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

Liquid metals were investigated as alloy diaphragms in molten salt electrolysis. Liquid metals have higher diffusion rates of elements than those of solid metals during electrolysis. Sn electrodes were used for the first step to study the electrochemical formation of Dy and Nd alloys in LiCl-KCl eutectic melts, demonstrating selective recovery of rare earth metals into liquid tin electrodes.

Mar 1, 2017

By Toshiyuki Nohira, Tetsuo Oishi, Hideki Ono, Hirokazu Konishi

The electrochemical formation of Tb-Ni alloys was investigated in a molten LiCl–KCl–TbCl3 (0.50 mol% added) at 723 K. Open-circuit potentiometry was conducted using a Ni electrode after electrodepositing Tb metal at 0.20 V (vs. Li+/Li) for 300 s. There were four potential plateaus at (a) 0.66 V, (b) 0.80 V, (c) 0.95 V and (d) 1.56 V, respectively. Alloy samples were prepared by potentiostatic electrolysis at 0.60 and 0.70 V at 723 K. The alloy phase was identified as only TbNi2. Anodic dissolution of Tb from the formed TbNi2 was conducted at 0.90, 1.20 and 1.60 V, respectively. In the sample obtained at 0.90 V for 3 h, the existence of TbNi3 was identified by the XRD. Phase of the sample obtained at 1.20 V for 3 h was TbNi5. The sample obtained at 1.60 V for 3 h was Ni. Alloy samples were prepared by potentiostatic electrolysis at 0.50–0.80 V for 1 h using Ni plate cathodes in a molten LiCl–KCl containing TbCl3 (0.50 mol%) and NdCl3 (0.50 mol%). The highest mass ratio of Tb/Nd in the alloy sample was 56 at 0.70 V.

Mar 1, 2018

By Y. J. Ferdosi

This paper presents the outcomes of the preliminary investigation focused on the potential usage of Electrochemical Impedance Spectroscopy (EIS) in minerals processing. Currently, Electrochemical Impedance Spectroscopy has been successfully employed in the characterization of multilayer structures formed as molecules adsorb on flat surfaces and is commonly used in bio-related research. Few studies have explored the application of EIS in minerals processing, particularly for mineral particles and flotation systems. In the first series of tests, the impedance response was investigated as a function of particle size, shape and hydrophobicity using model quartz particles. The particle size fractions and the shape were found to contribute to the impedance response. The more hydrophobic quartz particles resulted in a higher impedance values. Further tests involved pure sulfide minerals including chalcocite, bornite, chalcopyrite and pyrite. The AC impedance measurements were conducted as a function of collector (sodium ethyl xanthate) dosage. The AC Impedance data was modeled using the combination of reference circuits. It has been shown that adsorption of collector onto sulfide minerals surfaces results in a higher magnitude of impedance. Increasing the collector dosage resulted in an increase in AC impedance for chalcopyrite, while a decrease was observed for chalcocite. Significant variations in impedance were exhibited by bornite and pyrite with a gradual increase in collector dosage.

Sep 1, 2012

By M. Epiney, A. Ghahreman, R. Kim1and

"In the presence of sulfidic refractory ores, increasing the dissolved oxygen (DO) concentration can positively affect the gold leaching rate. To identify the role of DO in gold cyanidation, electrochemical behavior was studied in the presence of 3 different ores. Sample 1 was a low sulfide pyrite ore, contained 5.14% pyrite, 0.19% galena and 3.09% S. Sample 2 was a pyriticore as well, contained more sulfide as 8.35% S, and 12.4% of pyrite. Sample 3 was a tailing of silicate gold ore, still containing75 g/tAu, 0.13% Pb and 0.18% S. Gold cyanidation kinetics were studied by cyclic voltammetry (CV) and chronoamperometry tests. With sample 1, the gold oxidation peak current density from CV curve was increased to 1.38mA/cm2under oxygen injection, while it was only 0.66 mA/cm2with air injection. From chronoamperometry test, the reaction rate was also faster under oxygen injection. Sample 2 showed similar behavior with sample 1, but the gold oxidation peaks higher than sample 1, i.e. 1.75 and 2.27 mA/cm2, under air and oxygen injection, respectively. However, it seemed that the gold oxidation was impeded by sulfide ions for a longer period. In the presence of sample 3, the gold oxidation peak was the highest among three ores –2.75mA/cm2under oxygen injection, because of its lowest sulfide content. However, from chronoamperometry test, it was also shown that the gold oxidation was impeded because of a significant amount of Pb in the ore sample.INTRODUCTIONIt is well known that gold is leached under oxidative condition (Marsden &House, 2006). Through the most representative and oldest gold leaching technique, cyanidation, more than 90% of gold can be selectively leached from an ore. According to Elsner’s equation, gold is leached in cyanide solution by forming cyanide complex [Au (CN)2–], and oxygen is consumed as an oxidant(Eq. 1)."

Jan 1, 2017

By M. Girgis

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

Jan 1, 1987

By 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 K. A. Natarajan, Abha Kumari

In this paper, electroleaching and electrobioleaching of ocean manganese nodules are discussed along with the role of galvanic interactions in bioleaching. Polarization studies using a manganese nodule slurry electrode system indicated that the maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 and -1,400 mV(SCE). Electroleaching and electrobioleaching of ocean manganese nodules in the presence of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans at the above negative applied DC potentials resulted insignificant dissolution of copper, nickel and cobalt in IMH2S04 and in sulfuric acid solution at pH 0.5 and 2.0. Mechanisms involved in electrobioleaching of ocean manganese nodules are discussed. Galvanic leaching of ocean manganese nodules in the presence of externally added pyrite and pyrolusite for enhancement of dissolution was also studied. Various electrochemical and biochemical parameters were optimized, and the electroleaching and galvanic processes thus developed are shown to yield almost complete dissolution of all metal values. This electrobioleaching process developed in the laboratory may be cost effective, energy efficient and environmentally friendly. Keywords: Ocean manganese nodules, Electroleaching, Electrobioleaching, Galvanic interactions

Jan 1, 2003

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 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 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 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 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