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By James A. Voigt

"The efficient separation of metal species from aqueous streams by precipitation techniques requires a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems. The effects of solution chemistry, precipitator design, and solvent choice are considered.IntroductionThe application of precipitation technologies to the separation of metals from solution is widely used. Regardless of its application, be it in such diverse areas as the preparation of metal oxide powders for use in commercial products or as a unit operation in the removal of trace metals during wastewater clean up, the fundamental processes involved are the same. These processes include: nucleation from solution, either homogeneous or heterogeneous; growth from solution with chemical reaction either in solution or at the precipitate/solution interface; growth by particle agglomeration; and particle break-up by collisional or shear forces. The effectiveness of the operation and the properties of the precipitate formed, or ""quality"" of the product, are determined by the competing kinetics of the different processes. The kinetics of the processes, in tum, are determined by system-specific solution chemistries and the conditions used to carry out the precipitation operation. For example, generally, when system conditions are such that the supersaturation driving force for precipitation is very high, growth species normally do not have the time to organize themselves with a high degree of crystallographic order and the precipitate is amorphous. In this case nucleation rates are invariably extremely high and the primary mechanism for growth is the agglomeration of nuclei. Conversely, when the supersaturation levels for the same system are reduced, the kinetics of the nucleation and growth processes also are greatly reduced, and a crystalline precipitate can be formed, since the growth species have time to order on particle surfaces."

Jan 1, 1996

By Chris Doyle

From 1997-2000. PT INCO undertook the Fourth Line Expansion Project (FLEX) to increase annual production rates from 90-100 to 150 Mlbs Ni/year (68,000 MT Ni/yr). In 2003, PT INCO nickel production underwent a major sustainable step jump that finally exceeded the targeted rate. This paper presents the changes that led to this achievement. The focus of mining changed. Improving Ni grade was important but only if electric furnace feed met target chemistry so that on-specification slag could be produced. The intensity of diamond core drilling for exploration was dramatically upgraded, mine planning strategy was totally re- vamped and an ore chemistry quality assurance team was formed. In the processing plant, measurement systems were upgraded for better control. Teamwork between sections vastly improved. The final step jump in production occurred when the fifth hydro-electric power generator was added to the furnace grid to allow the power-starved furnaces to cruise in operation at 70+ MW. Keywords: Free cash flow, Ore Chemistry, Measure, Control, Improve

Jan 1, 2004

By R. W. Smith

Living and killed organisms, particularly microorganisms, and extracellular products derived from the organisms are increasingly finding use in minerals engineering. Goals include both enhancement of mineral processing/11.ydrometallurgica,l operations and remediation of mineral industry wastes. Some of the applications, such as biologically assisted leaching of ?sulfide ores and bioxidation of refractory gold ores, are well established commercial ?processes used around the world. Others, such as the use. of organisms for the removal of heavy metal ions from dilute aqueous streams, are nearing commercial application. Many other uses of microorganisms and. their derivatives are potentially possible. These include use of microorganisms in flocculation or flotation of minerals., remediation of organics potentially discharged from mineral engineering operations, degradation of cyanide, the recovery of bitumen from heavy oil reservoirs and tar sands and the solubilisation of lignites and low rank coals. In order to fully exploit these many possible uses of organisms and their derivatives, extensive fundamental .and .applied research work exploring the fundamentals, potential and practicality of the various possible uses of microorganisms in mineral engineering should be vigorously pursued. ?

Jan 1, 1991

By Jinrong (Patrick) Mang

Three of the most challenging problems in phosphate beneficiation are discussed: flotation efficiency, resource conservation and environmental impact. Some new flotation machines offer the opportunity of reducing power and reagent consumption significantly, while increasing specific capacity many fold. Efficiency might also be improved dramatically by replacing the "double float" process with a single-collector scheme. Model based software control is a powerful tool for improving overall plant efficiency. Recovery of phosphate values from the phosphatic clays could extend phosphorus reserve life significantly. phosphate recovery from the slimes might be achieved by sizing-flotation, selective flocculation and bioleaching. Reducing the volume of phosphatic clays produced is another key stop to minimizing phoephate logs. Such a reduction may be realized by floating at finer cut size. Although an ideal' dolomite separation process is yet to be developed, a cationic flotation process may prove to 'be economically feasible. Loss of phosphate in the desliming stage is the major problem with most of the flotation schemes for removing dolomite.

Jan 1, 1995

By Lloyd R. Nelson

Selective carbothermic reduction is the preferred method of treatment of electric arc furnace (EAF) dust (listed hazardous waste, K061). The process maximizes the recovery of recyclable constituents by concurrent production of saleable zinc metal (directly condensed from the furnace off-gases), an innocuous, disposable iron oxide-rich slag, and some metallic iron. Results of a mineralogical investigation of a foaming slag produced during selective carbothermic reduction treatment of EAF dusts are presented. Wiistite and tricalcium silicate were identified by reflected light microscopy as the primary crystalline phases contained in a glassy matrix, but this technique failed to reveal any solid phases that could have significantly contributed to foam stability. It was concluded therefore, that the foam had been unstable, and had been primarily generated by copious gas evolution associated with the sudden reduction of the slag by an inadvertent addition of carbonaceous reductant. This is consistent with the susceptibility to foaming, when subjected to sudden excesses of carbon, of the slags produced by selective carbothermic reduction, because they still contain unreduced components such as iron oxide.

Jan 1, 1994

By Corby G. Anderson

In the majority of industrial operations recovering gold and silver by hydrometallurgical means, cyanide is the predominant lixiviant. However, as an economic alternative, production of massive quantifies of silver chloride was done on an industrial scale in the nitrous-sulfuric acid pressure leaching of a refractory precious metals concentrate. This proven process required no cyanide. Thus, because of the large volumes encountered during day-to-day plant operation, the need for efficient and low cost methods of silver chloride precipitation, reduction and materials handling was mandatory. As such, this paper covers the evolution of plant scale precipitation, filtration, washing, reduction and control of silver chloride processing. As well, an in-depth description of the unique leaching system is included.

Jan 1, 1998

By H. Yin, T. Emi

"Advantages of gas/flux injection technology as materialized in the main stay unit processes for steelmaking are depicted covering hot metal pretreatment through secondary refining. Current status of micro-kinetic issues involved in the injection technology are reviewed including gas-in- metal, gas-in-slag, flux-in-metal, metal-in-flux and three-phase dispersion systems with reference to macro-kinetics. Key problems are briefly addressed to further develop injection technology for steelmaking processes.1. FROM PAST TO PRESENTApplication of gas injection to steel industry started in early 1950's when inert gas bubbling via stopper rod, lance, or porous refractory plug was practiced to make the temperature of steel melt in ladle uniform The gas bubbling in ladle was then extended to slightly removing hydrogen ti'om the steel melt tapped from Electric Arc Furnace (EAF) and Basic Open Hearth Furnace (BOH) when vacuum processing facilities were not popular. Later, oxygen gas injection via calorized steel pipe into molten steel bath in BOH Furnace was also put into operation to promote the decarburization to increase the productivity of the process. This line of development has been made in parallel with more profound processes, i.e, top blowing Basic Oxygen Furnace (BOF) for primary steelmaking and side blowing Argon Oxygen Oecarburization (AOD) vessel for decarburizing stainless steels.On the other hand, injection of fluxes into steel bath was first industrialized in Germany in 1960's, Primary objective was to desulfurize steel melt in ladle by injecting CaC2 or CaCrCaO mixture via lance under neutral slag cover with good success. Difficulties in injecting fluxes without clogging and rippling at a desired flux/gas ratio, and durability of injection lance were resolved in due time to bring forth many injection facilities to flourish for versatile refining operation. Top injection of fluxes from main oxygen lance to BOF was also industrialized as LDAC to promote early slag formation. A new process then emerged which injects oxygen gas and fluxes together through concentric annular tuyere, installed at the bottom of the BOE into steel melt. This process, developed in Germany [Oxygen Bottom Maxhutte (OBM)] and brought into maturity in USA (Q-BOP) and Japan in a large scale operation, became the predecessor of the combined blowing (top and bottom blown) BOF which dominates modern steelmaking."

Jan 1, 1996

By Paul C. Turner

In 1998, approximately 57,000 tons of titanium metal was consumed in the form of mill products (1). Only about 5% of the 4 million tons of titanium minerals consumed each year is used to produce titanium metal, with the remainder primarily used to produce titanium dioxide pigment. Titanium metal production is primarily based on the direct chlorination of rutile to produce titanium tetrachloride, which is then reduced to metal using the Kroll magnesium reduction process. The use of titanium is tied to its high strength-to-weight ratio and corrosion resistance. Aerospace is the largest application for titanium, and titanium cost has prevented its use in non-aerospace applications including the automotive and heavy vehicle industries.

Jan 1, 2001

By G. S. Victorovich

Technical progress in primary smelting has changed the face of the copper industry in the years since the Second World War. Much of this change has resulted from a wide acceptance of flash smelting technology. In addition, research has been directed toward devising converting processes to replace conventional Peirce-Smith converting technology. One major thrust has involved a revival of the old " ", idea of oxygen flash converting of comminuted mattes. This paper reviews the 60-year history of flash converting. Particular attention is paid to Inco's investigations into the processing of white metal containing significant amounts of nickel and, in some cases, iron. Thermodynamic analysis and laboratory experimental results are presented which throw light on the behaviour of nickel and other salient features of flash converting. The possible role of oxygen flash converting in the copper pyrometallurgy of the future is briefly discussed vis-a-vis direct production of copper.

Jan 1, 1993

By Joseph Gambogi

In 1998, approximately 57,000 tons of titanium metal was consumed in the form of mill products (1). Only about 5% of the 4 million tons of titanium minerals consumed each year is used to produce titanium metal, with the remainder primarily used to produce titanium dioxide pigment. Titanium metal production is primarily based on the direct chlorination of futile to produce titanium tetrachloride, which is then reduced to metal using the Kroll magnesium reduction process. The use of titanium is tied to its high strength-to-weight ratio and corrosion resistance. Aerospace is the largest application for titanium. In this paper, we discuss all aspects of the titanium industry from ore deposits through extraction to present and future applications. The methods of both primary (mining of ore, extraction, and purification) and secondary (forming and machining) operations will be analyzed. The chemical and physical properties of titanium metal will be briefly examined. Present and future applications for titanium will be discussed. Finally, the economics of titanium metal production also are analyzed as well as the advantages and disadvantages of various alternative extraction methods.

Nov 26, 1999

By David J. Roha

"The harsh environment of the Carbothermic Aluminum process makes necessary numerical modeling as a means of process visualization and understanding. A brief survey of the various numerical models, with emphasis on CFD, applied in the development of the process is presented.IntroductionThe environment of the Alcoa Carbothermic reactor is necessarily a harsh one, with temperatures approaching 2100 °C and plenty of reactive dust and vapors. As such, it is difficult to directly observe what is actually taking place. Thermocouples can last for a few minutes but are eventually destroyed. The openings to optical pyrometers become occluded with dust and condensation. Graphite sheathing embrittles, reacts away or becomes clogged with condensate. Dip-samples on steel rods are routinely taken, but their interpretation is often unclear.Those measurements that can be reliably taken are invaluable, but often do not provide a complete picture. Therefore from the very inception of the project both physical and computer based models have played an important role. Modeling provides an intuitive understanding of the processes that might be taking place and in very many cases approach quantitative prediction. I will briefly touch upon computer-based modeling performed at Alcoa over 12 years of the Carbothermic project, with special emphasis on CFD. The explanation of physical models is perhaps best left for those with the greatest familiarity with them"

Jan 1, 2012

By Zenon R. Llanos

"The disposal of spent hydroprocessing (HDP) catalysts in the petroleum refining industry has been a concern in the past due to their classification as listed hazardous wastes. However, because these catalysts have higher metal concentrations than regular ores, and the recent surge in prices for molybdenum, vanadium, nickel and cobalt what used to be considered as a liability for generators is now viewed as a valuable renewable source of strategic metals. At the same time the generation of spent catalysts has steadily risen due to new environmental regulations for low sulfur fuels and an increased appetite of gasoline consumers. This paper will examine spent catalyst market and the role played by Gulf Chemical & Metallurgical Corporation in the reclamation of metals over the last sixty years. Introduction Hydroprocessing (HDP) catalysts are used in petroleum refineries for two main applications: desulfurization and cracking. The catalyst support is alumina or mixtures of alumina and silica. Active metals include molybdenum, nickel, cobalt and tungsten. The selection of catalysts depends on the application and sometimes the cost. The life cycle of HDP catalysts is represented in Figure 1. The catalyst cycle in a reactor varies from continuous to one-two years. Catalysts used in various refining processes are deactivated by coke, sulfur, vanadium and other impurities in the refinery feedstocks and become spent. Refineries can optionally send the spent catalysts for regeneration, metals reclamation or landfilling. Catalysts used for refining heavy crudes often can not be regenerated. Catalysts used with light oils can be reused twice or three times after regeneration. When the option for regeneration is not viable, spent catalysts are send metal reclamation facilities or landfills."

Jan 1, 2008

By Zheng Wei, Jian Cheni, Zhenliang Weng, Wei Liang, Hongbo Zhu, Jinhui Peng, Linqing Dai, Qianxu Ye

"By testing the dielectric constant and the dielectric loss factor of concentrated Dahongshan, mill scale, anthracite and light-burned dolomite in different frequency and temperature, and by studying the temperature-rising characteristics of the materials in the microwave field of 2.45GHz in frequency, the research in the paper shows that to reach at 1250°C under the same condition -2KW the microwave power and 30g the mass --the time concentrated Dahongshan takes is 330s, whereas the millscale is 855s and the anthracite is 820s. About the last one, the higher the temperature is, the stronger the absorptivity is. After the temperature has rose to 400°C, the anthracite's absorptivity increases dramatically. The result of the research would serve as the foundation of the further study on making direct reduced iron by microwave heating.1. IntroductionUnder the microwave fields, materials' dissipation of dielectric bodies would generate thermal effect. Therefore, the dielectric constant and the dielectric loss factor are closely related to materials' ability of absorbing microwave energy-the larger the dielectric constant and the dielectric loss factor are, the stronger the material's ability of absorbing microwave energy is, and the better the thermal effect would be[1-2]. In order to research how to make reduced iron from iron ore fines by microwave heating deeply and systematically, the test of raw materials' dielectric constants and dielectric loss factors are of the essence. What's more, because a mineral' conductivity is influenced by its components and crystal structure[3], it is necessary to study different materials' different temperature-rising characteristics; hence such studies would provide theoretical foundation of further research."

Jan 1, 2012

By C. Twigge-Molecey

All projects that are implemented, have been given corporate go-ahead on the basis of a set of clearly defined targets. These are typically a production goal at a capital cost, operating cost and production schedule, that will yield an acceptable return on investment by the companies internal criteria. The challenge for the implementation team is two-fold, firstly to properly define the project criteria prior to board approval and secondly to deliver an operating facility that meets these objectives, in particular the ROI. The paper addresses the issues a project team and the company management must address for a successful project. Key questions that will be explored are: ? What is the status of key technologies? Are they well proven in commercial practice, completely novel or in between? ? Is the project schedule driven by market constraints or cash flow constraints? ? Are the risks of fast tracking worth the potential rewards? ? For a retrofit project, are all the technical and production interfaces and issues known at the time of approval to proceed? ? How much should be invested in technological development and engineering and at which phase? ? For an owner-operator, how much responsibility is it wise or appropriate to push down to vendors? The answers to these questions for a specific project will define how you go about a project, the resources required, the contracting strategies, the phasing and the appropriate level of investment in the definition and procurement phases, prior to starting major capital commitments and construction.

Jan 1, 1999

By Emanuel Negrao Macedo, Edinaldo Cunha, Mauro Oliveira, Jose Antonio da Silva Souza

"This paper presents the study of the increasing addition influence of the bauxite waste in some properties of polymeric matrices composites reinforced with natural fiber: Curaua (Ananas Erectifolius smith). There were evaluated properties as density, tensile and flexural resistances. The high pH provided by the waste is used as hydrolysis agent, providing the pectin cement dissolution of the fiber bundles, and therefore, improving the mechanical adhesion in the fibermatrix interface and the increase of the fiber bundles aspect ratio. Furthermore, the content of silico-aluminous material in the waste provides increase in the composite abrasivity, which is destined to civil and naval construction. The fact of being a low-cost and highly available waste turns the red mud in a high potential material as polymeric composite filler.IntroductionRed mud is an insoluble residue, originated from the bauxite refining through the Bayer Process [1]. It is an Iron Oxide rich material [2] (substance responsible for the red brick color), it has a complex chemical composition [3], and its composition is highly dependent of the type of bauxite used in the process [4]. It has high alkalinity (pH= 10 - 12.5) and a very small solids size distribution (95% diameter< 44µm) [1], what turns the red mud a serious environmental pollutant.The utilization of fillers on composite materials is done after many necessities; however, one of the major necessities is the cost reduction [5]. Furthermore, mechanical and thermal properties of polymers usually are improved by the addition of inorganic fillers [6], being an example of this improvement the reduction of the flammability of polymer matrixes due to the addition of functional clays [7]. In this way, the red mud becomes potential filler for composites, since cheap and easily available fillers (like red mud) are a good option to reduce costs [8]."

Jan 1, 2013

By N. R. Green, N. J. Humphreys, D. McBride, T. N. Croft, M. Cross, D. M. Shevchenko

"Centrifugal casting offers a route to high quality products in difficult to cast high temperature low superheat alloys and thin section molds. Under centrifugal forces metal is forced into thin sections and can fill thicknesses of less than a millimeter. However, due to the high liquid metal velocities there is a high risk of surface turbulent flow and air entrainment within the liquid metal. The combination of interacting flow-thermal-solidification phenomena and associated defects is a challenging modeling task which the authors have previously described and validated. Capturing the metal-air interface, on what are inevitably complex three dimensional geometries, results in highly computationally expensive simulations and simulating a single cast can take weeks on a single processor. This contribution reports on modeling a complex centrifugal cast, gas entrainment, bubble transport and solidification, employing meshes of up to a million elements and investigates the scalability of the model on high performance clusters.Introduction The ultimate goal of any casting procedure is to produce a defect-free product. For difficult to cast alloys, such as Titanium, centrifugal casting has a number of advantage over conventional gravity methods [1]. In the casting of thin sections, such as turbine blades, the metal is forced into the thin sections under centrifugal forces. The centrifugal force can overcome the backpressure due to surface tension and the metal can fill mould sections with thicknesses substantially less than a millimeter. However, the materials used in these castings [2] tend to be highly reactive and requires low superheat. High liquid metal velocity gives rise to a high risk of free surface turbulent flow and of associated entrainment through free surface turbulence [3] and trapping of gas present in the flow [1]."

Jan 1, 2012

By Dan Wang, Qian Li, Yong-bin Yang, Tao Jiang

"Thiosulfate is one of the most promising non-cyanide lixiviants for gold leaching. However, the undesirable reaction between thiosulfate and copper (II) gives rise to increased reagent consumption, which results in high cost and huge limit to its development. This paper presents study on the effect of ammonia, copper (II) and Cu(NH3)l+ ions on the oxidative decomposition of thioulfate. It shows that the presence of copper (II) and Cu(NH3)l+ can significantly increase the thiosulfate oxidation, while ammonia is relatively unaffected. The oxidation of thiosulfate by copper(II) in the absence of ammonia is fast at first and then decreases as time increased within a certain time, which can postulate that an intermediate product is responsible for the decreased consumption. The effect of ammonia is depended on the interaction with copper (II), which was found to significantly affect the consumption of thiosulfate.IntroductionFor over one century cyanidation is widely used in industrial production of gold, due to its simplity of process and low cost of production. However, cyanide is a highly toxic chemical reagent used dangerously and brings serious environmental pollution. What's more, cyanidation has slow speed of leaching gold and poorly leaching effective for refractory ores. With the exhausting of free-milling gold ores and promoted environmental protection requests, the disadvantage of cyanidation becomes a growing problem. In recent years, more and more research activities have been focused on alternative processes using non-cyanide lixiviants. Among the non-cyanide lixiviants, thiosulfate is considered as the most promising one[l-5].Compared to cyanide, thiosulfate is an inexpensive, nontoxic and less-pollution reagent, which can form complexes with many metal ions. Thiosulfate leaching of gold has an acceptable leaching rate and is insensitivity to impurities. Moreover it presents advantage on the treatment of refractory gold ores such as carbonaceous gold ores, copper gold ores, complex arsenic and sulfur gold ores, and so on[6]."

Jan 1, 2013

By G Hope, C Young, R. N. Gow

"The presence of enargite (Cu3AsS4) is problematic in gold processing as it is refractory, increasing cyanide and oxygen consumption, and enviromnentally hazardous. Selective leaching and treatment of the arsenic would prove advantageous to conventional gold leaching methods. The reactivity of enargite samples from Montana, US and Quiruvilca, Peru were studied under alkaline conditions, pH range of 8-13, using a cyclic voltammetry corrosion cell setup. Raman spectra of the surface were taken during and after cycling to compare surface species against theoretical predominance diagrams. Under slightly oxidizing conditions, covellite (CuS) peaks were found on the surface in a short matter of time, above - 200m V vs SHE for pH 9-13, suggesting arsenic leaching, but for longer conditioning times, elemental sulfur peaks were also found, which created a passivating surface layer. By operating above pH 12, under reducing conditions, ~-500mV vs SHE, arsenic can be leached as a thioarsenate (AsS4-xOx3-), without sulfur formation.IntroductionEnviromnental limitations on pyrometallurgical processing of arsenic has pushed the desire to process enargite-, Cu3AsS4, bearing concentrates towards a hydrometallurgical solution. Attempts to process can be broken down into two categories - the co-dissolution of arsenic and copper under acidic conditions or the selective leaching of arsenic under basic conditions. The selective leaching of arsenic would preferably leave behind a chalcocite, Cu2S, or covellite, CuS, phase that would be more amenable to conventional processing methods of the copper and gold industries. These methods employ bi- or poly-sulfides to leach arsenic as Assl· [1-4], hypochlorite leaching [5-7], ammoniacal leaching [8] or fine grinding to mechanically activate the enargite surface and increase normally slow reaction kinetics[9]. This study looked into the surface formations of an enargite electrode under alkaline conditions, in a pH range from 8-13, as it cycled from -1000 mV to 1000 mV vs SHE. The understanding of the formations and under what conditions they form will be helpful in further development of any of the aforementioned processes."

Jan 1, 2012

By Xin Wang, Hongmin Zhu, Shuqiang Jiao

"The behavior of electrochemically depositing silicon in a molten high-melting-point fluoride electrolyte was studied at 1300 °C. The cathodic product was characterized by XRD, SEM and EDS. Though the analysis of structure and composition of deposition, it could certify that silicon deposited on the Mo rod and alloyed with molybdenum. A series of tests had been performed on the cathodic behavior of Si4+ ions in BaF 2-CaF 2-Na2S iF 6 molten salt. The influence of electrochemical parameters on the cathodic deposition of silicon was also investigated. The electrochemical behavior of Si4+ ions in applied fluoride melts was observed to proceed according to one-step reaction.IntroductionGreenhouse warming has been a serious global issue. lt is increasingly urgent for clean and renewable energy. Effective utilization of clean and inexhaustible solar energy has become very important. Solar cell (especially poly-Si solar cell) production has significantly increased this decade, as there is a growing demand for clean energy. Since the early 1980s, the annual growth of the photovoltaic (PY) solar cell industry is more than 30%. More than 90% of the annual solar cell production is based on crystalline silicon wafers. This rapid growth leads to a shortage of silicon of the adequate quality and price for the continued growth of this industry [I , 2J. The most conunonly used technology to produce silicon is the so-called Siemens process. This technology, involves the forming of gaseous Si compounds such as trichlorosilane (SiHCli) or silane (SiH4) with subsequent thermal decomposition of these back to Si. This technology is associated with transformations from solid to gas, and then back to solid phase, which lead to high irreversible thermodynamic losses and subsequent high energy consumption, the energy cost being around 200kWh/kg Si [3l_ The purity of the material from this process is very high (9 to 11 N). In general, what is needed for solar cell purposes are reported to require 4 to 6 N quality. To promote continued growth of the silicon-based PY industry, there is need for a low-energy silicon production process which can produce large amounts of silicon with an acceptable quality and a lower price particularly."

Jan 1, 2012

By Michael S. Moats, Alexander Derrick

"The Winand Diagram was developed and has been used for decades to illustrate the interaction between polarization, mass transport and inhibition on the resulting structure of a metal electrodeposit. Recently, Adcock et al. criticized the Winand Diagram and developed their own structural diagram based on nucleation and plating overpotentials. Their work was based on zinc electrodeposition using a galvanostatic staircase method. This work explores the nucleation and plating overpotentials for copper electrodeposition using conditions typical for primary electrowinning and the galvanostatic staircase experimental technique. Additionally, the effects of organic additives and plating substrate on these overpotentials are reported.IntroductionThe control of electrodeposited structures is critically important to modem electrometallurgy operations to insure proper quality and efficient energy use. Electrodeposition of base metals for primary recovery (e.g. electrowinning or electrorefining), while similar to plating for decorative or device manufacturing, differs in the need to produce deposits that cover large areas and grow to significant thickness. Thus, controlling nucleation and particularly growth of electrodeposits is critically important for base metal electrometallurgical operations.The control of nucleation and growth on an industrial scale is most influenced by five parameters - current density, temperature, metal concentration, electrolyte agitation and additives. The effects of these parameters on electrodeposition are interrelated. To describe their effects on the type ofelectrodeposits generated and provide practitioners with a useful tool, Winand developed what is known as the Winand Diagram [1-2]. An adapted version of the Winand Diagram is shown in Figure 1.Winand characterized electrodeposits using Fischer's classification [3] and plotted the various deposit types versus inhibition on a vertical axis and the ratio of current density to bulk metal concentration on the horizontal axis. Inhibition intensity is a complex parameter and is still not well understood even though Fischer introduced the term in 1960 [4]. Often, inhibition intensity is simplified to equal the concentration of organic additive at the deposit surface and is related to the inverse of the exchange current density of the metal being deposited. The ratio of current density to bulk metal concentration is used to represent the ratio of crystallization overvoltage to mass transport of the depositing ion. As such i/iL could also be along the horizontal axis, where iL is the limiting current density of the electrodeposition reaction."

Jan 1, 2012