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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 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 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 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 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

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 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