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By Michael S. Moats, Scott C. Campin, J. Brent Hiskey

"Electrochemical techniques are a valuable means of analyzing the passivation of commercial copper anodes. Electrochemical impedance spectroscopy (EIS) provides information concerning transport and reaction phenomena occurring at an electrode surface. Commercial. copper anodes of varying compositions have been examined using EIS. Experiments were conducted in a flat cell with an electrolyte of 40 gil Cu2 + and 160 gil H2S04 maintained at 65 DC. Impedance spectra were obtained at the potentials characteristic of the open circuit voltage and passive region for each anode. The spectra of the passivating films exhibited a flattened resistive/capacitive loop at middle to high frequencies and an inductive loop at low frequencies. An equivalent· circuit utilizing an inductor-resistor series in parallel with the double layer capacitance and charge transfer resistance was adequate in modeling the impedance data. The influence of anodes impurities on the components of the equivalent circuit is discussed and correlated with a hi-layer passivation model.IntroductionPassivation of copper anodes during industrial electrorefining has received considerable attention in the past few decades. Great strides have been made in understanding the roles of anode impurities [1-25], electrolysis parameters [20,26], and electrolyte chemistries [20,26]. Even so, passivation still occurs even in the most modem of refineries. The exact cause of passivation is not fully understood. It is known that the anode surface becomes covered by a passivating film. This film has been proposed to be CuS04'&5H20, Cu20, or mixed oxides. The localized concentrations of Ft, Cu+, and Cu2+ ions determines which phase is more favorable. The presence of these ions is controlled by the reaction kinetics and diffusion of species through the slimes layer.Reaction kinetics between Cu, Cu +, and Cu2+ are based on the dissolution mechanism of copper. There exists four different models to describe the dissolution of pure copper. The classical model of Mattsson and Bockris [27] involves two single electron transfers with the cuprous-cupric reaction being the rate detennining step. More recently, Wong, Collier, and MacFarlane [28] used ac impedance to elucidate a more complex mechanism involving the affect of pH and anions. Their findings indicate that the formation of cuprous ions in solution, Cu(I)so~ is favored over Cu(1I) ions adsorbed to the electrode surface in the presence of sulfate and as pH increases from pH 1 to pH 5."

Jan 1, 1997

By WU Jian-hui

Keywords: metallic material, precursor synthesis, precipitation, nickel, fibrillar powder The composition and morphology of the precursor of fibrillar nanocrystalline nickel powder prepared by oxalate precipitation are characterized by XRD,IR and SEM analysis, and the effects of temperature, nickel concentration, pH, surfactant and drying process on the morphology and the dispersion of the precursor are investigated. By the experiment results, the fibrillar precursor is a complicated nickel salt. The precursor prepared in the of 60~70°C,0.6~0.8 mol/L nickel ion, pH=8.4~8.6 and with addition of PVP surfactant is well dispersive and in fiber form. The powder dried by azeotropic distillation is dispersive.

Jan 1, 2005

By Alexander Burns

Electrolytic salt splitting is a technology where acid and/or base is regenerated from a neutral salt using membrane electrolysis. Recent advances in the understanding of brine treatment, membrane stability, and cell design have made electrolytic salt splitting feasible on certain hydrometallurgical solutions. Meanwhile, environmental regulations have made the bulk disposal of salt solutions more difficult. In this paper, sodium sulfate salt splitting is examined from a cost perspective, compared to purchasing the reagents directly. Relative costs are estimated for several regions based on published electricity and reagent prices. The results show that salt splitting is economically favourable in some regions, and can be made more favourable by applying modifications to the traditional three-compartment desig

By G. N. Shannon

Keywords: inclusions, slag, modeling, interfacial energy, capillary force, particle flotation, particle separation A previously introduced model of inclusions separating across a steel-slag interface, developed by Nakajima/Okamura and Bouris/Bergeles, is expanded to include different inclusions shapes (octahedral and plate-like, besides spherical) as well as comparison between model ladle-, tundish-, and mold-slags. Investigation of the relation of these shapes with the interfacial capillary force ? which arises due to the dynamic interfacial energy during separation ? has shown that the force has a significant effect on whether the inclusion separates rapidly or settles at the interface. For the slags considered, the most significant physical property is found to be viscosity, which resulted in fast separation times for inclusions in the mold and ladle slags, relative to the more viscous tundish slag. Particle dissolution (using experimental data) is included in separation modeling.

Jan 1, 2005

By Emil B. Milosavljevic

Problems associated with distillation and other classical methods for analyzing operationally defined cyanide (CATC, WAD, Total and Free Cyanide) will be discussed. These methods often achieve incomplete, species dependent cyanide recoveries and suffer from serious interferences. Depending on the relative concentrations of interferents and other matrix constituents, underestimation (ultimately Type II errors probability of not detecting a constituent when it is actually present) or overestimation (ultimately Type I errors -probability of deciding a constituent is present when it is actually absent) of the cyanide levels present in a ,given sample may occur, causing in the first case false security and in the second case, excessive cyanide treatment costs. Mahy, if not all, enumerated problems can be solved by using novel flow injection (FI) gas-diffusion amperometric methods. A modification of the recently approved FI ligand exchange (FIILE) method for determination of available cyanide (USEPA Method OIA-'l677) that obviates sulfide interference will be discussed. Eight laboratory round-robin data obtained for the FI UV -digestion (FIIUV) method that determines total cyanide (Proposed Method OIA-1678) will also be presented. In addition, some methods for cyanide speciation will be presented. Finally, research needed for developing reliable methods for determination of operationally defined cyanide in solid samples will be summarized.

Jan 1, 1998

By Jin Qiu

Experiments were performed to determine the extent of minor element elimination that occurred when mixtures of copper smelter dust and copper concentrate, were calcined under vacuum. Almost complete removal of the As, Sb, Bi and Pb occurred due to the conversion of the minor element compounds of these elements into their highly volatile sulphides by reaction with sulphur from the concentrate. Heat and mass balance calculations of the slag-blow in a copper converter found that ~30 tonnes of the vacuum calcine could be used to produce 100 tonnes of copper as white metal. The use of dirty concentrate as the sulphidizing agent in the vacuum calcination means that the minor element treatment capacity of the smelter complex could be increased by 60 %. Also the productivity of the converters may be increased by up to 8 % due to the supply of copper values and oxygen in the calcined mixture.

Jan 1, 2005

By Y. Zhoa

The surface morphology of materials is of fundamental importance to many surface related applications, such as wetting, friction, reflection, drag, and adhesion. Various approaches for micro/nano patterning atop polymer surfaces have been proposed in recent years. However, a cost effective technique is still highly in demand. In this paper, we demonstrate a novel but rather simple and generic approach for surface micro/nano patterning using shape memory polymers (SMPs). Different types of novel patterns are realized and their 3-D surface features are quantitatively analyzed by a PLµ Confocal imaging profiler.

Jan 1, 2010

By Jeffrey D. Winterton

Keywords: Copper, ion exchange, sulfonic acid, bis-picolylamine, ion exchange modeling, ion exchange kinetics As part of an investigation into the feasibility of using ion exchange resins to recover copper from aqueous waste streams generated during the manufacturing of semiconductor devices, the uptake of copper onto two ion exchange resins was investigated. The resins studied were DOWEX G-26, a standard gel type sulfonic acid resin, and DOWEX M4195, a macroporous chelating resin with a bis-picolylamine functional group. The equilibrium and kinetic behavior of the uptake of copper were investigated over a range of copper concentrations with constant sulfate concentration and different levels of acidity. The homogeneous structure of the G-26 resin yields equilibrium relationships that fit the Langmuir equation, and equilibration times of less than 30 minutes. The uptake behavior of M4195 is complicated by the need to absorb co-ions to maintain electroneutrality, resulting in uptake profiles that change character with increasing copper concentrations, and extended equilibration times.

Jan 1, 2005

By George P. Demopoulos

In this paper the production and stability of crystalline scorodite (FeAsO4·2H2O) is discussed both on the basis of previously published work as well as recent work performed in our laboratory. The production of scorodite, especially from arsenic-rich and iron-deficient sulphate solutions offers a number of operational advantages such as high arsenic content, stoichiometriciron demand, and excellent dewatering characteristics. In addition to hydrothermal production of scorodite the work done over the last 10 years in our laboratory has determined that it is feasible to produce scorodite by step-wise lime neutralization at 90°C. The atmospheric scorodite possesses the same structural and solubility characteristics with the hydrothermally produced scorodite. Long term equilibration tests (up to 66 weeks) in the pH range 5 to 9 and temperatures from 22 °C to 75 °C revealed scorodite to undergo slow incongruent dissolutionyielding a highly metastable nano-sized 2-line ferrihydrite phase. The equilibrium arsenic concentration with this phase was 0.35, 0.96 and 5.87 mg/L at pH 5, 6, and 7 respectively at 22°C. In the presence of gypsum slightly lower concentrations were measured, this being more pronounced at pH>7. It was tentatively deduced that a Fe-Ca-AsO4 association (in the form of a phase resembling the mineral yukonite) contributes to the lowering of As concentration. Finally thermodynamic calculations determined that scorodite is stable in the presence of ferrihydriteunder oxic conditions up to pH 6.75 at 22 °C or higher pH at lower temperature and gypsum-saturated solutions. Keywords: Scorodite, Crystallization, Arsenic, Solubility, Stability, Precipitation, Disposal, Extraction, Processing, Metals, and Environment.

Jan 1, 2005

By Zhan Jing

Keywords: thermodynamic, Ni-Co alloy powders, composition, fibrous The mathematics model of Ni(II)-Co(II)-C2O42?-NH3?H2O-H2O of thermodynamic equilibrium system has been developed theoretically according to the law of conservation of mass and the law of simultaneous equilibrium, and the logarithm concentration-pH (log[Me2+]T-pH) diagrams of this system have been made. The effect of ligand and pH value was studied. Two issues in coprecipitation route to synthesize fibrous nickel-cobalt alloy precursor powder, com-position and morphology which are a first priority, are addressed based on thermodynamic analysis and experiments. The results show that suitable pH value range of coprecipitation of nickel ions and cobalt ions in theory can be obtained to maintain fibrous, excellent compositonal homogeneity and stoichiometry in coprecipitation products. Experimental demonstration is also carried out.

Jan 1, 2005

A three?stages countercurrent fluidized bed prototipe reactor to neutralize the SO2from smelter gases has been developed. For gases with 8 vol-%SO2, at 800°C and for 4 h mean reaction time of the limestone, the capture of SO2 is 99%, with off gases with 0.07 vol-%. For 2 vol-%SO2, the total capture of SO2 can be obtained at 750°C and 4 h reaction time. The calcine obtained contain a blend of unreacted limestone and calcium sulphatewith minor amounts of residual lime.

Jan 1, 2006

By Sergio N. Monteiro

Jute fiber reinforced polymer composites are among the most investigated and applied natural composites. In this past decade the mechanical properties of these composites has been assessed for various types of test conditions. However, the reported results correspond mainly to short-cut jute fiber composites, which do not present the highest mechanical strength as compared to continuous fibers of the same kind. In order to complement these results, the present work evaluated the mechanical behavior, by means of flexural tests, of polyester matrix composites reinforced with continuous jute fibers. Bend tests were conducted in standard specimens with up to 40% of jute. Fracture analysis by SEM displayed the rupture mechanisms. The results showed an improvement in some flexural properties with incorporation of jute fiber. However, a low fiber/matrix interfacial stress was responsible for limitation in the values attained by some properties.

Jan 1, 2010

By Elisa Alonso

Recycling is generally a more sustainable alternative to landfilling. Its financial costs however, do not always justify its practice, especially in the short term. As a result, even for precious metals such as platinum, significant amounts can end up unrecovered. In considering risks of materials scarcity for firms that require platinum and platinum products, this paper examines how recycling provides additional benefits as a risk-mitigating strategy against scarcity. The experimental platform for this examination is a System Dynamics simulation model that strives to capture the dynamics of platinum market supply, demand and price. The detailed structures of supply and demand are key features of the model. Results show that since the secondary supply of platinum depends on a supply chain separate from primary extraction, recycling can diversify the risks of primary supply instabilities and reduce the impact of price fluctuations upon firms.

Jan 1, 2009

By Jilai Xue

Fe-Ni alloys can be used as raw material in making stainless steel. Laterite nickel ore is one of mineral resources for producing nickel alloys. In this work, the laterite ore after dehydration at 800 °C and the anthracite as reducing agent were mixed for pre-reduction at 900 °C, and then reduced to form Fe-Ni alloys at 1550-1620 °C through carbon-thermal reduction process. A high Ni-content alloy component in the metallurgical mixture can be formed through pre-reduction. Better separation of the resulting metals from the slag is found with lower Ni-content alloys produced or higher temperatures during reduction. An effective processing of Fe-Ni alloys needs further understanding of the process fundamentals and optimizing of the process parameters.

Jan 1, 2010

By Pietro Navarra

A great deal of effort has been expended on how to optimize conventional water cooling circuits in furnace cooling elements, and the results have been largely satisfactory. However, there is a general agreement that the proximity of high-pressure water passages to the flow of molten furnace products is a safety concern. Nonetheless there exists little alternative to the formula: increasing furnace integrity implies the incorporation of more extensive forced-convection water cooling systems. Recent developments in evaporative cooling technology have resulted in the development of a high-capacity heat pipe capable of operating under the thermally intense environments of a metallurgical furnace. The system functions using several kg of a working fluid (water) in total, has no moving parts, and allows for a significant reduction in cooling water requirements. Full-scale pilot tests of a copper tap hole and slag launder were done in 2003 and2005, with detailed results given in this paper.

Jan 1, 2006

By Xi Zhang

A technique for fabricating free-standing, high-aspect-ratio porous and pillar-type Ni structures has been developed using wet Si processing. A wafer of (100) Si was initially etched in HF solution to form deep pores with micron-sized diameter. The aspect ratio can exceed 200. By introducing the as-etched Si into a defined aqueous Ni2+ solution, Ni deposits grew rapidly onto the sidewalls and replaced the Si. Long-time immersion allows the Si sidewalls to be completely converted and thus form a metallic Ni structure with high-aspect-ratio pores. It is known that close-packed submicron Si pillars can be formed by oxidizing and subsequent etching of the macropore sidewalls. Treated in the same Ni solution, high-aspect-ratio Ni pillars were correspondingly emerged by replicating the original pillar-type Si structure.

Jan 1, 2006

By P. F. Kerr

This is not a conventional professional paper. It deals mostly with personal experiences. These concern a background in applied mineralogy. Your committee asked me to do this. I accepted with a California enthusiasm which has since diminished with the approach of a Chicago winter. Nevertheless, I wish to thank your committee and also to apologize in advance for omissions and inadequate statements, as such a paper must possess. My introduction to applied mineralogy took place in 1922 at Stanford University. Physicists had recently demonstrated that crystalline powders would reflect x-rays in a systematic manner. Professor A.F. Rogers sug¬gested that significant x-ray reflections might be obtained from powdered opaque minerals. With the aid of Professor D.L. Webster in the Physics Department, I constructed an x-ray diffraction outfit. It was a crude affair, but it worked. Starting with 1924, we secured recognizable patterns of a goodly number of ore minerals (1,2,3). Today x-ray diffraction outfits are common, and a card system of mineral identification is constantly used.

Jan 1, 1981

In this study, the method of chemical co-precipitation?reduction?diffusion was developed for the preparation of magnetic SmCo5 alloy. In the chemical co-precipitation process, the effects of solution pH, the reactant concentration, the dispersant on the process were investigated. The optimum conditions of the process were determined, and the SmCo5 alloy oxide precursor particles with fine crystalline structure, narrow size distribution was obtained. Then, by reduction-diffusion treatment of the precursor particles, the SmCo5 alloy with high quality was produced. It is anticipated that the co-precipitation-reduction-diffusion is a novel method available for SmCo5 alloy production.

Jan 1, 2006

By Vincent Menard

The purpose of the present work is to demonstrate the removal of manganese from a neutral leach zinc-rich solution ([Zn] =150 g/L) at 80°C by oxidative precipitation using a gas mixture of sulphur dioxide (SO2) and oxygen (O2). In order to determine the optimum conditions for manganese removal, several bench-scale semi-batch experiments were performed, where the effects of ORP and gas mixing were investigated. These tests showed that SO2/O2 is a fast and effective oxidant for removing manganese down to ppm level as long as the appropriate ORP is attained/maintained and gas transfer kinetics are optimized.

Jan 1, 2006

By Art Cooper

Granulation systems are common in the metals industry. The process of granulating slags, mattes and metals is more than a century old, and a number of different systems have been developed to accomplish this task. These systems have followed an evolutionary path, and may be characterized by common elements in terms of molten material handling, granulation methods and post-granulation processing. This paper will summarize the more common systems used in the metals industry, with particular reference to non-ferrous applications.

Jan 1, 2006