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By Yasuhiko Ito

"This talk is concentrated on the topics of compound film formation on the substrate electrode by interdiffusion of substrate element and electrochemically deposited species and/or by direct electrochemical implantation of the component element of the film into the substrate. As a typical example, electrochemical implantation of nitrogen atom into Ti metal to form TiN surface film is described. Another example is the formation of various kinds of intermetallic compound films including Ni2Y, Ni2Dy and Pd3 Y by the electrochemical implantation of lanthanoid elements into transition metal electrodes. By combining these two methods, Sm-Fe-N ternary material film also could be formed. The principle and application of the ""electrochemical implantation"" are discussed in detail.IntroductionGenerally speaking, surface film formation by molten salt electrochemical process can be divided into the following three categories:(i) single element film formation on the electrode by electrodeposition,(ii) compound film formation on the electrode by electrocodepostion of more than two elements, and(iii) compound film formation on the substrate electrode by interdiffusion of substrate element and electrochemically deposited species and/or by direct electrochemical implantation of the component element of the film into the substrate.This talk is .concentrated on the topics of category (iii), especially on the electrochemical implantation. Typical example can be seen in the electrochemical implantation of nitrogen atom into Ti metal to form TiN surface film. Another example is the formation of various kinds of intermetallic compound films including Ni2 Y, Ni2Dy and Pd3 Y by the electrochemical implantation of lanthanoid elements into transition metal electrodes. By combining these two methods, Sm-Fe-N ternary material film also could be formed. The principle and application of the ""electrochemical implantation"" are discussed in detail with examples above as well as other experimental results also obtained very recently in the author's laboratory."

Jan 1, 2000

By Kirsten Corin, Margreth Tadie, Michael Nicol, Cyril O’Connor, Jenny Wiese

"The recovery of base metal sulfides has been emphasized in the study of the flotation of platinum group minerals (PGMs). However, in some ore bodies such as the Platreef of the Bushveld Complex, sulfide minerals do not make up the majority of the more significant PGM mineralization. It is therefore important to develop a fundamental understanding of how non-sulfide and sulfide PGMs respond respectively to the current reagents being used in the flotation of these minerals. The interactions between platinum and palladium sulfides and tellurides with the thiol collectors, ethyl xanthate and diethyl dithiophosphate, have been studied using the electrochemical techniques of mineral rest potential and voltammetry measurements. The differences in the interaction between the two types of minerals with these reagents were of key interest. Rest potential measurements indicated stronger electrochemical interactions of the minerals with ethyl xanthate than diethyl dithiophosphate. These measurements also indicated that there are different forms of oxidized collector present on the mineral surfaces after interaction with ethyl xanthates. Voltammetry measurements support these observations and suggest differences of adsorption on Pt and Pd sulfides than on Pt and Pd tellurides. Voltammetry also showed that there was minimal electrochemical interaction between the Pt and Pd minerals and diethyl dithiophosphate."

Jan 1, 2014

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 Guo Xueyi

The reaction mechanism for the manganese dioxide reductive dissolution in acidic chloride media in the presence of ferrous/ferric ions are based on theoretical delineation and dual cell experiments. In terms of the Buttler-Volmer equation and chemical kinetic principles, a electrochemical kinetic equation was deduced, which successfully provided a theoretical basis for describing the role of Cl-, Fe2+, Fe3+ and H+ in solution, as well as their interrelationship in manganese dioxide reductive dissolution. Dual cell experimental studies indicate that the increases of Cl- and Fe2 in solution are helpful to accelerate the couple process; while, Fe3and Mn2+ hinder the coupled reaction to some degree. Higher acidity in solution is beneficial to the dissolution of MnO2. All the dual cell experimental results are consistent with the theoretical deduction. This study will be useful to understand the mechanism for the leaching of manganese nodules from the deep ocean, as well as the leaching of manganese dioxide ore from land.

Jan 1, 2003

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 M. L. Free

Electrowinning is directly impacted by many parameters that include electrolyte composition, voltage, current density, contact resistance, temperature, electrode spacing, and fluid flow as well as many other interrelated factors. The effects of these parameters are primarily related to thermodynamics, mass transport, and electrochemical kinetics. In this study thermodynamic, mass transport, and electrochemical kinetic equations are simultaneously solved to determine the effects of such parameters on electrowinning current efficiency, power consumption, electrodeposit morphology, and electrodeposit distribution. Modeling predictions will be compared with experimental results.

Jan 1, 2006

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 S Totsuka, P Ortiz, E Prokkola

Electrochemical polarisation techniques can be successively applied to maintain clean surfaces in process environments. The applications are the result of extensive knowledge of the electrochemical nature of process environments, an innovative approach to problem solving and shared æcan doÆ attitudes between the supplier and process owner. Initial identification of suitable applications is based on over 20 years of process and electrochemical experience. The technologies discussed in this paper include Electrochemical Anti-Scaling [EAS], Electrochemical Protection Systems with both anodic [EPSA] and cathodic [EPSC] protection and Electrochemical Flocculation [EF]. Examples of industrial applications are reviewed. Good examples of metallurgical processes which can benefit greatly from an advanced electrochemical treatment are the wet processes involving precipitation, crystallisation and evaporation. Eliminating corrosion and scaling which would otherwise cause process disruptions and quality problems can make a big difference in process profitability. Clear advantages in both cost efficiency and environment friendliness are easily demonstrated. Continuous processing with minimum downtime is one clear advantage. In comparison to the use of corrosion inhibitors, anti-scaling agents and flocculants, the electrochemical polarisation does not increase the environmental load from the process as no additives of any kind are used. In most cases the cost benefits from pro-actively keeping surfaces clean with the help of advanced electrochemistry are substantial when compared to traditional re-active methods and other active treatments.

Jan 1, 2004

By Shun-ichi Satoh

A NEW method of treating steel by ammonia has recently been intro¬duced into the metallurgical industry, by means of which piston cylinders of internal combustion engines, shafts and other similar steel products can be made more resistant to wear than formerly. In 1929 the writer' published the historical notes and some experiments upon nitrification. He believes that the corrosion of nitrified steel is a matter of importance and worth studying; and as there have been few studies thereof, he has conducted experiments in this respect. L. Guillet,2 in 1927, reported corrosion tests made on nitrified and cemented steels with acid and salt solutions. In 1928, 0. Hengstenberg3 reported the high resistance of nitrified steel to water vapor and air. V. 0. Homerberg4 stated that nitrified steel has high resistance to water, air and salt solution; and G. Hagg5 studied nitrified layers of iron by means of the X-ray. Though F. Hanaman6 in 1913, measured the single potential difference of steel treated with ammonia at above 650° C., no one, it seems, has ever measured the single potential difference of the so-called nitrified steels having extraordinary hardness. The writer measured the single potential differences of nitrified special steels in various solutions with the object of studying the corrosion problem and, if possible, of knowing whether any new physical property would be caused by nitrification.

Jan 1, 1932

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 Milton E. Wadsworth, J. Brent Hiskey

INTRODUCTION Fifteen years ago a distinguished electrochemist referred to electrochemistry as an "underdeveloped science " In the article in question, Professor Bockris (1) stated that many areas of.natura1 phenomena and applied technology are not perceived as being electrochemically based At that time, this was especially true for much of non-ferrous extractive metallurgy and was a particularly accurate description of hydrometallurgy During the last decade, there has been considerable advancement in applying the theory of electrochemistry to our know1 edge of hydrometallurgical processes and in understanding the mechanisms of underlying electrode reactions. Impressive as these advances are, there is still a growing need for electrochemical research of mineral systems and electrochemical engineering to apply this work in practical situations In a broad sense electrochemistry is defined as the physical chemistry of ions in solution and of phenomena which occur at the electrified interface. Bockris and Reddy (2) refer to electrochemistry as being divided into two fundamental domains, ionics and electrodics ionics is restricted to the behavior of ions in solutions, examples being many familiar redox processes Electrodics represents the main part of electrochemistry, and is the study of charged interfaces and the conditions governing charge transfer reactions across them. Considering hydrometallurgical applications, electrodics suggests the following relationship for a conducting solid (bulk or surface)

Jan 1, 1981

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 V. A. Luganov

During the treatment of raw materials containing arsenic and antimony, problems in the distribution of these elements in the process products occur. In a number of cases in processing of copper-bearing materials, it is possible (or necessary) to obtain speiss. The purpose of the present research is to study the theoretical aspects and analyze the technological possibilities of producing copper-bearing speiss and the subsequent electrometallurgical processing with copper extraction as well as arsenic and antimony utilization. Copper arsenide (Cu3As) and copper antimonide (Cu3Sb) are the main components of the speiss. A thermodynamic analysis of the electrochemical oxidation of Cu3As and Cu3Sb, carried out using Pourbaix diagrams, showed that in a pH range from 0 to 2, oxidation potential 0.45-0.55V, ions of copper and arsenic and antimony trioxide are in the equilibrium. The kinetic study has shown, that with an increase in the polarization potential, the dissolution process changes from chemical to diffbsion control. An increase in temperature stabilizes the electrolysis process due to dissolution of arsenic trioxide forming on the anode. Electrolysis of speiss using a cathode diaphragm with the solution pH = 1-2, current density 150-200 A/m2 and temperature 60-70°C makes it possible to obtain cathode copper with a current efficiency of 95-96% and to remove the arsenic from the process during the electrolyte cleaning process. The arsenic content in the cathode copper did not surpass 0.002%. As the result of the research, a technological flowsheet for copper-lead speiss processing was developed. At the present time this technology is undergoing pilot testing.

Jan 1, 1999

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 L. Sun

Recently, micro-tubular solid oxide fuel cells (SOFCs) have attracted the attention of many researchers because of their numerous advantages over larger tubular and planar SOFCs. These include excellent thermal shock properties giving rapid startup/shutdown capability, a high volumetric power density compared to larger tubular SOFCs, and reduced sealing problem compared to planar SOFCs. In order to screen cathode materials for micro-tubular SOFCs, the perovskite cathodes were deposited, using a variety of methods, on 10.5 mol % yttria-stabilized zirconia (YSZ) tubes. Their electrochemical properties were then evaluated by using electrochemical impedance spectroscopy and steady-state polarization methods, based on a three electrode configuration, and with the reference electrode position carefully optimized. The oxygen reduction reaction kinetics at the cathode/electrolyte half cell were then investigated in detail.

Jan 1, 2005

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