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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

By T. V. Jayaraman, Kranti Kumar, Paul Praveen J., Dibakar Das, A. R. James

"Lead free piezoelectric ceramics with high piezoelectric coefficients are in great demand for sensor and actuator applications. Synthesis and characterization study of one such lead free system, barium zirconate titanate - barium calcium titanate [xBZT-(1-x)BCT] (x = 0.5), via solgel method have been carried out. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the formation of single phase BZT-BCT nanoparticles (<50 nm). The as-synthesized powders were calcined at 1000°C and the powders were pressed into cylindrical pellets. Solid-state sintering of the green pellets at 1550°C for 2 hrs resulted in single phase perovskite structure. Hysteresis loops were obtained which indicates the ferroelectric nature ofBZT-BCT. The bulk ceramic samples with the highest sintered density (~93%) were subjected to electrical poling and the piezoelectric properties ( d33, kp, & i:,) were measured. The structure and piezoelectric properties were investigated and correlated for the given composition of the BZT-BCT system.IntroductionPiezoelectric ceramics are widely used in various sensors and actuators and most of the piezoelectric ceramics, which are presently used, are lead based, which contains at least 60% lead (Pb) by weight. The critical disadvantage of these lead based piezoelectric ceramics is their hazardous effect related to the toxicity of lead, which poses a serious environmental concern starting from their processing to the disposal stage[l]. It is well known that a material to be a good piezoelectric it requires a morphotropic phase boundary (MPB) i.e. the composition induced phase transition between any two ferroelectric phases."

Jan 1, 2013

By Irsan Chandra

It is generally recognized that the gold thiosulfate leaching system requires the presence of copper and ammonia in order for acceptable leaching kinetics to be observed. However, the presence of copper and ammonia complicate the chemistry of the system as thiosulfate is rapidly oxidized by oxygen under these conditions. In addition, the environmental impact of ammonia would need to be considered before the adoption of this system. This paper describes fundamental studies into the thiosulfate oxygen system. The two reagents for this system are thiosulfate and oxygen, and leaching is carried out at pH < 7. It will be shown using electrochemical techniques that both the reduction of oxygen and the oxidation of gold-to-gold thiosulfate are hindered. Thus, if leaching is to work under these conditions, then both half reactions need to be improved. The use of additives, such as thiourea and lead have been shown to dramatically improve the oxidation of gold and the reduction of oxygen respectively. The leaching of gold in the presence of such additives is discussed.

Jan 1, 2003

By Ross Baldock, Ross Andrews, Gu Helin, Lan Xu, Markus Reuter, Song Xingcheng

"A commercial lead smelter using Outotec Ausmelt TSL Technology has been successfully commissioned and put into operation at Yunnan Tin Company Ltd operations near Gejiu City, in Yunnan Province, China. The plant was commissioned in July 2010 after three years in the design and construction phase. The process uses a three stage batch process to produce lead bullion and zinc fume, and a slag that is low in metal values. The paper provides details of this lead smelting project, including the theoretical evaluation of the multi-stage process chemistry, engineering design, plant commissioning and the final operation. Comparison of the design targets and actual performance of the plant is emphasized. The fast ramp-up to full production of the largest Ausmelt TSL lead furnace built to date is highlighted.IntroductionIn 2002, Ausmelt and Yunnan Tin Company (YTC) successfully commissioned a smelter to modernise the Yunnan Tin smelter in Gejiu City, Yunnan Province, China. A single Ausmelt furnace was installed by YTC to process tin concentrate and revert materials, to produce YT Brand tin product. The advanced Ausmelt Technology furnace at YTC replaced seven existing reverberatory furnaces and provided a flexible, energy efficient and environmentally beneficial system to complement the world leading refinery facilities of YTC."

Jan 1, 2012

By M. Urda-Kiel

Stainless steel is increasingly used as a cathode starting sheet. It was shown earlier that even when depositing copper on copper, a substrate-influenced zone appears in the deposit structure, followed by a transition zone and finally by the electrolysis-influenced structure. On copper, the substrate-influenced zone has a thickness of twenty micrometers and on titanium, eventually more than fifty micrometers. Initial nucleation and growth have a considerable influence. In this paper, copper was deposited in a channel cell on four different 304 stainless steel substrates: mechanically polished and anodized, respectively, at 0, +400 and +800 mV/SHE in 1M H2SO4 at 20°C. Copper was deposited under electrowinning conditions after solvent extraction (SX) (40 g/l Cu++, 180 gh/l, H2SO4, 20 or 60°C). The results showed that, although Auger surface analyses of the substrates were only slightly different one from another including the oxide thickness, nucleation and initial stages of growth were very sensitive to the surface treatment of the substrate. Potential step and current step methods gave similar results : progressive nucleation followed by 3D diffusion controlled growth. The highest nucleation frequency was observed on stainless steel anodized at 0 mV/SHE, under various electrolysis conditions. The potential influence of these findings on industrial practice is discussed.

Jan 1, 1999

By Andreas Dietrich

Laser off-gas measurement of CO, O2 and temperature has been carried online in EAFs. A visualization screen shows the values of CO and Oxygen and temperature for the entire heat, and includes the status of furnace equipment. The historical data of the heats are stored such that the furnace performance can be evaluated and optimized. A short comparison between laser based and conventional systems has been carried out related to speed, influence of dust, water, pressure, protection for bag house explosions. A high water and/or dust content in the sample does not represent a problem for this type of system. The measurement method works without interruption even under worst conditions such as dirty scrap, carbon injection etc. The installation was developed in conjunction with Marienhuette, Graz. They are 100% scrap based with a tap to tap time of ca. 46 min. Keywords: Laser Measurement, Off Gas, CO, O2, Temperature

Jan 1, 2003

By R. G. Hilton

This paper deals with application of Super Detox? stabilization technology to the treatment of electric arc furnace dust (US-EPA listed hazardous waste KO61 ). The process has been used on approximately 170,000 tons of electric arc furnace dust. In addition to the nearly four years of commercial experience at Sterling, Illinois, the process is now being permitted for application at two other locations. The process was originally developed by the Bethlehem Steel Corporation and then further improved by Conversion Systems, Inc. (Bethlehem Steel&apos;s Licensee). The treatment process offers many unique bases for its selection, including: A) Low cost compared to the treatment alternatives; B) Lowest available TCLP leachate levels for any process treating K061. Many other processes leave some residue that represents a disposal requirement, although often not addressed; C) Produces minimized final waste disposed, including the fact that the total volume of dust generated and less than the volume occupied by the residue slag from HTMR; and, D) Opportunities for the beneficial utilization of part or all of the waste stream through the development of chemical and physical characteristics. Each of these aspects will be specifically discussed in the paper, including that status of the operations now under permit.

Jan 1, 1994

By M. Kawakami

In the blast furnace, the reduction of iron oxide and gasification of coke occur simultaneously. It is well accepted that the gasification reaction controls the simultaneous reaction. Therefore, it is important to develop highly reactive carbonaceous materials. It is also known that the reaction is accelerated catalytically with the addition of some materials. In the present work, the catalytic effect of iron, nickel and CaO on the gasification of graphite and coke was examined. The catalytic effect of iron, nickel and CaO on the reaction rate of graphite was noticed The effect was larger at lower temperature. At 1373 K, the effect almost vanished. The effect was larger in the order of CaO, iron and nickel. The reaction rate of de-ashed coke increased by the addition of iron and nickel. The effect of iron was larger than that of nickel. The effect was larger at higher temperature, which was contrary to the case of graphite. The reactive surface area increased also by the addition. Therefore, the catalytic effect on reaction rate might be attributable to the increase in the reactive surface area.

Jan 1, 2006

By Milan Lj. Stamatovic

The hydrometallurgical recovery of zinc from recycled blast furnace dust from a steel plant (Smederevo Metallurgical Company - Yugoslavia) was investigated. The dust contained 22% Fe, 17% Zn and 0.2% Pb. X-ray diffractometry showed that the main components were hematite and magnetite, in combination with zinc oxide and a very low content of lead oxide. Individual particles were generally spherical and ranged in size from 10 to 150 microns; 63% were less than 33 microns in diameter. An effective hydrometallurgical approach proved to be by caustic leaching followed by electrowinning. Recovery of zinc in the form of zinc powder was over 90%. This powder can be used for the cementation of impurities in the conventional hydrometallurgical process for zinc production.

Jan 1, 1993

By Chen Ya

Layered LiMn0.5Ni0.3Co0.2O2 was prepared from Mn(NO3)2, Ni(NO3)2, Co(NO3)2 and LiOH by co-precipitation and solid state reaction. XRD, C-V and galvanostatic charge-discharge methods were used to examine the structural and electrochemical characteristics. The LiMn0.5Ni0.3Co0.2O2 delivered a high discharge capacity of 167 mAh/g between 2.5 and 4.3 V with excellent cycling stability.

Jan 1, 2006

By Funsho K. Ojebuoboh

With several "green" applications in the horizon, bismuth has become an even more important minor metal in the smelting and refining of lead. Smelters with a complex sulfide feed invariably deal with bismuth. Its behavior during the smelting of lead in conventional sinter - blast furnace operation is discussed. Because it readily deports to the lead phase during the refining of lead, its separation from refined lead remained unsatisfactory in early lead production. When commercial requirements of bismuth in lead became more stringent early this century, the procedure whereby calcium and magnesium is used to debismuthise lead was developed. The present conduct of this 1936 process, the Kroll Betterton process, is discussed with emphasis on operational improvements.

Jan 1, 1995

By M. Huang

A conductivity-based sensor for on-line measurement of free acid was recently built. This sensor is suitable for high ionic strength solutions and its corrosion-free operation is based on induction currents. It has been tested against literature data and measurements made using a previous developed contact-type conductivity cell, with an average difference within 1%. The electrical conductivities of H2SO4?H2O, H2SO4?MgSO4?H2O and NaCl?Laterite-H2Osolutions at temperatures up to 250 °C were discussed. It was found that the solution conductivity depends on various factors, such as the electrolyte concentrations, the type of electrolytes, temperature and the amount of dispersions. A semi-empirical model was developed to account for all the factors discussed. This model was further tested on actual process solutions from the hydrometallurgy of nickel where sulphuric acid solutions containing a variety of metal sulphates and solids. The average difference between the estimated acid concentration from this model and the one from titration was generally less than 5%, which is excellent for industrial applications.

Jan 1, 2006

By Masahiro Yoshimura, Sergiy Korablov

"Hydi-othermal corrosion ofTiN, TlAlN and CrN PVD films (3 µm thick) deposited on SUS-304 substrate was studied in 100MPa water in 20-950°C temperature range up , to 750h. The beginning temperature of their reaction was determined as 200°c for TiN and TiAlN and 500°C for CrN films, which are quite low in comparison with that of air oxidation of those powders. Very thin oxide scales. of TinO; n-I homologous series phases were formed above 300°C. TiO2 anatare. is observed for TIN and TiAlN films at 400°C. The· feature of hydrothermal corrosion of CrN films seems to be CrNxOy phase formation.Distinguishable weight changes were observed at higher temperature than 700°C for TiN, 750°C for· TiAlN and 800°C for CrN respectively. Hydrothermal corrosion kinetics .was constructed to calculate the activation energy of hydrothermal corrosions. On the base of obtained data, hydrothermal corrosion resistance was as follows: TiN – TiAlN - CrN. Facetted oxide crystals were formed at higher temperature than 500°C for TiN, TiAlN and 850°C forCrN.IntroductionThe metallic nitride (TiN; TiAlN, CrN) PVD films have high hardness, strength and wear resistance. Therefore these films are widely used in industry for wear resistij.nce application such as cutting tools and die molds. Their performances depend on not only the mechanical properties but also corrosion resistance of coated films. High temperature oxidation of metalliq nitride and nitride films was well studied [1-5]. However there are no reliable data concerning the .corrosion resistance of coated nitride materials. In high-temperature and high-pressure water. There are a few reports on hydrothermal corrosion of nitride films [6,7]. The increase of corrosion resistance of CVD films was observed in following succession TiC - TiCNO - TiCN - TiN at 300-680°C temperature interval and I 00 MPa pressure water according to data of the first report. Kawana et al. [7] have reported about excellent corrosion resistance of CrN films under 290°C and 8, 6 MPa water during I 000 h in the circulating type experimental loop. The films thickness was about 7-10 µm in both cases. However it remains unclear the chemical state of the surface species and especially in-depth distribution, oxide scale thickness and its growth, and defects formation in the oxide film."

Jan 1, 2000

By Seong-Jong Kim

The formation behavior and corrosion characteristics of anodic oxide films on pure Mg and Mg-AI alloys were investigated focusing on the effects of anodizing potential, Al content, temperature and NaOH concentration. Pure Mg and Mg-AI alloys were anodized for 10 min at 3, 10, 40, and 80 V in NaOH solutions. Mg(OH)2 was generated by an active dissolution reaction at the surface of the specimen and the product was affected by temperature while MgO generation increased with NaOH concentration. Moreover, the current density after anodizing for 10 min at a constant potential decreased with increasing AI content in Mg-AI alloys,

Jan 1, 2003

By G. Kugler, M. Tercelj

"The use of the up-to date light alloys and their development are in the sharp ascent especially in transportation industry. In the last years the use of the magnesium alloys for the various purposes was strongly increased. The aim of present research was to study the influence of solidification rate on hot workability and on obtained mechanical properties of AM60 magnesium alloy. The study was also focused on possibility to omit prior homogenisation process which would result in cost reduction. The solidification of gravity cast alloy has been investigated with various methods of the thermal analysis: in situ simple thermal analysis and simultaneous thermal analysis. In order to reveal optimal hot working conditions the deformation behaviour was studied in the temperature range 200-450°C and strain rates between 0.001-lOs-1. Mechanical properties have been studied with tensile and impact toughness testing.IntroductionIn recent years, the increased demand for magnesium alloys has been mainly driven by the need of automotive and transportation industry to reduce the weight, as this is the most important parameter to reduce the energy consumption. Beside their very low weight in comparison to other metals, the magnesium alloys are characterized by good machinability, corrosion resistance and good mechanical properties, and can thus compete with aluminium alloys and for some applications even with steels. Due their decreased workabilty they are typically used as cast alloys, but in recent years also the research of their wrought state has become more extensive [1-7]. Decreased hot workability of magnesium alloys originates from their hexagonal close-packed structure. One of the most popular magnesium alloys with great potential for many applications is AM60 (MgA16Mn), which is predominately used for casting. But its application could be increased if the mechanical properties, could be improved. This can be done by hot working. Namely it is well known that wrought microstructure is characterized by better mechanical properties in comparison to as-cast state. On the other hand due to its low hot workability the homogenization process is required prior hot deformation, which results in increased production costs. Thus the aim of the present research was to study the influence of solidification rate on hot workability of AM60 alloy in order to improve its mechanical properties and to check the possibility of producing near-net-shape casting products omitting homogenisation process by employing small additional deformations after casting. Within the framework of this research the solidification of gravity cast AM60 alloy has been investigated with various methods of the thermal analysis."

Jan 1, 2011

By Oszkar Bíró, Peter Mittag, Bernhard Aigner, Stefan Pirkeri, Philipp Glttleri

"This paper considers CFD modeling of processing and melting of small metallic particles by means of electrical heating. The particles fall continuously onto a liquid metal bath which is heated by an electric arc. After melting of the particles liquid metal is tapped.The charging behavior of the particles in the supply unit as well as in the reactor freeboard is studied by means of Euler-Euler granular simulations. The flow situation in the metal bath due to gas injection and magnetic fields is calculated by combining Navier-Stokes and Maxwell solvers. The macroscopic melting process occurring during the continuous charging of the particles is studied by kinetic laws for melting reactions. The temperature field is evaluated by balancing heat sources due to Joule's heating and heat losses due to latent heat of melting as well as convection and radiation.As a result of these simulations the fully three-dimensional flow fields of particles and gas in the atmosphere is obtained. Furthermore the flow field as well as the magnetic field in the metal bath can be studied. As a main result the three-dimensional concentration field of the still unsolved particles in the liquid metal can be evaluated.IntroductionIn this paper a metallurgical process for melting small iron particles is investigated by means of CFD-simulations. In a first process step the preheated and already mostly reduced iron particles fall continuously into the reactor through a vertical tube mounted at the lid of the furnace. In a second step the particles are melted in the liquid metal bath. Meanwhile the melt is heated by electric arcs to provide the heat needed for melting the incoming particles.In Figure I a sketch of the geometry setup considered in this paper is provided. The particles fall from a height of approximately 12 meters onto the bath surface in the center of the furnace. The melt is heated by electric arcs that are placed symmetrically around the center axis."

Jan 1, 2001

By P. Ruz

A melt transfer ladle was 3D modeled by means of a mathematical fluid dynamics and heat transfer program. Internal temperature profiles were calculated as a time function for a normal ladle and for a pre-heated refractory lined ladle. It was shown that in a normal ladle the molten metal cools down quickly forming accretions. By using an inner lining there are practically no accretions build up within a typical time of operation. Therefore, by applying a refractory lining to a melt transfer ladle and keeping it at a moderate to high temperature it is possible to reduce cold dope circulation in the smelter.

Jan 1, 1999

By Wenbo Luo, Kang Liu, Fusheng Mao, Jilai Xue, Jun Zhu, Chunlei Yang

Extracting alumina from coal fly ash (CFA) is of great interest for both environmental protection and recycling valuable alumina content. In this study, ultrasonic aided leaching process as an effective method was investigated to enhance extracting Al2O3 from CFA via concentrated sulfuric acid sintering. The influence of ultrasonic power and processing time were tested under the conditions as the same as those without ultrasound. It is found that the alumina extraction rate can reach 90.5 % with ultrasound assistance, while the ultrasonic treatment can reduce almost 15 ~ 30 min in leaching time and 5 ~ 10 oC in leaching temperature than those without ultrasonic operation at the same Al2O3 extraction rate. In addition, the ultrasonic can reduce calcium content by 6 ~ 8 % dissolved into the leaching liquid. SEM analysis also shows that the residue particle size with ultrasound is smaller than that without ultrasonic treatment.

Jan 1, 2015

By Mingzhou Li, Lin Wu, Changren Tong, Fengli Yang, Shaohua Yang

"According to characteristics of Tm, Yb and Lu enriched oxides composition and problems in its traditional extraction separation process, the computer simulation of a optimized fuzzy extraction separation process, in which three products with high purity(>99.99%) could be obtained at same time, was carried out. Distributing Curves of every element in both organic and aqueous phases were worked out. Distribution rules of rare earth elements in every stage of the optimized extraction process were studied. The computation results of economical and technical index showed the consumption of the acid and base chemical reagents in the optimized process would be saved more than 30%.IntroductionFor the solvent extraction separation process of rare earths, countercurrent extraction process was widespread in the industrial practice. Normally, rare earth ions were extracted by the saponificated extractant and transferred into the organic phase, where the acidic extractant was saponificated by the base firstly. Then, the loaded rare earth ions were stripped from the organic phase into the aqueous phase by the acid. Therefore, the acid and the base were the main consumptions in the process, and the equilibrium acid of the stripped rare earth solution was one of the main pollution resources. Meanwhile, for the heavy rare earths, such as Tm, Yb and Lu, stripping was more difficult, and the equilibrium acidity of the stripped rare earth solution was higher, so the acid consumption increased greatly."

Jan 1, 2012

By Kang-In Rhee

Nonferrous metal recycling not only provides energy saving and environmental benefits but also is a significant factor in the supply of various types of metals used in our society. Recycling plays an important role in establishing the sustainability of materials. The total amount of recycled nonferrous metals by weight accounts for less than 5% but their value is larger than 50% compared to ferrous metal recycling which consists of about half of the total metal recycling in weight. This paper describes trends and typical achievements in nonferrous metal recycling and overviews the present and future of nonferrous metal recycling technology and business in Korea.

Jan 1, 2006