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By G. Gu, B. Fang, R. W. Revie, M. Elboujdaini

Electrochemical behavior of an X-80 pipeline steel, including frequency-sweep electrochemical-impedance spectroscopy (EIS), time-sweep EIS at a constant frequency and open-circuit potential (OCP) monitor, was investigated using four-point bending specimens subjected to a stress-corrosion cracking (SCC) test in a near-neutral pH environment. The capacitive loop became smaller with test duration, revealing an increase in the corrosion rate. The resistance obtained in the constant-frequency EIS test showed two regions, of which the region with a remarkable decrease in resistance transformed into a region of slow decrease, whereas the capacitance increased with test time indicating that iron dissolution was fast at first, and then a corrosion product or film formed and covered the surface, leading to the pitting formation.

Jan 1, 2005

By J. B. Hiskey, V. M. Sanchez

Electrochemical oxidation of arsenopyrite (FeAsS) has been investigated as an attempt to gain a better understanding of its dissolution chemistry. Rest potential measurements, cyclic voltammetry and constant potential experiments were conducted in the pH range from 8 to 12 in the absence and the in the presence of cyanide. A two-step reaction sequence is suggested by the electrochemical measurements. The initial step is described by: [FeAsS+6H20=Fe(OH)3+H2AsO3- +S°+7H++6e] The second step involves the oxidation of the arsenite and sulfur according to the following reactions: [H2As03-+H20=HAsO24-+3H++2e and S° +4 H2O=SO4-+3H++6e] Stoichiometric determinations confirm that 14 electrons are involved in the overall reaction.

Jan 1, 1992

By S. Amira

The corrosion behavior of high pressure die-cast and thixocast AXJ530 magnesium alloys has been investigated in 0.05M NaC1 solution at pH 6.0 using potentiodynamic polarization tests, electrochemical noise (EN) technique, electro-chemical impedance spectroscopy (EIS) and scanning reference electrode technique (SRET). The behavior of die-cast and thixocast specimens were compared using each of these techniques and the results discussed. Further tests have been carried out with die-cast AZ91D alloy to better compare and interpret the results. Experiments indicate that the thixocast specimens of AXJ530 alloy have a better corrosion resistance than those of die cast alloy in neutral solution.

Jan 1, 2006

By Hojat Naderi

In this research assisted leaching of chalcopyrite using sodium peroxodisulfate was studied. Electrochemical techniques such as Tafel analysis and electrochemical impedance spectroscopy (EIS) were used to investigate the surface reactions of a chalcopyrite electrode in the presence and absence of Na2S2O8. According to the results, addition of sodium peroxodisulfate increases the current exchange of the corrosion process and prevents the formation of a passive layer on the surface of the electrode. EIS tests show the trans-passive dissolution of the passive layer on the chalcopyrite electrode in presence of Na2S2O8. Equivalent electrochemical circuits were modeled for Na2S2O8-free and -containing solutions and the model parameters were compared to determine the effect of S2O8 2− on chalcopyrite dissolution. Copper dissolution from pure chalcopyrite mineral and chalcopyrite concentrate was carried out using 15 g/L sulfuric acid solution with and without Na2S2O8. Simultaneous presence of 10 g/L ferric ion and 40 g/L peroxodisulfate salt results in about 40 and 18% of Cu extraction from chalcopyrite concentrate and pure chalcopyrite mineral, after 96 h, respectively.

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Zhong g. Shui-ping

A new type Pb-Ag (0.8wt%)-Bi (0~5.0wt %) alloy used as anode in electrowinning of zinc from sulphuric acid electrolytes was prepared. The electrochemical properties of this ternary lead alloys have been tested and compared with those of Pb-Ag (0.8wt %) anodes used in industry. Results show the anodic overpotential decreases with the increasing of Bi content in the alloys. When the content of Bi was 1.0 wt% and 5.0 wt%, the anodic overpotential is about 40?50 mV and 60?80 mV lower than that of Pb-Ag (0.8wt %) alloy, respectively. The formation of oxide layers on the surface of these alloys was traced by LSV methods and the composition of the anodic oxide layers was characterized by XRD and SEM analysis. The surface layer on the two type anodes examined is mainly composed of a?PbO2 and ß?PbO2. But different structure of the surface layer was observed, Pb-Ag (0.8wt%)-Bi (1.0wt %) has a more fine-grained structure as compared to Pb-Ag (0.8wt %). But the film on Pb-Ag (0.8wt%)-Bi (3.0wt %) alloy is rather friable, cracked and not tightly attached to the anode.

Jan 1, 2008

By Kenneth N. Han

Ammonia has been found to be an effective leaching reagent for gold, silver and platinum group metals in the presence of appropriate oxidants. Electrochemical and kinetic aspects of the dissolution of elemental gold in ammoniacal solutions have been investigated. The cathodic reaction of aurous di-ammine on the gold cathode has been investigated first. From this investigation, the standard electro-potential of the cathodic reaction .and hence. the Gibbs free energy of formation of the aurous di-ammine were established. The solubility of gold in ammoniacal solutions was also examined in relation to ammonia concentration, temperature and concentration of various oxidants. The anodic reaction of the gold disk in ammonia? in the presence? of various oxidants including oxygen, ozon, hypochlorite, hydrogen peroxide, cupric and cobaltic ammine, and iodine was also examined and the results have been discussed. Excellent dissolution yielding of gold and many other metals, typically better than 95% recovery in 1'-2 'hours of leaching at a temperature ranging 80°C to 190°C has been observed. Test results of the dissolution of gold from elemental state as well as other sources including sulfidic ores and scrap are presented.

Jan 1, 1998

By Harold Markus, Gerhard Derge, Arthur Grobe

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from ½ to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.1°. Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By Harold Markus, Arthur H. Grobe, Gerhard Derge

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study. has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from 1/2 to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.? After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been damped. The pH of the electrolyte was controlled? by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.10. Potentials were measured against a saturated calomel electrode connected. to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By R. A. Williams

Surface and electrochemical techniques have been used to describe the surface chemistry of ferrosilicon powders, as a function of pH and electrochemical potential, for conditions typical of operating DHS plants. The practical consequences on the likely corrosion behaviour and associated electro- kinetic particle-particle interactions (which affect stability to sedimentation) in the suspension, are discussed.

Jan 1, 1987

Electrochemical Behaviour of Massive Chaclopyrite Bioleached Electrodes in Presence of Acidithiobacillus ferrooxidans and Acidithiobacillus caldus In this work, the monitoring of bacterial and chemical dissolution of massive chaclopyrite was evaluated using cyclic voltammetry (CV); the mineral surface was examined using scanning electron microscopy (SEM) and the elements were examined by Energy Dispersive X-ray Analysis (EDAX). The electrolyte employed for the electrochemical tests was the medium used to bioleaching the electrodes (3.0 g/L (NH4)2+SO4, 0.5 g/L K2HPO4, 0.5 g/L MgSO4+7H2O and 0.1 g/L Ca(NO3)2).The results showed differences in voltagramms carried out by Acidithiobacillus ferrooxidans and Acidithiobacillus caldus: In bioleached electrodes tested in the presence of Acidithiobacillus ferrooxidans, the anodic and cathodic current signals were larger than with Acidithiobacillus caldus. The analysis of CV results allowed attributing the different peaks observed in both the direct and reverse potential scanning to the oxidation of chaclopyrite to a secondary copper mineral (bornite, chalcocite and covellite) and its reduction via different non stoichiometric copper sulphides intermediaries. Surface evidences were observed by SEM, and chemical elements evidences were also investigated by EDAX.

Sep 13, 2010

By A. M. L. Cushing, S. Kelebek, A. Ghahreman

Iron sulfides are part of many ore deposits affecting flotation separation of non-ferrous base metals from them. Open-circuit potential (OCP), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) measurements were carried out with pyrite and pyrrhotite electrodes to investigate their reactivity under various flotation conditions, which involved the use of TETA, SMBS, and their combination. TETA was found to adsorb on the electrode surfaces causing a significant increase in charge transfer resistance of the product formed, which was most significant at OCP. This effect is much less with SMBS, indicating its greater surface reactivity compared to TETA. The combined use of these reagents decreases charge transfer resistance to a greater degree than that experienced with their individual uses. Addition of Cu2+ as a potential activator to this system nearly eliminates the action of TETA on the electrode surface, which can be attributed to sequestration/chelate formation in liquid phase. The relative effects of these reagents on pyrrhotite electrode are similar to that of pyrite. The main difference between the pyrite and pyrrhotite electrodes is that the observed charge transfer resistance on the pyrrhotite surface with each reagent case is significantly lower by 3 to 4 fold. This is compatible with its anodic nature and ease of oxidation since the OCP value of pyrrhotite is lower than that of pyrite. Results are discussed in relation to flotation/depression behavior of these iron sulfide minerals in mineral separation processes.

Jan 1, 2017

By Xiaofei Guan, Adam C. Powell, Uday B. Pal, Srikanth Gopalan

This paper reports a solid oxide membrane (SOM) electrolysis experiment using an LSM– Inconel inert anode current collector for production of Mg and O2 at 1423K. The electrochemical performance of the SOM cell was evaluated by using various electrochemical techniques including electrochemical impedance spectroscopy, potentiodynamic scans, and potentiostatic electrolysis. The effects of Mg solubility in the flux on the current efficiency and the YSZ membrane stability during SOM electrolysis were discussed and examined through experiment and modeling. The electronic transference number of the flux were measured to assess the Mg dissolution in the flux during SOM electrolysis. A negative correlation between the electronic transference number of the flux and the current efficiency of the SOM electrolysis was observed.

Jan 1, 2014

By Wan-Kyu Choi, Arpad E. Torma

The electrochemical reactions involved in a zinc sulfide flotation concentrate leaching with sulfuric acid in presence and absence of Thiobacillus ferrooxidans, as well as with ferric chloride - hydrochloric acid containing media, have been investigated. The cyclic voltammetric measurements revealed that many intermediate electrochemical reactions are involved in the zinc sulfide leaching. Using chronoamperometric and chronopotentiometric techniques, it was found that the leaching process is controlled by solid - state diffusion. The activation energy of solid - state diffusion process was determined by the Price's approach to be 21.3 kJ. The leaching mechanism is discussed in terms of solid - state properties (energy bondings) of the high energy gap solid zinc sulfide semiconductor and energy density states of redox systems of acidic leach media. A generalized model for the mechanism of zinc sulfide oxidation is present.

Jan 1, 1990

By F. A. Schinner

The present study has investigated the leachability of cadmium sulfide minerals by Thiobacillus ferrooxidans and the electrochemical reactions involved in the process. Using a cyclic voltammetric technic and carbon-paste-CdS electrodes, it was found that the bio-oxidation of semiconductor cadmium sulfide minerals consisted of a number of intermediate electrochemical reactions. The overall reaction was found to be controlled by solid state diffusion as suggested by the chrono-amperometric and chrono-potentiometric measurements. The activation energy of solid state diffusion was determined by the Sand's method to be AE=24.3 kJ. A generalized mechanism was proposed for the bacterial oxidation of cadmium sulfide by T. ferrooxidan and an explanation given for the importance of high redox potential of leach solution versus the decomposition potential of the sulfide mineral. Furthermore, the effects of n-type or p-type character of CdS substrates relative to their bioleachability was discussed.

Jan 1, 1993

By S. Chander

The results of an investigation to characterize the chalcopyrite/solution interface are presented. Several techniques including galvanostatic and steady state polarization, cyclic voltammetry and impedance spectroscopy were used. The results show that the dissolution of chalcopyrite is incongruent. Initially, at low potentials(<O.34V), iron species are released which give rise to the growth of an iron-deficient sulfide (IDS) layer. The dissolved iron might reprecipitate as a hydroxide layer depending on solution composition. Continued oxidation involves diffusion of species through the product layer. At higher potentials (>O.48V) further oxidation leads to dissolution of copper and sulfur species with a resultant breakdown of the IDS layer. The changes in properties of surface coatings resulting from various electrochemical treatments are discussed.

Jan 1, 1991

By O. Forsén

A new cell construction was designed for the study of the electrochemical behaviour of additives in conditions that simulate real copper, electrorefining. The behaviour of gelatine and thiourea was studied by applying different electrochemical methods, i.e. polarization resistance and voltametric measurements. In this study, individual galvanostatic electrolysis experiments were carried out for 120 hours. The organic additives were introduced to the electrolyte at certain intervals and their concentration was varied in the range &om zero to four ppm. An optical microscope was applied for the examination of copper cathode deposit microstructures. The results show that gelatine has a polarizing effect on the deposition potential of copper whereas even small amounts of thiourea depolarize the electrodeposition of copper. The maximum inhibitor efficiency of gelatine was obtained at a gelatine concentration of slightly lower than two ppm. When both gelatine and thiourea were present in the electrolyte, the depolarizing effect of thiourea exceeded completely the polarizing effect of gelatine. If chloride ions were added to gelatine and thiourea containing electrolyte, the electrochemical behaviour of the system was altered drastically. Chloride ions resulted in the prevailing of polarization effect caused by gelatine while the depolarizing effect of thiourea disappeared in this system. The polarizing effect of gelatine increased until chloride ion concentration of 30 ppm was reached. Also, the above electrochemical phenomena could be detected in the optical examination of copper deposit microstructure.

Jan 1, 1995

By Akram Alfantzai, Farzad Mohammadi, Maysam Mohammadi

"Degradation of lead anodes has always been a major concern among the electrowinning industries. In this study, the effect of agitation of the zinc electrowinning solution on the integrity of lead anodes was investigated. Galvanostatic experiments were performed at 37±0.5°C using 0,600 and l000rpm magnetic stirring rates for 24 hours. The Pb02 layer formed on the anode surface was reduced to PbS04 (discharged). The discharge information was used to calculate the amount of Pb02 present on the surface. Weight loss measurements along with the discharge calculations revealed that the degradation rate of the lead anode increased as the solution was stirred more vigorously. Furthermore, the amount of remaining Pb02 on the surfaces was decreased as a function of solution velocity. Therefore, it may be concluded that, degradation rate oflead anodes is controlled by detachment of the corrosion products from the surface rather than by electrochemical reactions. IntroductionElectrowinning is one of the extraction stages of zinc, in which pure zinc is deposited from acidic solution after froth flotation, roasting and leaching processes. The anode electrode materials play important roles in the electrowinning process. Their electrocatalytical capacities determine the oxygen evolution overpotential, and consequently the cell potential and energy efficiency of the zinc electrodeposition [l]. Purity of the zinc deposited on the cathode is affected by the solubility and corrosion resistance of the anode materials. Using insoluble materials as anode in the electrowinning leads to the higher purity of the deposited metal on the cathode[2]. Lead (Pb) and its alloys have been used as the anode in the zinc electrowinning because of its special properties such as relatively low cost, low melting point, insolubility in solutions containing sulphuric acid and high conductivity in both states of metallic and oxidized [3, 4]. In zinc electrowinnig, zinc reduction occurs on the cathode (reaction 1) and the oxygen evolution reaction (OER) (reaction 2) is the main anodic reaction [5, 6]."

Jan 1, 2013

By J. Pang, S. Chander

The results of an investigation to characterize the chalcopyrite/solution interface are presented. Several techniques were used, including galvanostatic and steady-state polarization, cyclic voltammetry and impedance spectroscopy. The results show that the dissolution of chalcopyrite was incongruent. Initially, at low potentials (< 0.12 V), iron species were released that led to the growth of an iron-deficient sulfide (IDS) layer (referred to as the "reacted layer" in this paper). Depending on the solution&apos;s composition, the dissolved iron might reprecipitate as a hydroxide layer. In the potential range of 0.12 V < E < 0.23 V, the IDS layer was passivating. In comparison, development of a passivating IDS layer under galvanostatic conditions led to a jump in potential to 0.48 V. The IDS layer began to dissolve at potentials greater than 0.24 V. The dissolved species precipitated to form a product layer in alkaline solutions. Continued oxidation involved diffusion of species through the reacted and product layers. At higher potentials (> 0.48 V), further oxidation led to the dissolution of the copper and sulfur species, with a resultant breakdown of the IDS layer. The changes in surface-coating properties, resulting from various electrochemical treatments, are discussed.

Jan 1, 1993

By J. E. Gebhardt, D. A. Rice, P. E. Richardson

An improved understanding of the significant role of electrochemical reactions in sulfide flotation has evolved in the past 20 years, This understanding has been accompanied by a corresponding increase in attempts to control the electrochemical potential of flotation pulps for monitoring and controlling sulfide flotation circuits to improve metallurgical performance. This paper discusses the basic electrochemistry of sulfide flotation and the use of electrochemical potential as a control parameter.

Jan 1, 1993