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By Matthew Tunnicliffe, Akram Alfantazi, Paul Nesbitt, Farzad Mohammadi

"Lead and its alloys are proper candidates for anodes in electrowinning processes mainly because they are insoluble in the leach solutions and relatively cheap. However, the annual cost of corrosion problems associated with these anodes is millions of dollars. In this study lead-silver and lead-calcium anodes were tested under typical nickel electrowinning conditions and the effect of chloride on the corrosion performance of the anode materials was investigated. Corrosion rates of the anodes were calculated using the discharge plateau (reduction of lead dioxide to lead sulfate) after galvanostatic experiments. It was found that lead calcium anodes have the highest corrosion rate both in the presence and absence of chloride. Surface morphology of the electrodes was studied using SEM and the corrosion products were characterized using XRD.IntroductionLead (Pb) is usually the preferred material for commercial anodes since it is insoluble in the leach solution and the costs are manageable. One advantage of using an insoluble material as an anode is the higher purity of the cathodic deposits and better quality of the end product. During nickel electrowinning, metallic nickel is deposited on the cathode while oxygen evolution reaction (OER) takes place on the anode. In practice, relatively high potentials are necessary for the reaction to proceed at the desired rate because of the high overpotential of OER on lead. Lead anodes get oxidized in typical electrowinning conditions and usually have two to three years of lifetime. Although the price of each anode is insignificant, the overall cost of corrosion of these anodes is considerable, which is due to the large number of anodes used in a plant, typically two to three thousand. Therefore, corrosion is a significant problem associated with lead anodes in commercial nickel electrowinning plants and industries show interest in addressing this problem. Corrosion of lead electrodes in acidic environments has been previously the subject of many research studies [I-7]. It has been reported that, during the anodic polarization of lead, several phases may be present on the surface, depending on the potential range that is being studied [8]. Lander showed that lead is oxidized at potentials higher than 0.252 YsHE with tetragonal lead monoxide being the main reaction product [9]. At 0.666 YsHE lead can transform to lead dioxide; however, it is not stable and transforms to lead sulfate and lead oxide. At potentials higher than 1.684 YsHE, lead dioxide is eventually a stable phase and forms a protective layer on the surface [I 0, 11]. Under conditions of a typical nickel electrowinning plant, usually a 200 A/m2 current density is passed through the electrodes."

Jan 1, 2012

By J. Vander Linden, R. De Ketelaere, M. Verhaege

In this paper, results are presented concerning the search to implement Supported Liquid Membrane (SLM) technology for the recovery of copper from electroplating effluents. Acid copper electroplating rinse solutions or effluents resulting from the post-treatment of, for example, cyanide-containing copper electroplating baths all contain copper (2+) in the lower concentration levels. A thorough study of the influence of the individual parameters and of their combined impact on mass transfer in small scale laboratory SLM modules has been performed, enabling to set forward the appropriate operating conditions for a pilot plant installation. The pilot plant, containing two SLM modules. of 18 m2 of surface area, has been tested extensively, including short and long term runs, with real process solutions. It was demonstrated that this installation is able to treat 40 l/h of acid copper sulphate rinse solutions· containing 500 ppm of copper. The final copper concentration in the effluent can be reduced to a few ppm while copper metal is recovered by electrolysis of the concentrate. This technology is also applicable to the treatment of solutions with low copper content of origins other than plating shops, such as tailings from copper plants or mine waters.

Jan 1, 2000

By Rak-Jun Choi

Plasma-induced damage of InGaN/GaN multiple quantum well (MQW) light-emitting diodes (LEDs) has been studied in terms of forward turn-on and reverse breakdown voltages, together with etch rate and surface morphology. The physical degradation of sidewall along with rough surface morphology of n-GaN caused by increased ion scattering induced the deterioration of the forward and reverse voltages. It was found that the turn-on voltage is sensitive to the surface roughness of the etched n-GaN and the breakdown voltage is strongly affected by the sidewall contamination. Annealing under nitrogen after the mesa etching improved the electrical properties of the InGaN/GaN MQW LEOs. Efficient blue light-emitting diodes (LEOs) were fabricated using InGaN/GaN triangular MQWs. The LEOs with triangular QWs showed a lower operation voltage and 2.4 times higher light output power than those with the rectangular MQW LEOs at 20 rnA and 20 "C. The intensity of electroluminescence (EL) at 20 mA was almost independent of ambient temperature in the triangular QW LEO, but decreased substantially in the rectangular one.

Jan 1, 2003

By A. Vahed

The Goro Nickel Project is situated in the Southern Province of New Caledonia. Inco Limited and Goro Nickel S.A. have developed a process that features the use of pyrohydrolysis to produce nickel oxide. The process treats a blend of laterites by Pressure Acid Leaching followed by solvent extraction of nickel and cobalt using Cyanex 301®. Purified nickel chloride solution is converted to high purity NiO product and 6M hydrochloric acid, which is recycled back to the SX circuit. In co-operation with Andritz AG, spray roaster and fluid-bed pyrohydrolysis technologies were examined for this purpose. Tests were conducted at the Andritz AG pilot plant in Vienna, Austria, and at Goro in larger scale installations. The latter served to establish process engineering design parameters for scale-up. Several process variables were investigated in both technologies and the off-gas characteristics were established. Fluid-bed pyrohydrolysis was selected for the Goro commercial plant, primarily because it produced a granular nickel oxide. The main focus of this paper is to outline the results obtained in pilot plant studies of liquid fueled fluid bed pyrohydrolysis for the Goro Project. Keywords: lnco Goro Nickel, Fluid Bed Pyrohydrolysis, Pilot Plant Tests

Jan 1, 2004

By Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn't significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By A. J. Paul

Traditionally, 16"/50 caliber projectile shells have been fabricated from forged steel. The Naval Surface Warfare Center (NAVSWC) has determined that cost savings of approximately 60% (-$4.7M/year) as well as improved shell fragmentation can be achieved by casting these shells from austempered ductile iron. One of the technical concerns arising out of this material substitution is the role of the casting process in controlling the quality of the cast shells. Optimizing the process through proper orientation of the mold, placement of chills, superheat, etc., can minimize shrinkage porosity and, consequently, flaw size. For this purpose, the mold filling and subsequent solidification of the projectiles was simulated using a 3-D, fully transient, coupled fluid flow and heat transfer model based on finite differences. Several casting orientations were investigated and the casting parameters were varied to optimize the process and minimize casting defects. A comprehensive software tool, which was developed using state-of- the-art visualization techniques, has been used to analyze the process of casting. Emphasis is placed on the use of this visualization tool as an aid to the foundry engineer for process optimization.

Jan 1, 1992

By André L. de Vegt

Soil and groundwater beneath a zinc production plant in The Netherlands are contaminated with metals and sulfate. To avoid contamination of nearby drinking water aquifers, a hydro-geological containment system and a biological treatment plant for the extracted ground water have been installed. Currently about 5000 m3/day of groundwater is extracted from a combination of 12 shallow and deep wells. Heavy metals and sulfate have to be removed from the extracted water before it can be discharged into a river. Several water treatment methods have been studied and pilot tested at the site. The preferred and selected process is based on the activity of sulfate reducing bacteria (SRB) and combines sulfate removal and heavy metal removal in one single installation. Anaerobic bacteria reduce sulfate to sulfide resulting in the precipitation of metal sulfides. Excess sulfide Is biologically converted to elemental sulfur. A full scale biological treatment system was started up in May 1992. Design, start-up, commissioning and operational experiences are reported in this paper. Concentrations of metals and sulfate in the SRB water treatment plant effluent are well within the limits set by the Dutch Authorities for discharge to surface water.

Jan 1, 1995

By Kevin L. Gering

A detection method and apparatus have been developed to perform real-time measurement of aqueous free cyanide, C-. A laboratory prototype can measure cyanide ranging from 5 micrograms ,per liter to 100 milligrams per ?liter for analysis times as short as 2 minutes per measurement. Sample size per measurement is typically only a few mI, thus? minimizing the waste volume produced from spent samples. The basis for this detection device is a quantifiable, stable affinity between the electrode material and free cyanide in the sample; The electrode exhibits piezoelectric behavior, allowing it to be used as a microbalance. This technology 'has experienced two generations of laboratory prototypes, and has been thoroughly tested to determine the operational sensitivity toward process variables such as pH, competing reactions, etc. The speed and ,accuracy of this method make it superior to conventional wet chemistry methods used for quantifying cyanide levels in water. A device based on this technology could be useful in areas involving process monitoring and environmental compliance, .particularly in the cyanide-based leach mining industry. Interest for this detector has been shown by the gold mining industry and others. Patent application is in progress.

Jan 1, 1998

By Michael E. Stout

M.A. Industries, Inc. has developed and is now offering on a commercially available basis, complete systems to recover and recycle lead from spent SLI batteries. The system begins with the breaking and separation of the component parts of the batteries and subsequent treatment of the effluent water produced by this operation. The recyclable materials recovered from this process are metallic lead, lead paste and polypropylene. The lead paste is introduced into a process to convert it from a lead sulfate to a lead carbonate. The process also regenerates the salt solutions into reusable carbonate. The lead carbonate is then leached into an acid bath where it is later recovered by a proprietary electrolytic process. The metallic lead is recovered in a short rotary furnace producing metal for further refining and alloying. The polypropylene is further washed and then introduced to a reclaim extruder along with the proper modifiers and additives. The resulting resin can then be sold on the open market to injection molding processors. This complete system greatly reduces the amount of waste to be disposed of and completely complies with all applicable EPA guidelines.

Jan 1, 1993

By C. Lupi

The electrorefining of primary copper is a well known technology: in this work copper scrap was directly processed in the same way. he copper and copper alloy scrap was previously pressed by means of a 20 tons apparatus in order to avoid pyrometallurgical operations. The samples obtained in this manner showed a good compactness so that they were used as anodes in the electrorefining tests. The tests were carried out on anodes made by copper scrap, copper alloy scrap and a mixture of the two. The electrorefining tests were performed at both 303 and 333 K, in a perspex cell having a volume of 500 ml using a current density of 250 A/m2. The cathode used was always a sheet of pure copper and the electrolyte composition was 40-50 g/l Cu as CuS04 and 150-200 g/l H2SO4. Current efficiency in the range of 92-97% and specific energy consumption ranging from 0.14- 0.20 kWg of copper were reached in all the tests. The refined copper deposits were analyzed by AAS to verify their purity and observed by SEM to highlight their morphology.

Jan 1, 1998

By Christopher Solnordal

A mathematical model was developed to simulate the performance of the reaction shaft at BHP-Billiton?s Olympic Dam copper flash smelter. In order to have confidence in the predictions of the mathematical model, validation was performed by comparing and reconciling the predictions from the model with the results from a campaign of sampling and plant measurements. The model was based on the computational code CFX4.4 utilizing a combustion sub-model purpose-built by CSIRO. The combustion sub-model employed the concept of a composite particle which contained the three components of the solid charge: concentrate, flux and returned dust. Plant measurements were made and samples taken immediately below the burner and through a port halfway down the reaction shaft. Parameters measured included temperature, solid loading and SO2 concentration in the gas. Comparison of the measured and predicted values then showed that: predicted far field gas temperatures were within ±50C of measured values; predicted temperatures in the central plume were lower than measured, and, the predicted plume width was slightly smaller than measured. An optimum composite particle size of 19 m was identified for use in future modeling work at Olympic Dam.

Jan 1, 2006

By Shize Jin

Effect of four polyols, namely ethylene glycol (EGL), glycerol (GCL), propanediol (PDL), butanediol (BDL) and three organic acids, namely oxalic acid (OA), malonic acid (MA) and succinic acid (SA) on the current efficiency (CE) and the cell voltage during zinc electrowinning was studied. Galvanostatic polarization was conducted in a supporting electrolyte (SE) containing 180 g dm-³ H2SO4, 60 g dm-³ Zn2+ and 8 g dm-³ Mn2+ at 38°C with magnetic stirring. The imposed current density was 50 mA cm-². The anodes were made of a Pb-Ag alloy and the cathodes were made of an aluminum alloy. The results showed that all the polyols tested in this study decreased the current efficiency and the cell voltage, but the decrease of the cell voltage was not important. Oxalic and succinic acids decreased the current efficiency to a less extent than the polyols, but did not decrease the cell voltage much. The only compound that increased the current efficiency was malonic acid, and its capacity of decreasing the cell voltage was the highest within the seven tested organic compounds.

Jan 1, 2003

By H. Kurokawa

Sumitomo Metal Mining decided to expand copper production capacity of Toyo Smelter and Refinery to cope with the recent copper demand growth in Asia, and to survive by reducing cost. The expansion plan is promoted to increase electrorefined copper production capacity from 270,000 metric tons in 2001 to 450,000 metric tons in 2007. The major changes in smelting section are introduction of the rotary steam dryer, renewal of the feeding system for flash furnace, improvement of the concentrate burner, modification of the flash furnace cooling materials, renewal of the slag cleaning furnace, modification of the flash furnace waste heat boiler, installment of a new converter furnace, enlargement of two anode furnaces. In addition, the gas cleaning system was upgraded and the second acid plant was installed. In the refinery section, the existing tank houses have been operated at high current density of 300A/m2 using the conventional starting sheet cathode technology and moreover a new tank house utilizing the permanent cathode technology was constructed. Although the copper production capacity has been increased, SO2 emission has been kept the lowest in the world through consideration of influence on the environment by expansion project.

Jan 1, 2006

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By Y. Suzuki, J. Nagao, Y. Ueda, K. Shimokawa

"A Ti- Ni intermetallic compound could be formed rapidly from Ti and Ni powder compact with SHS process. Microgravity experiments using a drop shaft are carried out, This report shows the effect of microgravity or high gravity on formability of an intermetallic compound. It is concluded that the specimen forms a porous and nearly amorphous alloy by rapid cooling under microgravity but with rapid cooling under high gravity after microgravity, the specimen forms a uniform and dense structure with better crystallinity.IntroductionTi - Ni inter1etallic co1pounds have been produced and have beco1e si1ilar to the a1orphous and porous structure as a result of the SHS (Self Propagating High-te1perature Synthesis) process under 1icrogravity. SHS process is being applied to the synthesis of cera1ics and inter1etallic co1pounds (1). The technique is characterized by a large a1ount of heat being emitted within a very short ti1e interval as regards the sistering reaction. One SHS process, acco1panying 1elting by a reaction was observed, and that was due to the quick heating of a Ni-Ti co1pact containing 50 ato1ic percent of Ti under a low pressure (2-4). In this report, we have researched the use a drop shaft which is 1ore effective during a short ti1e under 1icrogravity and high-gravity, so as to obtain high dense speci1ens with the exception of porous specimens (5). Mechanical properties of each specimen were esti1ated from these 1icro-structures with a discussion about the effect of changing gravity regarding 1elting and solidification of the Ti-Ni intermetallic comounds."

Jan 1, 1996

By Cody Burcher-Jones

The recovery of rare earth elements (REEs) through heap leach/in situ techniques from so-called ion adsorption clays (IACs) is attractive due to their inherent simplicity. However, the underlying mechanisms of these processes are poorly understood. In this study, the deportment of REEs in a typical IAC material has been investigated and was found to concentrate in the phyllo-layers of the clays, especially hallyosite, and was readily desorbed by various ion-exchange reagents indicating various potential routes to liberate them. Here we are reporting the use of seawater (0.5 M NaCl), spiked with various amounts of (NH4)2SO4, and found better extraction using a reagent mixture than NaCl on its own. Further, the leaching of REEs from a bed of clay material was investigated over time to understand the rate of transport through the stagnant material. Results indicate that REE release is likely to be controlled by diffusion through the clay material, while desorption in agitated systems is rapid. A degree of fractionation between different REEs can be observed during diffusion. Nonetheless, the successful operation of in situ leach operations for this type of material would depend primarily on how easily solution cocktails can be made to flow through the bed material.

By Kumar Ganesan

Elevated mercury levels are expected in aged gold mine tailings due to residual mercury from the amalgamation process, The fate of mercury in tailings is not well understood, Its potential health risk depends mainly on the degree to which mercury is mobile in soil. Mercury is re-moved from soil by evaporation, plant uptake, microbial activities, leaching, and other physico-chemical processes. In this research the amount of mercury lost by evaporation was evaluated. Several aged gold mine tailings in Montana were sampled for total mercury and its flux into the atmosphere. Mercury levels in tailings were higher than the general background levels in most sites. The mercury levels in some cases were as high as 10,000 ug/g. The field measurements using flux chambers indicated a wide range of mercury flux from aged gold mine tailings. The mercury flux ranged from 0-11,000 ng/m2/hr. The mercury loss by evaporation helps rid the soil of mercury but the mercury vapor then will participate in the atmospheric mercury cycle, The low solubility of elemental mercury in water helps to minimize mercury leaching from tailings, however, conversion of elemental mercury to more soluble forms by bio-geo-chemical processes can enhance its mobility posing increased health risk.

Jan 1, 2003

By J. A. Eisele

There is currently much interest in how extraction of gold and silver from ores with acidic thiourea solution compares with extraction using alkaline cyanide solution. Agitation leaching tests were performed by the Bureau of Mines on 14 precious metal ores using sodium cyanide (?NaCN) and thiourea [(NH2)2CS) as extractants. The objective was to compare the results of the two extractants. NaCN was used at a concentration of 2 g/L with and without H202 as an oxidant. (NH2)2CS was used at concentrations of 2 and 20 gjL, and the solution potential was controlled at 390 to 420 mV standard hydrogen electrode (Eh) with Fe2(S04)3. With both reagents a.t 2 g/L extractant levels, NaCN extracted more gold and silver than (NH2liCS from all of the ores. At 20 g/L (NH2)2CS compared with 2 g/L NaCN, (NH2)2CS extracted more gold than NaCN from two ores, the same amount from one ore, and more silver from one ore. NaCN extracted more gold than (NH2 )2CS from 10 ores and more silver from 4 ores.

Jan 1, 1989

By C. J. N. Buisman

THIOPAQ technology developed and marketed by PAQUES Bio Systems in Balk, Netherlands, has been successfully used at commercial scale at the Budelco zinc refinery in the Netherlands for the treatment of contaminated groundwater since 1992. In essence, THIOPAQ technology consists of two biological process steps in series: sulfate reduction to hydrogen sulfide (anaerobic) and sulfide oxidation to elemental sulfur (aerobic). The biogenic sulfide produced can be employed for the chemical precipitation of metals in solution either inside the anaerobic reactor or in a separate vessel. Since the solubilities of most metal sulfides are much lower than of their respective hydroxides, considerably lower effluent metal concentrations can be achieved with THIOPAQ systems than in neutralization processes which immobilize metals predominantly by hydrolytic precipitation. In recent years, PAQUES has made significant advances in the design and operation of aerobic and anaerobic bioreactors for metal-sulfur systems. Moreover, the company has increased its technology portfolio to allow the development of more process oriented applications of THIOPAQ technology. A new PAQUES designed plant at Budelco treating sulfatecontaining proceswaters will be started up in 1999. The sulfate reduction is accomplished in a 500 m3 reactor in which hydrogen is used as electron donor. The endproduct, ZnS, is used for Zn and H2S04 production.

Jan 1, 1999

This symposium is dedicated to the lifetime achievements of Professor H.Y. Sohn. It covers the scientific fields, processing routes and investigation techniques in which Prof. Sohn has worked during his career and is based in the equally important three topical areas: Principles, Technologies, and Industrial practice. Professor Sohn was General Chair of the very first TMS Fall Extraction and Processing Symposium in 1983 in San Francisco which led to the Annual such symposia as this International symposium. Furthermore, the theme of that symposium was sulfide smelting, which is also included in this symposium. [ ] Professor Sohn was born in a beautiful dynastic capital Kaesung, Korea on August 21, 1941. He received his B.S. degree in 1962 from Seoul National University, M.Sc. in 1966 from the University of New Brunswick, Fredericton, N.B., Canada, and his Ph.D. degree in 1970 from theUniversity of California at Berkeley all in Chemical Engineering. After working as a Research Associate at the State University of New York at Buffalo and as a Research Engineer at Du Pont?s Engineering Technology Laboratory, Dr. Sohn joined the Department of Metallurgical Engineering at the University of Utah in 1974 and currently holds the ranks of Professor of Metallurgical Engineering and Adjunct Professor of Chemical Engineering.

Jan 1, 2006