GONZALO VIRAMONTES GAMBOA1*, SILVANO VELSQUEZ ROQUE1, LAURA A.

IBARRA BRACAMONTES2, RENATO GONZALEZ BERNAL2 1 Laboratorio de Fisicoqumica, Facultad de Ciencias Fsico-Matemticas 2 Facultad de Ingeniera Mecnica Universidad Michoacana de San Nicols de Hidalgo Francisco J. Mujica s/n, Col. Felicitas del Ro, CP 58060, Morelia, Mich. Mxico *Corresponding author: gvgamboa@umich.mx RESUMEN En este trabajo se presenta, por una parte, el comportamiento de la calcopirita cuando se expone a potenciales elctricos transpasivos en medio sulfato, teniendo como resultados sobresalientes la existencia de una ventana de potencial a la cual las partculas de calcopirita se disuelven en su totalidad en tiempos que van de los 2 a los 5 minutos, sin importar el origen geolgico del concentrado, as como el hecho de que esta disolucin rpida no requiere necesariamente de un medio cido, ya que las partculas se disuelven incluso ms rpido a pH neutro. Por otra, se presentan los avances en el desarrollo de un reactor electroqumico cuya meta es lograr la lixiviacin de concentrados de cobre en cuestin de minutos, se presentar tanto los detalles del diseo y su construccin, como los retos que se han ido sorteando en busca del logro de este objetivo. ABSTRACT In this work, on one hand, the behavior of chalcopyrite in a sulfate medium when exposed to transpassive electrical potentials, is presented. This study demonstrated the existence of a potential window, in which chalcopyrite particles are completely dissolved in 2 to 5 minutes, without regard to the geological origin of the concentrate or even if the leach is in an acid medium, since the particles actually dissolve faster in a neutral pH. On the other hand, advances in the development of an electrochemical reactor, whose purpose is the leaching of copper concentrate in a question of minutes, are shown; details of its design and construction are presented, as well as the challenges that have been surpassed in the quest for this objective. Keywords: chalcopyrite, transpassive leaching, electrochemical reactor INTRODUCTION According to Davenport et al. (2001) from 70 to 80 % of the world total reserves of copper are contained in the mineral chalcopyrite, making it the most economically important among all copper minerals. Its economic importance has triggered many fundamental and applied studies around the

CHALCOPYRITE LEACHING IN MINUTES

globe aimed to understand its chemistry, in the search for alternative hydrometallurgical routes for copper production. In summary, what we know about the chemistry of this mineral is that it is extraordinarily difficult to leach using economically viable processes. Practically every known leaching method has been applied to chalcopyrite, ranging from atmospheric acidic leaching, high pressure leaching, bioleaching, chloride leaching, galvanic leaching, etc. (Dreisinger, 2006; Crdoba et al., 2008 a y b; Nazari et al., 2011; Javad Koleini et al., 2010; Kametami and Aoki, 1985; Pinches et al., 2001; Third et al., 2002; Ballester and Crdoba, 2005 a & b; Rivera-Vasquez et al., 2007; Viramontes-Gamboa et al., 2006; Viramontes-Gamboa et al., 2007 a & b; Viramontes-Gamboa et al. 2010; Tshilombo, 2004; Hiroyoshi et al., 2008; Velsquez-Yvenes et al., 2010; Ahonen and Tuovinen, 1993; Nicol and Miki, 2005; Zeng et al., 2011). Unfortunately a viable alternative to smelting has not yet been found. Every tested methodology has found one or more challenges that have rendered the extraction of copper either technically unviable or economically unprofitable. Fortunately, the research is on-going and new results and phenomena regarding chalcopyrites behavior are reported continuously. OXIDATIVE BEHAVIOR OF CHALCOPYRITE Chalcopyrite is a mineral that displays electrochemical active-passive and passive-transpassive transitions as a function of the potential applied to its surface (Figure 1). Such surface potentials can be applied using external sources of potential or through the use of chemical redox couples in the leaching solution. Between the open circuit potential of the mineral ( EOCP) and the evolution of oxygen, it is possible to identify four distinct ranges of potential where chalcopyrite exhibits different behaviors, which are shown in Error! Reference source not found. for 50 C and different concentrations of sulfuric acid. In the first range of potentials, EOCP < E < ~440 mV vs. SCE, which is called the active range, the dissolution rate of the mineral follows a very well defined Tafel behavior. In the second range, ~440 < E < ~510 mV, the dissolution rate ceases to follow Tafel behavior, and a tilted current plateau is observed. In the third range of potentials, beginning at approximately 510 mV, chalcopyrite experiences passivation effects characterized by a gradual decrease of the dissolution current until it reaches a limit steady state value. That limit value can be as little as one tenth of the maximum dissolution rates observed in the active range, although this is dependent on temperature. This third, passive, range is the one to be avoided in any hydrometallurgical process, since the rates of copper recovery are exceptionally slow. The upper limit of the third range is the beginning of the transpassive regime, which is the fourth and, for the objectives of this paper, the most important range of potential. The third range can therefore be expressed as ~510 < E < Etranspassive mV. The exact value of potential at which the transpassive behavior of chalcopyrite begins is strongly influenced by acidity and temperature (Rivera-Vasquez et al., 2007; Viramontes-Gamboa et al., 2006; Viramontes-Gamboa et al., 2007 a & b; Viramontes-Gamboa et al.,

2010). Increasing the concentration of sulfuric acid from 2 to 100 g/L increases the onset of transpassive leaching from ~ 650 mV to ~ 1100 mV at room temperature. When acidity is maintained constant, increasing temperature also increases the onset of transpassive dissolution. In the transpassive regime, the oxidation rate of chalcopyrite increases abruptly by up to six orders of magnitude (one million times) with respect to typical values observed in the active or passive ranges. Unfortunately, transpassive potentials are not achievable using common redox couples available industrially. Hence, chemical leaching in the transpassive regime at economic industrial rates is virtually impossible. However, if there is no reason to restrict ourselves to chemical leaching, this extremely fast dissolution rate of chalcopyrite creates an opportunity to design innovative processes by applying transpassive external potentials to chalcopyrite concentrates using adequately designed electrochemical reactors. MAIN OBJECTIVE OF THIS STUDY The present work explores the behavior of individual chalcopyrite particles during the application of high potentials that lie in the transpassive regime. This was made possible by the application of single particle microelectrochemical techniques. Total dissolution of single particles was possible since the high potentials applied dissolved the tiny mass of chalcopyrite present in the particles in matter of minutes. During the dissolution process, the formation of sulfur was explored in detail. This work demonstrates that near instantaneous dissolution of chalcopyrite is possible at high potentials without the addition of chemical oxidizing agents or catalysts. In the last section, the advances in the development of a laboratory prototype electrochemical reactor designed to leach chalcopyrite concentrates are presented.
a 50 C, H2SO4 = 2 g/L

50 C b
Potential, mV (SCE)

ty , A/c 2 m

50 0 40 0 30 0 20 0
0

900 H2SO4, g/L 800 700 600 500 400 300 10 100
2 10 30 50 70 100

den si

Curr ent

520 500 480 460 440 420 150 200 250 300 350 400

10 0 73 10 6 0 ) 20 6 80 5 30 CE 30 (S 53 80 V 4 0 40 ,m Time, min 4 80 ial 50 t 38 30 n te 33 0 60 Po 0

1000
2

10000

Current density, A/cm

Figure 1. Potentiostatic anodic polarizations for chalcopyrite from Chihuahua,

Mexico at 50C. a) i-t-E surface at 2 g/L of H2SO4; b) Anodic potentiostatic behavior of chalcopyrite at the various concentrations of H2SO4. The arrows indicate the trends with increasing concentration of acid. The inset zooms in on the behavior between 420 and 520 mV. No added ferric, ferrous or cupric ions.

METHODOLOGY MICROELECTRODE FABRICATION In order to study the electrochemical behavior of micron size particles, microelectrodes of the mineral were constructed (Perdicakis et al., 1997) as shown in Figure 2. First, an electrically conductive carbon microfiber having a 25 m diameter (from World Precision Instruments, WPI) was welded to a 0.5 mm diameter platinum (or copper) wire using conductive carbon/silver epoxy (WPI). The platinum wire and the carbon microfiber were then placed inside a borosilicate glass capillary with a 0.86 mm internal diameter and 10.0 cm length (WPI). The array was then placed inside a WPI microelectrode having a gold pin connector. The tip of the capillary end with the carbon microfiber was pulled using a Sutter Model P-30 vertical micropipette puller, in such a way that the melted glass tightly covers the carbon microfiber leaving only a very short (100 to 250 m) bare tip, which is used to make the electric contact with the chalcopyrite microparticle.

Figure 2. Actual microelectrode Figure 3. Schematic setup of the three (right), and schematic electrodes micro-electrochemical cell. representation (left) showing the construction details.

MICRO-ELECTROCHEMICAL ARRANGEMENT The electrochemical cell is depicted schematically in Figure 3, it consisted of a small glass container surrounded by a heating tape for temperature control. The container was filled with a known amount of leaching solution (prepared only with deionized water and sulfuric acid at the desired pH), having inside a piece of glass porous frit, on top of which the chalcopyrite particles were placed. The use of the glass frit is optional; its only role is to hold the particles in place. If not used, it is more difficult to keep an uninterrupted electric contact between the chalcopyrite microparticles and the tip of the carbon microfiber. To achieve electric contact between the microparticles and the carbon microfiber, and to manipulate the particles, it was necessary to use high resolutions (40nm/step) micromanipulators. The whole arrangement is placed under a 400X stereoscopic microscope coupled to a video recording system, which allows filming simultaneously with the recording of electrochemical curves by the Versastat 4 PAR potentiostat software. A common three electrode electrochemical arrangement was used. The working electrodes were chalcopyrite microparticles connected to the potentiostat through the microelectrodes described above. Particles from more than 15 different sources were tested (both from chalcopyrite concentrates and from ground chalcopyrite chunks) from many locations all over the world, including Mongolia, Africa, Canada, Chile, Mexico, United States of America, Peru, Australia, etc. The reference electrode was either an Ag/AgCl or a Standard Calomel Electrode whose tip was placed around 100 m away from the microparticle. Potentials in this work are all referred to the Standard Calomel Electrode scale. The counter electrode was simply a 0.5 mm width pure platinum wire. RESULTS AND DISCUSION BEHAVIOR OF CHALCOPYRITE PARTICLES IN THE TRANSPASSIVE LEACHING Sets of new and important results are obtained when the electrochemistry of chalcopyrite is studied at the microparticle level. Figure 4 show the oxidative behavior of chalcopyrite microparticles at 25, 40 and 60 C and 90 g/L H 2SO4 at a scanning potential rate of 20 mV/s. Essentially, it is possible to observe the same four different ranges of potential mentioned in the introduction, the Tafel range, the tilted plateau, the passive range, and finally the onset of transpassivity. However, with microparticles the potential for the beginning of transpassivity decreases with increasing temperature. Figure 4 shows that transpassivity comences at 600 mV for 60 C, while it starts around 760 mV for 20 C. The opposite trend is observed when the active-passive behavior of chalcopyrite is studied using massive electrodes instead of microparticles [11-

15], in that case the potential where transpassivity starts increases with increasing temperature. The most striking result regarding the electrochemistry of chalcopyrite microparticles is shown in Figures 5 and 6. Figure 5 shows the current vs. time behavior when a chalcopyrite particle of approximately 150 m in size was polarized at 1.2 V, within the transpassive range. Figure 6 show a set of continuous pictures taken from the recorded video while the same particle was reacting; each picture has a time tag (minutes:seconds) indicating the time from the beginning of the experiment. The electrolyte was only water and sulfuric acid at 10 g/L and 25 C, with no other added chemicals.

Figure 4. Oxidative behavior of chalcopyrite microparticles at 20, 45, and 60 oC with 90 g/L of H2SO4 at a scanning rate of 20 mV/s.

Figure 5. Current vs time behavior of potentiostatic experiments carried on a chalcopyrite particle at 1.2 V (SCE), room temperature and 10 g/L of H2SO4.

Initial Particle

Sulfur

Chalcopyrite

Figure 6. Time sequence of the leaching process of chalcopyrite particles in the transpassive range of potentials.

Notoriously, the particle dissolved to completion in as fast as 5.5 minutes, which is an extraordinary result considering that when similar particles are leached at potentials within the Tafel range, it ordinarily would take from weeks to months to achieve the same result. The noisy behavior of Figure 5 is due to the fact that the only residue left behind is an amorphous layer of crystal clear transparent sulfur, which is an electrical insulator. As the chalcopyrite microparticle shrinks, the carbon microfiber momentarily losses the electric contact; fortunately it can be easily restored with the gentile application of additional pressure with the micromanipulator. As copper and iron ions leave the crystal structure of the chalcopyrite, they remain inside the sac of sulfur formed, which swells continuously due to the increase in osmotic pressure. From time to time, it is possible to observe under the microscope how the sac of plastic sulfur explodes, releasing concentrated amounts of the brownish electrolyte. EFFECT OF pH It is extraordinary to observe that the transpassive transformation of chalcopyrite microparticles to sulfur and copper and iron ions, most probably as cupric and ferric, is not dependent on pH. The phenomena can be also seen even when the electrolyte is pure deionized water, with no sulfuric acid added at all. Figure 7a and 7b show two typical current vs. time curves at pH 5.6 and only deionized water, respectively. The picture in Figure 7 is typical of the before and after appearance of the tested particles; under the microscope, a total transformation to sulfur is clearly observed. Three minutes were enough to leach almost to completion particles in the order of 70 m in size. The almost is due to the fact that it is very difficult to contact the last bit of unreacted chalcopyrite because the residual sulfur glues with the carbon microfiber and is not easily detached. Notoriously, the sulfur formed in these high pH cases is not entirely transparent. As the particle is reacting (or few minutes after it dissolves), it is possible to observe the formation of tiny amounts of some precipitates on the exterior of the sulfur layer, which according to thermodynamic might be copper and iron hydroxides. This behavior with pH is very relevant, since it demonstrates that very little consumption of acid is required in any possible technological process based on the fundamental transpassive knowledge explained so far. SCANNING ELECTRON MICROSCOPY Special emphasis was placed on how the sulfur begins to form on the surface of the particle. Images of chalcopyrite particles during the first 10 seconds of leaching at 1.2 V, 90 g/L of H2SO4 and 25 C were captured by Scanning Electron Photographs (Figure 8a). The particles were only attacked on certain parts of its surface, preferably at dislocations and along grain boundaries. Most of the surface did not show clear evidence of attack, and the only manifestation of sulfur, as globules, were sparsely distributed on the

chalcopyrite surface. Figure 8b shows another particle leached at the same conditions for 20 seconds, the residual plastic sulfur already covers the entire surface of the particle. Interestingly, when this sulfur layer is intentionally broken apart (with the help of the micromanipulators) in order to analyze the chemical composition of the surface of the remaining chalcopyrite, no evidence of corrosion was found, as if the particle was never polarized. EDX analysis of the exposed chalcopyrite surface gave a S/Cu/Fe ratio of 2/1/1. This suggests that chalcopyrite dissolves directly to plastic sulfur, and Cu and Fe ions, without the formation of any intermediate compound.
a) 50 40
pH 5.6 E 1.4 V (SCE) T 25 oC

Current, A

30 20 10 0 0 1 Time, (min) 2 3

b) 30 25
Deionized water T 25 oC E 1.2 V (SCE)

A Current,

20 15 10 5 0 0 1 Time (min) 2

Figure 7. Typical current vs. time behavior of chalcopyrite microparticles polarized to 1.2 V at a) ph 5.6 and b) in deionized water at room temperatures. The imagess to the right show the initial and final aspects of the leached particles at pH 5.6.

PROPERTIES OF THE RESIDUAL SULFUR LAYER Sulfur dissolution in carbon disulfide is the most reliable method to distinguish if a sample of sulfur has the yellow orthorhombic crystalline structure with crowns of eight atoms, or the amorphous plastic-like structure consisting of long polymeric chains of sulfur atoms (Steudel, 2003). In the first case sulfur is soluble in CS2, in the second case it is not. This solubility method was used to examine the solubility behavior in CS2 of the sulfur produced by the transpassive dissolution of chalcopyrite microparticles. It was found that soon after it is formed, it is not soluble, indicating that at the very beginning of the formation of the residual layer of sulfur, it is very far from thermodynamic equilibrium. The solubility increases with time; after 24 hours it is almost completely soluble, which indicates a slow relaxation process of the internal structure of the sulfur formed. At the beginning, it has a sticky very soft jellylike structure. After two to three hours, it has a glass-like behavior; a small amount of pressure is enough shatter it into many smaller parts; it is not soft or sticky any more.

Figure 8. SEM of chalcopyrite particles leached at 1.2 V, 90 g/L of H 2SO4 and room conditions by a) 10 seconds (cross section), b) 20 seconds. SULFUR AND SULFATE CALCULATIONS AT HIGH POTENTIALS Mass balances were performed during the dissolution of chalcopyrite particles at constant high potentials of 1.2 V and 1M of H2SO4. To achieve this, 50 particles from 70 to 150 m were transpassively dissolved at 1.2 V in 0.25 ml of leaching solutions at 1.0 M of H2SO4 and room conditions, in order to obtain measurable quantities of copper and iron in solution. Using the Cu2+ concentration in solution measured by both atomic absorption spectroscopy and inductively coupled plasma, and the charge measured by the potentiostat, an approximate yield of sulfur to sulfate was calculated. The charge transferred from the surface of each microparticle to the solution with the potentiostat is given by the integral of its current vs time curve (Figures 5,

and 7a-b). The reactions that were considered to be taking place at transpassive potentials are CuFeS2 Cu2++Fe3++2S0+5eCuFeS2 +8H2OCu2++Fe3++2SO42-+16H++17e[1] [2]

Considering the high potentials at which the transpassive experiments were performed, iron is assumed to enter the solution as the ion ferric. The results obtained for the estimation of elemental sulfur yield, S 0, was 88.8% and the rest was assigned to sulfate production, SO42-. The average number of electrons (n) involved in the reactions was 6.34, indicating the primary role of the first of the two chemical reactions. This result is in agreement with the visual observation, since elemental sulfur is the main residue of the reaction, even though the high potential conditions thermodynamically favors the formation of sulfate. ELECTROCHEMICAL REACTOR On the basis of the fundamental behavior of chalcopyrite microparticles exposed to transpassive potentials explained so far, a electrochemical reactor prototype was designed and built with the objective to study its performance in the search of the development of an entirely new process to leach chalcopyrite concentrates based on the transpassive behavior of chalcopyrite. The electrochemical reactor, shown in Figures 9 and 10, consists of seven different parts, assembled together. Some of these (Parts 1, 2, 5, and 7 ) are made of non conductive Teflon or PVC, while the others (Parts 3, 4, and 6) must be constructed from electrically conductive material, resistant to chemical corrosion and wear. When the reactor is functioning, Parts 1, 2, 3 and 4, assembled together, rotate at an angular speed controlled by a variable speed engine, which is connected through Part 1. Meanwhile, Parts 5, 6, and 7 remain static. Parts 4 and 6 are essentially two conductive metallic discs that will gently press the chalcopyrite microparticles between them, while Part 4 rotates slowly and Part 6 remains static. These two parts are under wear and are designed to be replaceable. Parts 2 and 3 are essentially hollow cylinders. Part 2, made of PVC, has a vertical cone to feed the ground chalcopyrite concentrate, which will pass from the cone to the inner hollow cylindrical line trough three small holes at the bottom of the cone. As shown in Figure 9, the concentrate arrives by gravity to the bottom of Part 4. In the event that the hollow cylindrical cavity is clogged, Part 2 is provided with an inner piston large enough to push the concentrate down to the bottom of Part 4. Part 5 is essentially a container where the leaching solution is introduced, in its bottom Part 6 is firmly placed under pressure in such a way maintain its immobility. Part 7 is essentially the lid of the container, with some holes to introduce the reference and counter electrodes. It also avoids undesirable splashing of the electrolyte when part 4 is pushed down a few microns above Part 6. The essence of the reactor is to form a thin layer of concentrate, which

will be pressed between parts 4 and 6. Part 4 is then polarized to the transpassive potential while rotating at a desired speed. Actually, Part 3 is physically connected to the Working Electrode cable of the potentiostat through a brush-like connector. In this way, the chalcopyrite particles are leached at transpassive potentials, while being fed continuously from the cone through the hollow interior of Parts 2 and 3. Parts 4 and 6 must be electrically conductive because they are directly in contact with the chalcopyrite microparticles, and it is through them that the transpassive potential is applied. All of the other parts are should be constructed with cheaper, nonconductive materials, in order to reduce its electrochemical corrosion.

Figure 9. Electrochemical reactor. Schematic view of the reactor and details of parts 2, 3 and 4.

Figure 10. Details of Part 5, the main chamber of the reactor. On the bottom of this chamber a corrosion resistant disk (Part 6) is placed. The main challenge of this electrochemical reactor is to find accurate materials of construction for parts 4 and 6, since they are simultaneously under strong corrosive conditions and wear. Stainless Steels 304 and 316L are, electrochemically speaking, passive enough at the transpassive potentials where chalcopyrite leaches almost instantaneously, from 1.2 to 1.4 V (vs SCE). Unfortunately they are not the best frictional wear resistant candidates. Currently, the research is focused on the characterization of the performance of the reactor itself and the search for different surface coats to make Parts 4 and 6 more resistant to the simultaneous effect of electrochemical corrosion and frictional wear. CONCLUSIONS A fundamental study of the transpassive electrochemical behavior of chalcopyrite microparticles, taken directly from copper concentrates or ground chunks of massive samples of the mineral, shows that microparticles with typical sizes ranging from 20 to 150 m can be leached to completion in a matter of two to five minutes in aqueous solutions containing only sulfuric acid. The only residue is a jelly-like structure of amorphous sulfur, which gradually crystallizes to a more thermodynamically stable orthorhombic structure. This nearly instantaneous leaching of chalcopyrite opens the window to the development of new technologies. A prototype electrochemical reactor has been designed and constructed with the objective of developing a technology capable of electrochemically leaching chalcopyrite in minutes; its characterization and performance are currently under study. ACKNOWLEDGMENTS The authors gratefully acknowledge the financial support from the National Council for Science and Technology of Mexico, Basic Science Project #

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