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By J. Mirza, E. Nicol, J. Lipkowski

Gold passivation in thiosulfate leaching media is a major barrier to its implementation. Addition of Cu (II) into the leaching solution has shown to aid in gold dissolution, but the mechanism by which it acts, and its role in the passive layer, remains unknown. Surface Enhanced Raman Spectroscopy (SERS), in tandem with linear sweep voltammetry, were employed to determine the dependence of leaching currents on mass transport and for fingerprint identification of sulfur species on the surface of gold. SERS leaching experiments were performed using gold nanorod electrodes that showed increased stability compared to other SERS active surfaces.

Jan 1, 2011

By Y L. Ma, M Chen, W Bruckard

With the extensive exploitation and gradual depletion of high-grade copper reserves, the mining industry is paying more and more attention to the hydrometallurgical extraction of copper from lowgrade and arsenic bearing copper ores. Hydrometallurgical processing, such as heap leaching, column leaching and bioleaching, provide a viable alternative to the traditional pyrometallurgy due to its harmony with the environment, moderate capital investment, and low operating costs. However, the slow leaching kinetics of enargite (Cu3AsS4) and chalcopyrite (CuFeS2) remain problematic for commercial leaching practice. The formation mechanism and the nature of the passivating layers during leaching is still a matter of debate in hydrometallurgical research. In this study, the dissolution mechanism of enargite and chalcopyrite in sulfuric acid solution was investigated using a range of electrochemical and spectroscopic analysis methods. Electrochemical oxidation of enargite demonstrated an obvious passivation region from 500 to 750 mV (Ag/AgCl). The formed passivation film was found a n-type semiconductor behaviour, which is different from the original enargite with a p-type behaviour. The results of X-ray photoelectron spectroscopy (XPS) suggested that a nonstoichiometric film Cu(3−x)As(1−y)S4 (x>>y) accumulated on the electrode surface, which accounted for the obvious decrease in current density in the passive potential region. For chalcopyrite, three important potentials of 550, 680 and 730 mV which are related to the formation and dissolution of passivation film were observed based on the cyclic voltammetry (CV) and potentiodynamic polarisation. Raman and X-ray absorption near edge structure (XANES) spectra studies of the chalcopyrite electrodes after being treated under these three potentials indicated a metal-deficient sulfide of Cu1−xFe1−yS2 (y>>x) might be responsible for the passivation phenomenon. Hence, it is concluded that the passivation of enargite and chalcopyrite are similar which are caused by metaldeficient sulfide surfaces although the compositions of the metal-deficient sulfide are different.

Aug 24, 2022

By Ignacio González, Marcos Monroy, Valerie Bertrand, Roel Cruz

Results of an electrochemical study using carbon paste electrodes of pyrite and pyrrhotite samples suggest that the mineralogical impurities associated with these minerals are the determinant factor on their reactivity under alteration systems. These results were supported by mineralogical and leachate chemistry data from leach cell tests run on these samples. Pyrite reactivity decreases in the presence of associated impurities due to a galvanic effect whereas pyrrhotite reactivity appears to be controlled by the formation of a passivating layer, which overcome impurities effect. Electrochemical responses of sulfide-bearing samples provided valuable information on the prediction of ARD generation.

Jan 1, 2000

By Tadao Nagai, Masao Sato

Electrochemical measurements have been carried out in an auto- clave to investigate the electrochemistry of hydrogen precipitation of nickel from acetate buffered solution. After having previously obtained the rate equation for this reaction we have now made a concentrated effort to explain the rate equation electrochemically. A saturated NaC1-type Ag/AgC1 reference electrode has been improved so that it can be used in an autoclave. Polarization curves for the reaction, [H2=2H+ + 2e,] on nickel electrode were measured in solutions free from nickel ions at 185°C, and the parallel curves were obtained by changing PH2 and pH for normal and reverse reactions, respectively. Polarization curves in nickel solutions were complex, probably because the potential of hydrogen electrode is close to that of nickel and of the nickel surface altered during polarization. Then the nickel electrode potential and the reaction rate were measured simultaneously during pressure reduction at various hydrogen pressures and at various nickel concentrations. The reaction rates in terms of current density were plotted to obtain the local polarization curves for reactions Ni2+ + 2e ? Ni and H2 ?2H+ + 2e. The anodic and cathodic local polarization curves exhibit potential dependency. Therefore it is likely that the pres- sure reduction can be regarded as a coupled electrodes reaction.

Jan 1, 1973

By H. E. Wilde

"Zinc has been used for many years as a galvanic coating for the protection of steel. Electrochemical measurements show that zinc actually overprotects steel. The corrosion rate of DQSK (drawing quality semi-killed) steel in air saturated salt water was determined as a Junction of applied cathodic potential. The resulting data indicate that at a critical cathodic over potential of - O. 725 Vsce an acceptably low corrosion rate of less than 1 mpy occurs. Using the developed criterion, alloys of Zn/X and AL/X were produced and evaluated in galvanic contact with steel in a standard laboratory test. The results indicate that Zn /Mn, Zn /Co, AI/Mg/Si and AI/Mg/Ge alloys offer excellent galvanic protection along with (a) no hydrogen evolution, and (b) improved dissolution life over Zn coatings.IntroductionZinc coated (galvanized) steel has been successfully used in applications where bare (or painted non-galvanized) steel would suffer corrosive attack. In general, galvanic coupling to zinc, as either an anode or a coating, is an effective means for combatting steel corrosion. Because of this, the use of galvanized steel has increased markedly, stimulated primarily by automobile manufacurers seeking to extend the corrosion warranties on automobiles(1).Although effective, zinc coatings are not without a number of drawbacks which warrant efforts to improve them. For example, because of the widely differing electrode potentials between zinc and steel ( - 1.05 Vsce and - 0.60 Vscc, respectively, in air saturated NaCl solutions), the zinc corrodes at a rapid rate to protect the steel. This is reflected in the limited lifetimes of galvanized unpainted siding. The basic electrochemistry controlling the situation is shown in Figure 1, for a system controlled by oxygen reduction. The zinc corrodes sacrificially to protect the steel, while cathodically polarizing the steel to a potential near that of zinc's open circuit anode potential."

Jan 1, 1990

By Q. Zhang

The flotation behavior of jamesonite was investigated with ethyl xanthate as a collector. It has been shown that jamesonite has good floatability from pH 2 to pH 12, and relatively poor floata-bility at pH>12. The flotation of jamesonite was also dependent on pulp potential at certain pH val-ues. The potential-pH range for jamesonite flotation was established. The FTIR spectroscopy analy-sis and XPS measurement showed that the major adsorption product of ethyl xanthate on jamesonite was lead ethyl xanthate and antimony ethyl xanthate. The intensity of the FTIR signals of metal ethyl xanthate adsorbed on jamesonite and the flotation response of jamesonite were correlated with pulp potentials.

Jan 1, 2014

By L Dzinza, K C. Corin, M Tadie

The recycling of process water comes with increased electrolyte concentrations that affect water quality, which may in turn affect the flotation performance of valuable minerals (Hirajima et al, 2016). Electrolytes such as Ca2+, SO4 2- , Mg2+ and S2O3 2- have been surmised to have an impact on the action of flotation reagents such as collectors (Ikumapayi et al, 2012). Xanthate collectors are known to play a significant role in imparting hydrophobicity on mineral surfaces to enhance their flotation. The interaction between minerals and xanthates is well known to be electrochemical in nature. Such redox processes may be elucidated by electrochemical techniques. Since the mechanisms involving the interactions between electrolytes in process water with sulfide minerals and the subsequent adsorption kinetics of collectors are not well understood, this study therefore aims to provide fundamental knowledge to unpack the mechanisms involved when electrolytes interact with Platinum Group Minerals (PGMs) and how these interactions may affect xanthate adsorption. The interaction of sodium iso-butyl xanthate (SIBX) in the presence of electrolytes at increasing ionic strength was investigated by rest potential measurements, to explain the impact of electrolytes on the adsorption of SIBX on PGMs in the flotation process. Rest potential measurements for PdTe2 and PdS were conducted in an air saturated 0.05 M di-sodium tetraborate decahydrate solution, in the absence and presence of SIBX and electrolytes. It was found that the existence of sulfide and telluride on palladium affects the mechanisms in which electrolytes interact with Pd mineral surfaces. An increase in the ionic strength of Na2S2O3, CaCl2 and MgCl2, increased the interaction between the salts and PdS, thus decreasing the extent to which SIBX interacted with PdS. An increase in ionic strength for Na2S2O3 increased the interaction between Na2S2O3 and PdTe2 and therefore decreased the extent to which SIBX interacted with PdTe2. Other salts investigated in this study increased the rate of oxidation of PdTe2 with an increase in ionic strength thereby enhancing the interaction of SIBX and PdTe2. This study has shown that mineral type, electrolyte type and concentration all have an impact on the mechanisms that result in the adsorption of SIBX on PGMs.

Aug 24, 2022

By M. J. Nicol

The leaching of gold with thiosulfate solutions in the absence of ammonia and copper ions was investigated using electrochemical and kinetic methods. In sodium thiosulfate solutions, the electrochemical oxidation of gold was hindered and the leaching rate using pure oxygen as the oxidant was very slow. It was found that the addition of a small amount of thiourea or formamidine disulfide to the thiosulfate solution greatly enhanced the oxidation of gold. However, the enhancement to the overall dissolution of gold using dissolved oxygen as the oxidant was limited. This was attributed to the fact that the oxygen reduction process was unaffected by the additives and remained slow, which limited further improvement to the overall kinetics. An alternative oxidant, the ferric EDTA complex having a reduction potential of approximately 0.12 V, was found to be promising. The cathodic reduction of ferric EDTA was fast and reversible at neutral pH. While the ferric EDTA complex was effective in oxidizing gold, it did not appear to significantly oxidize thiosulfate. A thiosulfate solution containing thiourea and ferric EDTA has been shown to quickly dissolve gold in the form of a powder as well as from gold ores. In the leaching with the ores high gold recoveries of above 90% was achieved with the best performance obtained in neutral solutions (pH 6-7).

Jan 1, 2005

By P. E. Richardson, N. P. Finkelstein, Z. Chen

The large band gap and insulating properties of sphalerite have limited the application of standard electrochemical techniques for studying its reactions with flotation reagents. This problem has been overcome by developing electrodes that rely on the surface conductance produced when sphalerite is activated with copper or other heavy metals. A brief exposure of the mineral in copper sulfate solutions results in electrodes that exhibit significant electrochemical activity characteristic of copper sulfides. Voltammetry studies conducted on sphalerite activated in 10-4 M CuS04, solutions at pH 4.6 provide information on both the amount and the nature of the activation product(s). It is shown that copper activation is strongly dependent on the electrochemical potential applied during activation. Activation at potentials increasingly negative of the rest potential causes a progressive increase in the amount of copper on the surface; activation at potentials positive of the rest potential decreases the amount of copper on the surface. The results indicate that both the kinetics of copper uptake and, possibly, the chemical composition (stoichiometry) of the activation product are controlled by the electrochemical potential.

Jan 1, 1995

By M. J. Nicol, T. Moyo

Ammoniacal solutions are an effective lixiviant for the oxidative dissolution of some mineral sulphides. A detailed study of the anodic dissolution of chalcopyrite in ammonium sulphate-ammonium hydroxide solutions has been carried out using cyclic voltammetry, chrono-amperometry and rest potential measurements. The role of the copper(II)/copper(I) redox couple in the oxidation process has been evaluated. Rest potentials have been found not to be affected by oxygen but to increase with an increase in initial copper(II) concentration. Pseudo-steady-state anodic current densities measured in the absence of copper(II) ions at the rest potentials obtained in the presence of copper(II) ions increase with increasing concentration of copper(II) ions, confirming the positive effect of copper(II) ions on the rate of dissolution of the mineral. Cyclic voltametric and chrono-amperometric data show that in the absence of initial copper(II) ions, the rate of dissolution in the presence of dissolved oxygen is significantly lower. These results confirm that the effective oxidant for the mineral under the conditions of the study is copper(II) and not dissolved oxygen. Coulometric measurements have been used to establish the stoichiometry of the anodic reaction at different potentials.

Jan 1, 2014

By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By Gerhard Derge

THE chemical and physical properties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use, These processes are carried out at high temperatures and involve such complex chemical systems that fundamental scientific knowledge of the properties and behavior of these slags is inadequate. Various hypotheses have been proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenck1 and the recent papers of Chipman and co-authors.2-5 Another proposal is that these compounds dissociate by completes or partial ionization, the evidence for which has been reviewed by Martin and Derge.7 Whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: I, Studies of solidified slag samples by X-ray diffraction, petrography, and similar methods that can be used at room temperature, The correlation of this information with the high-temperature properties of the molten slag is uncertain, 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature, However, even these data present problems of interpretation because they require a complete knowledge of the metal phase, 3, Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret, Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information, The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems CaO-SiO2 and CaO-A1203-Si02 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1946

By I. Iwasaki, K. A. Smith, X. Cheng

The reaction mechanism for the cathodic decomposition of pyrrhotite in deoxygenated solutions at natural, near neutral pH levels was studied using potential and cyclic voltammetric measurements. Reaction products on the pyrrhotite surfaces were examined by Auger Electron Spectroscopy (AES), by X-ray photoelectron spectroscopy (XPS) and by analyzing the voltammograms for the electron balance of the reactions. Surface properties of the pyrrhotite/solution interface were characterized using an ac impedance technique. The parameters of an equivalent circuit were determined by the nonlinear least-squares fit (NLLSF) technique. The effect of cathodic polarization on floatability was investigated by performing microflotation tests. Possible implications to the flotation separation of chalcopyrite-pyrrhotite ores are discussed.

Jan 1, 1995

By X. Cheng

The mechanism of cathodic decomposition of pyrrhotite was studied in deoxygenated solutions at natural, near neutral pH using potential and cyclic voltammetric measurements. Reaction products on pyrrhotite surfaces were examined by AES and XPS, and by analyzing the voltammograms for the electron balance of the reactions. Surface properties of the pyrrhotite/solution interface were characterized using ac impedance technique. The parameters of an equivalent circuit were determined by the nonlinear least squares fit (NLLSF) technique. The effect of cathodic polarization on floatability was investigated by micro-flotation tests. Possible implications to the flotation separation of chalcopyrite-pyrrhotite ores are discussed.

Jan 1, 1993

The dissolution behavior of gold and copper from their elemental states and from Au/Cu alloys in cyanide solutions has been investigated using a rotating disc electrode. The anodic and cathodic reactions were studied separately and the resulting polarization curves were combined to examine the overall dissolution reactions. The dissolution rate of pure gold in the aerated cyanide solutions was inhibited by the anodic passivation on the gold surface, while the dissolution rate of pure copper was found to be mass-transfer-controlled. On the other hand, the dissolution of gold and copper from the alloys was partially controlled by electrochemical reaction and largely by mass transfer.

Jan 1, 1994

By William E. Foreman

The results of the electrokinetic study of the activation of quartz by divalent cations showed that the charge reversal was related to the point at which the cation hydrolyzed. The reversal was not due to the presence of solid hydroxide at the surface of the quartz but due to the charged ions in the solutions. The charge reversal for beryllium at a log molar concentration of 1x10-4 was observed at pH 5 and 9. The quartz was positively charged between a pH reading of 5 to 10. Magnesium at the same log molar concentration did not show a charge reversal from pH 2 to 12. The probable cause of the charge reversal was due to the ionized Be3 (OH)3+3 or Mg (OH)+ . Variations in the electrokinetics of quartz were minimized by heating the sample to 300° C.

Jan 1, 1968

By W. W. Wen

The objective of this investigation was to study the electrokinetic behavior of oxidized coals to indicate the feasibility of separating oxidized coals from ash materials and pyrite by an mine flotation process. The effects of soluble inorganic electrolyte products from coal oxidation were also examined. The electrokinetic behavior of coals of different rank and degree of oxidation were studied by an electrophoreses technique. Generally, increasing the oxidation increases the negative value of the zeta-potential and decreases the isoelectric point (IEP). Flotation results indicate that the flotation recovery increases with decreasing pH values, and that with ferrous sulfate at pH 6.5 the flotation recovery is optimum while the pyrite was depressed. Comparing the flotation results with the electrokinetic results verified that in the presence of ferrous sulfate, the maximum hydrophobicity of oxidized coal with dodecylamine and frother is near its IEP which is around pH 6.5 to 7.0.

Jan 1, 1976

By W. W. Wen, S. C. Sun

The objective of this investigation was to study the electrokinetic behavior of oxidized coals to indicate the feasibility of separating oxidized coals from ash materials and pyrite by an amine flotation process. The effects of soluble inorganic electrolyte products from coal oxidation were also examined. The electro-kinetic behavior of coals of different rank and degree of oxidation were studied by an electro-phoreses technique. Generally, increasing the oxidation increases the negative value of the zeta-potential and decreases the isoelectric point (IEP). Flotation results indicate that the flotation recovery increases with decreasing pH values, and that with ferrous sulfate at pH 6.5 the flotation recovery is optimum while the pyrite is depressed. Comparing the flotation results with the electokinetic results verified that in the presence of ferrous sulfate, the maximum hydro-phobicity of oxidized coal with dodecylamine and frother is near its IEP, which is around pH 6.5 to 7.0.

Jan 1, 1978

By G. Marchand, R. H. Hay, E. C. Pearson

"AbstractA polishing .technique is described together with two anodic etching methods for aluminum and its alloys. Some of the optical and structural characteristics of the film formed by •these etching methods are discussed and it is shown to what degree these properties of the film are related to the crystallographic orientation of the metallic substrate. Applications to the study of recrystallization and twinning phenomena and to the study of plastic deformation, banding, and texture estimation are discussed. Micrographs are shown .to illustrate the manner in which the technique is particularly well suited to the study of such phenomena.IntroductionThe physical metallurgist is constantly faced with the problem of polishing and etching of metallic sections. Mechanical polishing is tedious, time consuming, and not applicable whenever a surface entirely free from plastic deformation is required. Etchants are generally required to reveal the grain structure in order to determine its size, shape, and regularity, or to bring up constituents. In the case of aluminum, the .most common etchant to reveal grains is a mixture of three acids: HC1, HN03, and HF. This etchant is fairly satisfactory on certain alloys and for certain metallurgical conditions but in general fails to give a good definition of the grain on castings, on highly alloyed products, and whenever the grain is smaller than 100 microns in diameter. Besides size and shape, a grain, or crystal, has an orientation and may be endowed with several types of imperfections."

Jan 1, 1952

By W. G. Pfann

THE problem of forming points on wires that were from 0.002 in. to 0.010 in. in diam arose in the recent appearance of silicon and germanium point contact rectifiers as elements in microwave radar.1 In these devices a pointed tungsten wire makes a delicate contact with the surface of a semiconductor. Because the quality of such rectifiers is largely determined by the nature of this contact, considerable attention has been given to the formation of the metal point. Reproducibility of contour and freedom from burrs and even microscopic irregularities are considered essential. The operations involved must be simple and rapid enough for mass production. Previously tungsten wires had been provided with conical points by a grinding method which involved rotating a wire about its axis and causing it to bear at an oblique angle against a spinning abrasive disc. This was later complemented with an electrolytic polishing treatment which removed irregularities from the ground point and also rounded it off at the tip-a desirable feature. Finally, these operations were supplanted by the electrolytic pointing method described here. MECHANISM OF POINT FORMATION The wires to be pointed are partially immersed- in an electrolyte in a .vertical position whereupon they are provided with smooth rounded points entirely by electrochemical action. The process is independent of the depths to which the wires penetrate the electrolyte because the points are formed at the surface level. It may be used to point a single wire or many of them simultaneously and is applicable to wires of different diameters within a limited range. Solution of the immersed portion of a tungsten wire is accomplished by making it the positive electrode in an electrolytic cell, as shown in Fig I. While the wire is maintained at constant voltage the current through the cell falls continuously, principally because of the decrease in wetted area which results from solution of the tungsten. This increase in resistance occurs in a reproducible manner and is used as a control in the process. As the immersed portion of the wire dissolves, it remains cylindrical in shape except for the short section which is wetted by the meniscus. Here the rate of solution is lower and decreases as the top of the meniscus is approached. The result is the formation of a tapered section inside the meniscus. As solution continues, the cylindrical section either dissolves entirely or drops off just before complete solution, leaving only the taper which is now sharply pointed. Further action causes this point to become rounded and then quite blunt, until finally the end of the wire is almost plane. Fig 2 shows the stages in this development. Contour PF is most representative of those used in point contact rectifiers. Thus a variety of point

Jan 1, 1947