acid solutions containing In(III). In this study, the removal of Sn(IV) ions by a potentiostatic electrolysis method was examined. The polarization measurements and potentiostatic electrolyses were carried out under a nitrogen atmosphere. In the Sn(IV) solution, current begins to rise at the cathode potential of -0.26 V vs. SHE, and increases with a reduction in the cathode potential. In the In(III) solution, current begins to rise at a cathode potential of -0.43 V vs. SHE. Metallic tin was electrodeposited without indium electrodeposition at the cathode potentials of -0.30 and -0.40V vs. SHE. More than 98% of the Sn(IV) was removed at the cathode potential of -0.40 V after the electrolysis for 3hrs. Both tin and indium were electrodeposited at the cathode potential of -0.50V vs. SHE.

Jan 1, 2006

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 Toshiyuki Nohira, Eiichi Takeuchi, Tetsuo Oishi, Hideki Ono, Hirokazu Konishi

The Dy-Nd-Pr-Ni alloy sample was prepared by cathodic potentiostatic electrolysis at 0.65 V (vs. Li+/Li) for 1 h using a Ni plate in a molten LiCl-KCl-DyCl3-NdCl3-PrCl3 system at 723 K. The highest mass ratio (Dy/Nd+Pr) in the alloy sample was observed to be 50 at 0.65 V. Anodic potentiostatic electrolysis at 2.20 V for 12 h was conducted using the Nd-Fe-B magnet electrode in a molten LiCl-KCl system. All elements were almost dissolved from the magnet, and the original form of the magnet disintegrated. After anodic potentiostatic electrolysis at 2.20 V, cathodic potentiostatic electrolysis was conducted at 1.00 V for 5 h using a Mo plate in order to remove the dissolved Fe from the bath. Finally, cathodic potentiostatic electrolysis was conducted at 0.65 V for 12 h using a Ni plate. The mass ratio of Dy/Nd in the alloy sample was determined to be about 18.

Jan 1, 2015

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