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By Andriy Burbelko, Daniel Gurgul, Wojciech Kapturkiewicz, Marcin Gómy

"The mathematical model of the globular eutectic solidification in 2D was designed. The proposed model is based on the Cellular Automaton Finite Differences (CA-FD) calculation method. The model has been used for studies of the primary austenite and of globular eutectic grains growth during the ductile iron solidification in the thin wall casting. The model mentioned above takes into account, among other things, non-uniform temperature distribution in the casting wall cross-section, kinetics of the austenite and graphite grains nucleation, solute diffusion and non-equilibrium nature of the interphase boundary migration.Some aspects of stochastic nature of the solidification processes are taken into account. The results of the CA solidification modeling have been shown, that differences between cooling curves obtained in the same conditions of the casting solidification may be a result of the stochastic nature of the grain nucleation.The results of modeling were compared with the experimental microstructure. The model is well worked for thin walled ductile iron casting, for fast solidification process.IntroductionNodular graphite cast iron, also known as ductile iron (DI), has major applications in critical engineering parts due to its mechanical properties and castability. The mechanical and physical properties of this material depend on the shape and number of the graphite grains andmicrostructure of the metallic matrix.Solidification of DI was a subject of many computer modeling programs described in literature [ 1-5], in which the stationary conditions of carbon diffusion in austenite is pre-assumed. Recently, a tendency for production of thin-walled castings has been observed [ 6-8]. In this technology, the process of the fast solidification may be very far from equilibrium and steadystate conditions [9].The purpose of the present work is a two-dimension model development for simulation of the DI structure formation during the solidification in the condition of non steady-state temperature and diffusion fields in the thin-wall casting.Model of process The CA-FD is one of the known methods of the simulation ofmicrostructure formation during the solidification [ 10, 11]. In the CA microstructure modeling the outer grain shape is the result of the simulation and does not superimposed beforehand. The model development for a onephase microstructure evolution is a subject of the numerous researches [12 -23]. Model of the eutectic solidification of DI in the uniform temperature field and superimposed cooling rate is known [24]."

Jan 1, 2013

By Kazuki Morita

A new route to produce solar grade silicon (SOG-Si 6N) from metallurgical grade (MG-Si 98%) has been developed in Japan, which may satisfy the increasing demand for solar cells in the near future. Since some elements such as P and B have very large segregation coefficients, solidification refining is not effective for their removal and costly processes, such as electron beam vacuum melting and oxidation plasma refining, are required. According to our previous results which showed the effectiveness of leaching procedure with Ca addition for Fe and Ti removal, possibility of P and B removal by acid leaching was focused expecting that their affinities for Ca in molten silicon might be considerable. Hence, the effects of Ca addition on the thennodynamic properties of P and B in molten silicon alloys have been investigated for overall control and optimization of the SOG-Si production process in the present study. The interaction parameters between Ca and P, and Ca and B were determined by chemical equilibration techniques at 1723 K. Although the interaction parameter between Ca and B was slightly negative, that between Ca and P showed a large negative value. Also, the results for the leaching test with various amount of Ca addition revealed that the removal fractions of both elements, especially P, drastically increased with increase in the Ca content, which showed very good agreement with the prediction from the interaction parameters derived in the present work. The present results suggest that the preliminary leaching procedure can reduce the processing time and energy for SOG-Si refining. Keywords: Silicon, Solar Cell, Refining, Acid Leaching, Thennodynamics. Interaction, Phosphorus, Boron, Calcium

Jan 1, 2003

By Hiroyuki Sano

A closed recycling process for the low-grade scrap of Al-based composite materials was developed. In this process flux treatment with water-soluble halide is a key technique. In the present work, flux treatment conditions were discussed from the viewpoint of the separation and the recovery of the base material, reinforcement and flux. Optimum separation condition was obtained for the NaCl-KCI-KF flux treatment. The recovered aluminum alloy can be recycled for various usages. The recovered SiC particles cannot be reused as reinforcement because of the coexistence of the contamination, therefore it is necessary to eliminate these contaminates or to find another use. The recovered flux is reusable with supplemental addition of fluoride.

Jan 1, 2003

An iridium oxide coated titanium electrode was tested as anode in copper electrowinning. Initial results confmed that the DSA-type anode was significantly more active for oxygen evolution than traditional lead anodes. However, during longer runs, the anode potential was observed to increase linearly at a rate of 220 mV/year. Scanning elecuon microscopy (SEM) and energy dispersive spectroscopy (EDS) showed that the anode passivation could be attributed to elecuochemical dissolution of the coating. The effect on the anode potential of organic additives (glue and thiourea) and lead in solution was also examined. A preliminary economic evaluation of the anodes is given.

Jan 1, 1992

By Ole Rud Bendixen

Topsoe has developed a Wet gas Sulphuric Acid (WSA) process which effectively recovers SO2 in off-gases from non-ferrous smelters and roosters. The product is concentrated sulphuric acid of typically more than 96 wt% irrespective of SO, concentration in off-gas. The process does not generate any waste products or waste water and does not use any absorbents or other chemicals. In the process, up to 99.3% of the SO2 is converted catalytically into SO3, which reacts with water in the gas, hereby forming gaseous sulphuric acid. The acid is condensed in a WSA condenser of proprietary design. Excellent heat economy and practically no sensitivity to the water balance mean that no extra sulphur burning is required at any S02 concentration, The process is especially well suited for treating off-gases where the SO2 content is lower than approx. 5-6%, and it is a good alternative to a complete renovation of a smelter. However, also off-gas from flash smelter may be treated. The process has found good use in both molybdenum and lead roosters. An example from a molybdenum roaster in Chile shows that 97-98wt% acid is produced from a 2.3 % S02 gas. This plant is situated in the outskirts of Santiago and represented a major local source of SO2. The plan was started in May 1993.

Jan 1, 1996

By Jose R. Parga

In mining operations, cyanidation is the ,predominant method by which gold and silver are recovered from their ores and it is recognized that cyanide consumption can be a major factor that contributes to the operating costs for such operations. Also after extraction and recovery of precious metals a certain amount of cyanide is delivered to the tailings pond and must be considered with respect is environmental problems due to the toxicity of cyanides. In this regard, the Air-Sparged Hydrocyclone (ASH) has been used as a reactor for the treatment of cyanide solutions in two ways; first for cyanide recovery by acidulation using the Mexican modification of the Mills-Crowe process and second for cyanide destruction by oxidation with the use of chlorine dioxide (ClO2). In both cases, excellent performance can be achieved using the high capacity ASH system.

Jan 1, 1998

By Toshiaki Tsuru, Takeshi Ohgai, Hisaaki Fukushima, Shigeo Kobayashi, Tetsuya Akiyama

"Electrodeposition behavior of Zn-Cr alloys from the methanol baths was investigated. In the methanol baths of low Cr3+ concentration, Cr (III) compound was incorporated in the deposits and no lusfrous Zn-Cr alloys was deposited. However, Cr was existed as metallic state in the deposits obtained from the baths of higher Cr3+ concentration. With an increase in water content in the baths, the chemical state of Cr in the deposits changed from metallic to trivalent state. Under the condition that metallic Cr can be electrodeposited, Zn deposition was significantly polarized to the potential of Cr deposition.INTRODUCTIONAn attention has been paid to Zn-Cr alloy plated steel sheet because of its excellent properties for body panels of automobile and electrical appliances [1]-[4]. This plating process can be operated using the sulfate solutions containing Cr3+ ion [1] - [6].In decorative single Cr plating, on the other hand, many attempts have been made to electroplate Cr from trivalent electrolytes, which is motived by environmental deficiencies of the presently used hexavalent process [7]. [8]. However, it has been reported that in the aqueous solutions the behavior of the electroreduction of 0 3+ is atypical due to the complicated nature of the chemistry and electrochemistry of cr3+ species [9]-[11]. Even in Zn-Cr alloy plating, it is difficult to codeposit metallic Cr with Zn in simple sulfate electrolytes [l]-[4], [12]. Therefore, it can be expected that the electrodeposition behaviors of Zn-Cr alloys as well as Cr are significantly changed when the electrodeposition is conducted in non-aqueous plating solutions.In this study, the electrodeposition of Zn-Cr alloy was conducted from methanol solutions to clarify the electroreduction mechanism of Cr3·-Cr0 in the alloy deposition process."

Jan 1, 2000

By Nicole de Jager, Michael J. Nicol

"In order to liberate gold from refractory gold ores and concentrates it is generally necessary to oxidise the surrounding sulphide minerals, typically pyrite and arsenopyrite. Traditional methods of oxidation include pressure leaching, roasting and bacterial oxidation. In recent years, bacterial and pressure oxidation have found increasing favour, although these methods are by no means completely satisfactory and each is subject to particular disadvantages.A novel process has been developed as an alternative to the traditional methods whereby electro-generated ferrate(VI) ions in alkaline solution are used to oxidise a pyrite concentrate. This process has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. As an added benefit, operating in an alkaline environment is advantageous for downstream cyanidation processes.Ferrate(VI) is a relatively unknown species, due mainly to its instability in acidic solutions. However, in alkaline solution it has been observed to be sufficiently stable for use as an oxidant when used under favourable conditions. Ferrate(VI) is most conveniently manufactured electrolytically via the dissolution of high-carbon anodes in strongly alkaline solutions. Some literature has been published on the electrolytic generation of ferrate(VI) and relatively high efficiencies have been observed by both the authors and other researchers.This study utilises both electrochemical techniques and leaching experiments to examine the kinetics of the oxidation of pyrite by ferrate(VI), which is produced electrolytically. Cyclic voltammetry, rotating disk voltammetry and potential step experiments have been used to investigate the kinetics and mechanism of the oxidation process."

Jan 1, 1997

By Yasuhiro Konishi, Kazunari Mizoe

"This paper describes a new processing of ultrafine, magnetic ferrites from sulfuric acid pickling solution in steel industry. In the ferrite processing, the iron (II) in the pickling solution was first oxidized to iron (III) by using the acidophilic thennophile Acidianus brierleyi. The bio-oxidized pickling solution was treated with solvent extraction to separate the iron (III) into the organic solution of tertiary aliphatic monocarboxylic acid. After that, the carboxylate solutions of iron (III) and other metal (cobalt) were hydrolyzed and precipitated ultrafine particles of crystalline ferrites at l90°C and l. 3 MPa for 20 min.IntroductionHot-rolled steel sheet has always a layer of oxides on its surface. The oxide layer arises as scale in hot rolling processes in steel industry, and the scale consists of the three iron oxides such as hematite Fez03, magnetite Fep4, and wustite FeO. Pickling removes chemically the scale layer that adheres to the steel surface. For normal steels, pickling is carried out in 15-20% hydrochloric acid at 60-70°C or in 20-25% sulfuric acid at 95-100°C. When steel is pickled with sulfuric acid, the scale oxides dissolve to give iron (II) sulfate.Spent pickling solutions are hazardous wastes containing a large amount of dissolved iron (II) and sulfuric acid, e.g., about 40 kg/m3 of dissolved iron (II) at pH 0. In typical commercial processes, spent pickling solution is usually cooled evaporatively to 5°C, and then to 0°C to crystallize iron (II) sulfate as its heptahydrate. After the crystallization operation, the sulfuric acid can be reused in the pickling operation.In this paper we describes a new processing of ultrafine, magnetic ferrite from sulfuric acid pickling solution, in order to recover dissolved iron (II) in the form of a valuable product. In the ferrite processing, the iron (III) was first supplied by the microbial oxidation of iron (II) in the pickling solution, and then the biooxidized pickling solution was treated with solvent extraction to separate the iron (III) into the organic carboxylate solution. After that, the carboxylate solutions of iron (III) and other metal (cobalt) were precipitated crystalline ferrites under hydrothermal conditions."

Jan 1, 2000

By Shengli Wu, Jinming Zhu, Wei Huang, Xinliang Liu

The sinter of high basicity would interact with lump ores or acid pellets in the cohesive zone of blast furnace due to the difference of chemical composition and micro structures. The results of this work showed that the softening-melting properties of lump ores and acid pellet would be obviously improved by the high temperature interaction. However, the high temperature interaction index (INI) would be influenced by many factors, such as chemical composition, porosity, interaction interface and so on. The INI between sinter and porous limonite lump ore (L-2) was much higher than that of dense hematite lump ore (L-1) and acid pellet (P-1). In addition, though the softening and melting properties of L-2 were poorest in respective iron ores, the softening and melting properties of integrated burden B (consist of sinter and L-2) were not worse than other integrated burdens due to the strong high temperature interaction.

Jan 1, 2015

By I. H. Gundiler

Sandia National Laboratories (SNL) is tasked to support The Department of Energy in the dismantlement and disposal of SNL designed weapon components. These components are sealed in a potting compound, and contain heavy metals, explosive, radioactive, and toxic materials. SNL developed a process to identify and remove the hazardous sub-components utilizing real-time radiography and abrasive water-jet cutting. The components were then crushed, granulated, screened, and separated into an aluminum and a precious-and-base-metals fraction using air-tables. Plastics were further cleaned for disposal as non-hazardous waste. New Mexico Bureau of Mines & Mineral Resources assisted SNL in investigation of size- reduction and separation technologies.

Jan 1, 1995

By A. J. van der Zeeuw

The use of SME 529 in the extraction of copper from acidic liquors and of copper and nickel from ammoniacal solutions, is illustrated with results of laboratory and bench scale mixer/settler experiments. Special features of SME 529 are its high loading capacity and the ability to keep the complexes dissolved in the organic phase up to quite high concentrations.

Jan 1, 1976

By Jie Ma, Bo Wang, Jieyu Zhang, Jian Zhao, Zheng Chen

"In this paper, solidification process of steel ingot was simulated by ProCAST software, based on cellular automaton-finite element (CAFE) model. A 22 t steel ingot was divided into continuous small zones (100x150x180 mm) in radial direction, then the temperature field, shrinkage cavity and porosity, particularly, the microstructure were simulated. The results show that: there was a columnar-to-equiaxed transition in microstructure on radial direction. Zones, closing to the center of the ingot, had a more developed and fined equiaxed zone, while zones closing to the periphery of the ingot had a more developed columnar zone. It indicated that temperature gradient has a great influence on microstructural morphology. Thus, the simulation results were highly agree with the experimental results, verifying the feasibility of this simulation method. It significantly reduces the time of simulation, and has important significance for predicting the microstructure of large steel ingot.IntroductionSolidification microstructure of steel ingot have a significant effect on the quality of the final steel products. Although many experimental works have been carried out in order to obtain the optimum condition for solidification process of continuous casting, it is also very desirable to establish mathematical models to simulate the evolution of solidification structure. The simulation methods can be divided into deterministic models and stochastic models, which have been developed rapidly over the last couple of decades. Cellular automaton method is one of the stochastic models. Rappaz and Gandin [1, 2], Nasatac and Stefanescu [3, 4] are the earliest researchers engaged in the this field. Moreover, Rappaz and Gandin simulated the solidification structure and CET (columnar grain to equiaxed grain transition) of metals using the CAFE method (cellular automaton-finite element method) for the first time [1, 2]. Recently, the CA (cellular automaton) model also considered the effects of fluid flow on the solidification process. Zhu, et al. [5-11] improved method of CA , they used the KGT model to describe the undercooling needed during the growth of the dendrite tip."

Jan 1, 2014

By G. Lissens

In this work the electrochemical combustion of dissolved organic species in a single compartment cell containing a titanium mesh cathode and a boron doped diamond anode has been studied, The organic molecules involved were complexing agents such as EDTA (ethylenediaminetetraacetic acid) or NTA (nitrilotriacetic acid) used in metal plating shops and bright nickel plating bath additives, From batch experiments, it is shown that complete decomplexing of EDTA and NIA is feasible. Complete TOC (Total Organic Carbon) removal from solutions containing 0.01 M EDTA, 0.02 M NTA and bright nickel plating bath additives could also be achieved. Recycling experiments show that decomplexing of EDTA and NTA solutions can be obtained at an average electrical energy input of ~20kWh.kg-1 of complexing agent. Decomplexing rates of respectively 3.l3 mmol.Ah-1 for EDTA and NTA have been obtained, The Instantaneous Current Efficiency (ICE) was 71% for EDTA and 95% by NTA, Simultaneous recovery of Cu from a 0.01 M Cu-EDTA solution has also been evaluated. A solution (1.8 dm3) containing 0.01 M EDTA and 528 ppm of Cu was treated in a single compartment cell at a current density of 2 A.dm-2. 73% of the TOC could be removed and a final copper concentration of 8 ppm was obtained.

Jan 1, 2003

By P. R. Khangaonkar

The industry of tin ore mining, beneficiation and smelting gives rise to a number of waste products like the beneficiation plant wastes (called amang), tin smelting slags, refinery dross etc. Some of the wastes deserve treatment to obtain economically useful products or to recover the metal values. The paper describes studies conducted on two materials, viz., struverite-middling (struverite-magnetic tin), which is an intermediate product of beneficiation circuits of tin tailings, and tin-smelting slags. The struverite middling was studied for treatment by chlorination using carbon tetrachloride, so as to yield vapour products separable by convenient condensation. The treatment was also found to lead to a tin-rich product amenable for treatment by known hydrometallurgical routes. The tin smelting slag was studied by alkali-leaching so as to avoid any dissolution of iron and it was possible to obtain an iron-free product solution suitable for high purity tin recovery.

Jan 1, 1996

By S. Neven

The smelting of copper anode slimes, a material which contains mostly lead, silver, copper and selenium, has been practiced for many years with a view to recovering the silver and associated small amounts of gold. However, a theoretical understanding of the process has been lacking and this handicaps efforts to improve and intensify smelting operations. In the past few years work has been done in this area and this work will be reviewed in the paper. The underlying thermodynamics of the oxidation of silver-copper selenide mattes has been developed and used as a basis for the construction of a computational thermodynamics model which attempts to predict the composition of all condensed phases during the course of smelting. The model will be outlined and its successes in matching experimental data, as well as its current deficiencies, will be considered. Supporting work on the thermodynamics of silver solubility in slags, on activity-composition relationships in the Ag-Se system and work in progress on the oxidation state of copper in the slags will be reviewed. These projects are designed to provide further detailed data which will improve the robustness of the thermodynamic model.

Jan 1, 1999

By Xiping Chen, Wangxing Li, Jiemi Zhou

"Desulfurization methods suitable for anode-grade petroleum coke (coke for short) used in primary aluminum industry are coke desulfurization during calcination, desulfurization in soakage and desulfurization in mediums. Coke desulfurization during calcination is discussed in this paper. Influences of calcination temperature, holding time and coke granularity on coke desulfurization were discussed. Experimental results show that calcination temperature has a remarkable influence on coke desulfurization. When the temperature is high enough desulfurization ratio of coke can reach 85% only by calcination. Holding time has a definite influence on coke desulfurization, but desulfurization ratio is low at the temperature of 900~1300°C. The influence of holding time is obvious when calcination temperature surpasses 1400°C. The influence of coke granularity is smaller compared with calcination temperature and holding time.IntroductionPetroleum coke is main raw material for carbon anode in primary aluminum industry, and its weight percentage in carbon anode is about seven percent. Green coke can not be directly used for anode production because of its immanent moisture and volatiles. Green coke must be calcined in order to meet the request of anode production. Calcination is a heat-treatment process during which green coke is heated to a given temperature to remove volatiles, moisture and some sulfur. Real density, strength, electrical conductivity and anti-oxidation ability of petroleum coke can be improved by calcination and calcined coke can be received [1, 3, 4]. Sulfur in calcined coke finally goes into carbon anode. During baking or aluminum smelting, the sulfur in anode ultimately changes into SO2 and emits from anode into the atmosphere. Excess SO2 easily leads to acid rain which brings heavy pollution to the environment [1, 2]. With the development of Chinese aluminum industry, consumption of anode-grade petroleum coke increases year by year, the total consumption in 2007 surpassed 4.5 million tones and the yearly emission of SO2 from aluminum smelters has exceeded 270 kilotones. From 2005 Chinese government began to limit the emission of SO2 from primary aluminum industry, so desulfurization of anode-grade petroleum coke becomes more and more urgent. Some relationship need to be found and used to guide desulfurization of petroleum coke."

Jan 1, 2008

By Motohiro Horiguchi, Kazuo Ichii, Toshio Oishi

"As a fundamental study to prepare copper-based alloys with rare earths (RE: La, Gd, Nd, Ce and Y) without any inclusions, the solubility of rare earth in liquid copper was experimentally determined. Liquid copper alloys were equilibrated with carbon and rare earth carbide in a graphite crucible in an argon atmosphere at 1523-1873 K.Solubilities of rare earth in liquid copper were determined by approaching the equilibrium values from both the lower and the ·higher concentrations than those expected· in the preliminary experiments. They were expressed as a function of temperature. Carbon in Cu-RE alloy was also analyzed and thermodynamically discussed.IntroductionOver the past several years, the demand for highly conductive and high strength copper-based alloys, such as Cu-Cr, Cu-Zr and Cu-Cr-Zr for use in electronic materials has increased.1 -7 These alloying elements are very reactive and easily oxidized to form oxide inclusions during melting. To avoid the oxide inclusions, it may be effective to utilize the strong reducing power of carbon in conditions under which no carbides form.In this study, to provide fundamental data for producing Cu-RE( rare earth) alloys without any inclusions, the solubility of rare earth in liquid copper in equilibrium with .carbon .was determined and discussed on the basis of the experimental results and the thermodynamic data.ExperimentalSample preparation for equilibrium experimentsOxygen-free copper (99.99%), lanthanum (99.9%), gadolinium (99.9%), neodymium (99.9%), cerium (99.9%) and yttrium (99.9%), and their oxides were used as starting materials.Each rare earth carbide was prepared by mixing rare earth oxide with carbon, which is a little more than the stoichiometric composition, pressing it into a tablet form and sintering at about 2000.K for 20 ks in a vacuum furnace using a graphite crucible. Powder X-ray analysis showed that only the carbon and rare earth carbide (REC2) was present in each sample.Cu-RE mother alloys (5-20 mass % RE) were prepared beforehand by mixing metallic rare earth with oxygen-free copper, and melting in an electric arc furnace."

Jan 1, 2000

By Andreas Siegmund

During the decade of the nineties the conventional method of primary lead smelting (sinter machine/blast furnace) was successfully challenged by the introduction of novel direct and continuous smelting processes. In combination with a significant shift in market structure, as well as more stringent government regulations these modem technological innovations like the QSL, Kivcet, and Isa/Ausmelt processes became more than major competitors. They have proven to be economically and environmentally viable. The intensification of the metallurgical reaction by applying oxygen enriched or pure oxygen bath or flash smelting principles resulted in cost savings and a higher flexibility with respect to raw materials and additives usage. By synchronizing individual auxiliary plant sections with the smelting process a virtually waste-free production and low-emission mode of operation with nearly optimum energy exploitation is achieved. The primary lead industry will gradually substitute the sinter -blast furnace operation with novel high-energy efficient technologies in the new millennium.

Jan 1, 2003

By K. Sanjay

Factorial optimisation technique has been used to develop regression equations at different time intervals for extraction of manganese from precipitated manganese oxide/hydroxide in sulphuric acid using charcoal as the reductant. The three parameters chosen for a 23 full factorial design were : acid concentration, amount of carbon and temperature. The regression equations were used to predict >> 90% extractions as well as kinetic data.

Jan 1, 1996