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By Henrik Gudbrandsen, Geir Martin Haarberg, Ana Maria Martinez, Karen S. Osen, Sverre Rolseth

"The Several approaches were tried for developing an electrochemical route for producing high purity silicon from molten salts. K2SiF6 and metallurgical grade silicon were used as the source of silicon. Molten LiF-KF and pure KF with additions of K2SiF6 were used as electrolytes at temperatures from 550 - 900 oC. Silicon was cathodically deposited and anodically dissolved in the fluoride electrolytes. High electrorefining efficiency was obtained for many elements after electrolysis experiments at constant potential or constant current. The main challenge was to reduce the contents of boron and phosphorus. Another difficulty was to remove inclusions of solidified electrolyte. The lowest energy consumption was estimated to be ~ 3 kWh/kg Si, while the best current efficiency for Si deposition was found to be ~ 95 %.IntroductionSilicon is the most important material for photovoltaic power generation devices because of high feasible efficiency, low ecological impact and slow degradation. Development of a new and less expensive route for producing silicon of the desired quality is necessary in order to make solar cells competitive. Electrochemical routes may be an alternative possibility, and many laboratory studies have been reported over the past few decades. Most of the studies have been performed in molten salts, chloride or fluoride, at moderate temperatures so that solid silicon was deposited at the cathode. The production of high purity silicon has shown an annual increase of about 25 %, due to the increasing demand of solar grade silicon (SoG-Si). For future increased use of solar energy it is important to develop alternative, more energy efficient and cheaper processes for SoG-Si production compared to the Siemens process.Common silicon sources have been SiO2 and K2SiF6 for electrowinning and MG-Si in the case of electrorefining. A serious challenge is to find an oxygen evolving anode for electrolytes containing dissolved oxides. Especially at moderate to high temperatures and in molten fluoride electrolytes this is a difficult task.Many experimental results have been reported in molten chloride electrolytes. Nohira et al. [1-3] and Chen et al. [4] cathodically deposited silicon by electrodeoxidation of solid SiO2 in molten CaCl2 by potentiostatic electrolysis. An alternatice approach is to use electrorefining of low-cost metallurgical grade silicon (MGSi) to produce SOG-Si. In previous studies [5], an MG-Si anode was used, and silicon was successfully electrodeposited on a molybdenum wire in a CaCl2 based melt. It was found that the anode was strongly passivated due to the precipitation of silicon. Also, some deposits detached from the molybdenum wire because of the poor adherence to the cathode.Considering the Cu-Si alloy which has a good segregation effect for some impurities, and should not passivate, could be a good candidate anode for electrorefining. [6]."

Jan 1, 2014

By Rzyman Michal, Nakamura Takashi, Shibata Etsuro, Grabda Mariusz, Oleszek-Kudlak Sylwia

"Tetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in many materials such as plastics and textiles. Thermal degradation of BFR containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3. Our thermodynamic considerations indicate that these gases can act as bromination agents for metallic oxides such as ZnO, Cu2O, CuO, PbO and FeO. Moreover, these metallic oxides have the thermodynamic tendency to brominate easier than does Sb2O3. The aim of this study was to investigate experimentally the reactivity of ZnO with 1) HBr originating from the thermal decomposition of TBBPA and 2) SbBr3, which is formed during thermal degradation of brominated flame retardant plastics. The thermal treatments of the mixture of compounds of interest were investigated by thermogravimetry coupled with mass spectrometry.IntroductionTetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in materials such as plastics and textiles. For instance, 4.5 million tons of flame retardant plastics containing BFRs are produced in Japan each year. Thus, in thermal treatments such as the incineration and melting of solid wastes, BFR containing plastics are intentionally or unintentionally included in the wastes. Thermal degradation of BFR-containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3 [1-5]. Our thermodynamic considerations [6] indicate that heavy metal oxides such as ZnO, Cu2O, CuO, PbO and FeO should easily react with HBr prior to Sb2O3 and also with SbBr3, the main gaseous product in the thermal decomposition of TBBPA, forming low boiling point metallic bromides suitable for the volatile separation of heavy metals. The metal oxides are also expected to qualitatively and quantitatively affect debromination and decomposition of the flame retardant."

Jan 1, 2008

By T. T. Chen, J. E. Dutrizac

Noranda Inc., CEZinc presently employs a cement-stabilization (jarofix) process to stabilize its jarosite residues for direct disposal. In this process, Portland cement partly decomposes Na-jarosite to form Ca6Fe2(SC>4)3(OH)i2.nH20, ferric hydroxide and sodium sulphate which further reacts to form gypsum; approximately one-third of the Na-jarosite reacts in the current commercial product. The cured jarofix products also contain minor amounts of various Ca-Al-Fe silicate-sulphate-hydrate phases and traces of calcite. Together with gypsum and a Ca-Fe sulphate phase, these species bond the various particles together, imparting mechanical strength and reducing the permeability. Water-soluble Zn and Mg are stabilized in the Ca-Al-Fe silicate-sulphate-hydrate phases. The freshly cured products usually contain small amounts of moisture and traces of residual Portland cement, which provides additional alkalinity for the neutralization of any residual acid species. Jarofix products stored for more than six years in the laboratory, after curing, are usually dry and exhibit the same micro-textures as those of the freshly cured products. However, the stored products are depleted in the Ca6Fe2(S04)3(OH)i2.nH20 and Portland cement phases, and are enriched in gypsum and calcite which reflects the highly alkaline environment of the jarofix products. The aged products also have increased amounts of the Ca-Al-Fe silicate-sulphate-hydrate phases which have elevated Zn and Mg contents. This implies a further immobilization of residual water-soluble Zn and Mg during stora

Jan 1, 2000

By M. Radwan

This research reports on the synthesis of advanced silicon-based structural ceramics from mixtures composed of natural sand (Sinai white sand), reclaimed silicon and graphite by the nitriding combustion synthesis method. With pulverized sand (? 40 m), we found that the nitriding combustion can be realized at self-sustaining mode in the SiO2?Si?C system under 3 MPa nitrogen pressure. Depending on the composition of the starting mixtures, single-phase silicon oxynitride (Si2N2O) powder as well as new Si3N4?Si2N2O and Si2N2O?SiC composite powders with controllable chemical compositions were successfully developed. The measured thermograms of various combusted mixtures and the thermodynamic characteristics of possible exothermic reactions in this system were discussed to explain the nitriding combustion behaviour and mechanism. Near-full dense Si2N2O were fabricated from synthesized Si2N2O powder with 5 wt % oxide additive by the spark plasma sintering (SPS) method at 1600 °C. The dense Si2N2O samples had good mechanical properties (18.7 GPa Vickers hardness, 3.3 MPa m1/2 fracture toughness and 363 MPa strength) and excellent chemical and oxidation resistance. The synthesized composite powders were also densified to high densities (> 90 % of theoretical values) by SPS technique. The results obtained in this study can be seen as a new route to prepare important silicon-based structural ceramic powders with various compositions/properties from cheap starting materials which makes them potential for wide range of applications.

Jan 1, 2006

By A. V. Tarasov

In the course of research aimed at improving the performance of the Vanyukov smelting process (VP) for treating sulfur raw materials in a pilot-scale furnace it has been found that an increase in the calcium oxide content up to 12% to 14% in case of smelting to produce high-grade matte results in a decrease in the copper content of slag by 0.05% to 0.3%. The residual copper content of slag can be computed by a formula taking into account an increase in the calcium oxide content of the feed material and that in the slag. In the course of research for improving the performance of the zinc-containing slag fuming process with blowing of the slag bath with combustion products of natural gas it has been found that the silica and calcium oxide contents have an effect on the degree of zinc sublimation. In case of slag containing 24.4% SiO₂ and 6.95% CaO by weight (SiO₂:CaO = 3.51), the residual zinc content of slag was 3.25%. The minimum residual zinc content of 1.95% was obtained in case of slag containing 22.5% SiO₂ and 14.5% CaO by weight (SiO₂:CaO = 1.55). An increase in the CaO content of slag up to 16% by weight with a ratio of SiO₂:CaO = 1.25 to 1.35 permits minimization of zinc losses in slag by achieving a residual zinc content of final slag in the order of 1%.

Jan 1, 2006

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

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

Jan 1, 2012

By Guanghua Wen, Jian Li, Mingmei Zhu, Fei Xiong, Shengjian Cao

"Small inclusions removal from molten steel in a continuous casting tundish by gas bubbles, which were generated in the turbulent flow region by introducing inert gas, was analyzed theoretically and the inclusion-bubble adhesion and flotation process was also observed by high-speed photo-graph in water model. Results showed that small inclusions in the range of 20-50µm removal from molten steel by bubbles flotation involves three stages: contact, adhesion and flotation. The inclusion-bubble adhesion processes include two ways: inclusions adhering to the upper part of the bubble and inclusions adhering to the lower part of the bubble. As the bubble floats up, the number of inclusions adhering to the bubble are increased. The proper size of bubbles, which could enhance small inclusions removal efficiency, should be controlled in the range of 1-2mm.IntroductionReducing inclusions content in molten steel is a very important way to improve quality of steel, and one of the main tasks in steel making process.A variety of methods have been used for inclusions removal in molten steel. At present, the main approaches to remove inclusions are gas stirring, slag cleaning, filtering, centrifugal separating, and by means of ultrasonic or electromagnetic field. Among these techniques, gas stirring is the most widely and effectively method for inclusions removal. Inclusions in molten steel will be aggregated and generated to form larger size inclusions, and subsequently floated to the surface of molten steel by buoyancy; meanwhile, some inclusions will be adhered to bubbles and floated together to metal-slag interface where inclusions are absorbed by the covering slag layer. Some research work showed that flow behaviors of small bubbles are different from that of big ones [1-2], and smaller bubbles are more efficiency for fine inclusions removal in molten steel.There are many methods to generate bubbles. During steelmaking process, highly turbulent flow in the ladle shroud can split introduced inert gas into small bubbles, which enhances the removal of fine inclusions from molten steel. Turbulent flow of molten steel injected into tundish from ladle shroud has a high speed and it is a strong turbulent area in continuous casting. The gas can be introduced into the shroud below the slide gate. The high turbulence flow would break up the gas into small gas bubbles. Fine inclusions will be easily adhered to small bubbles and subsequently floated to the surface of molten steel. Generation of small bubbles in ladle shroud have been studied in some literatures [3-4]. Some research have analyzed the fine inclusions removal with injecting gas from the ladle shroud by mathematical simulation, and the results show that the refining method can obviously improve the removal efficiency of fine inclusions in tundish [5-8]."

Jan 1, 2013

By Ehsan Vahidi, Fereshteh Rashchi, Ataollah Babakhani, Alireza Zakeri

"The synergistic effect of Cyanex 302 on solvent extraction of nickel and cadmium from sulfate solution with D2EHPA diluted in kerosene was investigated with the aim of increasing separation efficiency. Experiments were carried out within a pH range of 0.1-5.0 using sole D2EHPA and D2EHPA-Cyanex 302 mixtures in different ratios. Increasing Cyanex 302 to D2EHPA ratios in the organic phase caused a left shifting of the extraction isotherm of cadmium and a right shifting of the extraction isotherm of nickel. As a result, optimum separation was found with a Cyanex 302 to D2EHPA ratio of 0.1M:0.5M. In the present system, effect of a modifying reagent such as TBP was studied. The influence of various diluents including kerosene and carbon tetrachloride was also investigated.IntroductionBatteries are popular sources of portable energy. Ni-Cd batteries are manufactured in two main groups of small domestic cells and large industrial batteries with 80% being in domestic use. Ni-Cd cells have various uses, for example in cordless electric utensils, cordless telephones, airplane engine starters, and communicational distribution systems [1].Depleted Ni-Cd batteries are classified as hazardous waste since nickel and cadmium are heavy metals and suspected carcinogens. Given the risk associated with uncontrolled disposal, directions for issuing legislation on disposal and recycling of used batteries have been made in industrialized countries [2]. Recycling of Ni-Cd batteries is important from both economic and environmental points of view. Different methods have been used for recycling these wastes through pyrometallurgy [3], biotechnology [4,5], and hydrometallurgy [1,2].Due to the advantages of hydrometallurgical processes, several studies have been implemented on leaching and solvent extraction (SX) of the used Ni-Cd batteries. Leaching of batteries is usually done in sulfate or chloride media; while solvent extraction has been used in different extractants: two-stage solvent extraction by D2EHPA and Cyanex 272 [6]. Solvent extraction of Cd from leach solutions has been studied using various extractants; Cyanex 301 [1], D2EHPA [7], Cyanex 302 [8], Cyanex 923 [9], Cyanex 272, Tops 99, PC88A [10]. Application of phosphorus based extractants for the solvent extraction studies of Ni such as TOPS 99 [11], D2EHPA [12], Cyanex 272 [2], has been investigated. Separation of Cd(ll), Ni(II), and Co(ll) from chloride leach liquor of spent batteries [13], were explored in the earlier studies. Cd extraction with D2EHPA involves co-extraction of both Ni and Co [14], which causes issues in the separation process efficiency."

Jan 1, 2012

By Jeffrey Shepherd, Scott R. Smith, Eduard Guerra

"Electrochemical and spectroscopic evidence for the dissolution of a Au electrode by meso-2,3- dimercaptosuccinic acid (DMSA) from an acidic LiCl04 electrolyte is presented. Near the potential of zero charge, DMSA was determined to form a stable layer on the metal surface but at more anodic polarizations, DMSA was displaced from the metal through an oxidative process. The anodic displacement of the layer from the electrode resulted in a small amount of Au that was detected in the electrolyte using atomic absorption analysis. The extent of Au dissolution, was monitored while holding the potential of the electrode for 24 hours at the thermodynamic Eo/H,O in LiCl04 electrolytes containing 10 mM DMSA. This routine resulted in detectable quantities of a soluble Au-DMSA complex in the electrolyte and the greatest leaching was observed at a pH = 2.0. At room temperature, the leaching rate was stable at 10.9 µg cm·2 hr·' however, upon increasing the temperature to 50.0°C, the rate of Au dissolution increased yielding an average rate of extraction of 40.1 µg cm·2 hr- 1. Interestingly, after the first 12 hours of leaching at 50.0°C, the leaching current decreased dramatically suggesting surface passivation which prevented further Au extraction. The implications of this process in the industrial leaching of Au will be discussed.IntroductionThe use of cyanide in the industrial process of leaching Au from ores has raised concerns regarding both operational safety and environmental issues surrounding the disposal of spent leaching eftluents in tailings ponds. Depending on the chemical nature of the processed ore, the spent solutions that are released into the tailings ponds can contain toxic cyanide, either dissolved or complexed with different metals and may pose serious risk to wildlife as well as freshwater contamination to nearby water systems. Because of these issues, some recent studies have focused on the exploration of more environmentally-friendly molecules to selectively leach Au with appropriate kinetics. However, to effectively leach Au into an aqueous solution, a suitable ligand that reacts to form a stable chemical bond with Au is needed to form soluble Au complexes that can be later recovered [I]. Recently several sulfur bearing alternatives have been shown to leach significant quantities of Au in aqueous solutions. These include thiourea [2], thiocyanate [3], and thiosulphate [4]. However, alkylthiols are also known to quickly form a stable covalent Au-S bond [5], but have been relatively understudied in term of their ability to leach Au in solution, even though some short chain thiols are water soluble and relatively nontoxic."

Jan 1, 2012

By A. D. Neuman, C. C. Davis, M. R. Lopez, A. C. Martinez, T. A. Nothwang, F. G. Hampel, S. L. Voit

"One of the thrust areas for the Global Nuclear Energy Partnership (GNEP) program is the development of actinide bearing fuels for transmutation in a fast reactor. Mixed Oxide (MOX) fuel has an extensive fast reactor irradiation history and thus is being considered for use as a baseline composition from which minor actinides can be incorporated for use as a transmutation fuel. The current study involves characterization of precursor powders and pellets destined for the Advanced Test Reactor in Idaho. These pellets will have three compositions: one standard MOX composition, (U0.80Pu0.20)O1.98, and two compositions of minor actinide mixed oxide (MAMOX) with oxygen to metal ratios (O/M) of (U0.75Pu0.20Am0.03Np0.02)O1.98 and (U0.75Pu0.20Am0.03Np0.02)O1.95. The precursor powders were characterized using a field emission gun scanning electron microscope (FEG-SEM) to determine particle morphology, size, and size distribution. An electron probe microanalyzer (EPMA) was used to characterize element distributions in the pellets.IntroductionThe fundamental purpose of GNEP is to enable a fuel recycling partnership between member nations. The customer nations utilize the fuel for electricity generation provided by and subsequently recycled by the supplier nation. The supplier nation recycles the actinide constituents, mainly uranium and plutonium, in advanced nuclear power reactors, and thus reducing waste volumes [1, 2]. Nuclear materials are strictly controlled through the International Atomic Energy Agency. One of the thrust areas supported by the GNEP program is the development of actinide bearing fuels for transmutation in a fast reactor under the U.S. Advanced Fuel Cycle Initiative (AFCI) in order to transmute long-lived transuranic actinide isotopes into shorter-lived fission products [3].MOX fuel has an extensive fast reactor irradiation history and thus is being considered for use as a baseline composition into which minor actinides can be incorporated for use as a transmutation fuel [4]. Irradiation performance data on oxide fuels with high concentrations of minor actinides is limited, which has prompted this study. This paper discusses the characterization results of precursor powders and pellets prepared for the Advanced Test Reactor in Idaho to determine the effects of including minor actinides in the fuel, and addresses two fuel test matrices proposed by Hilton et al. [3]. The pellets will have three compositions: one standard MOX composition, (U0.80Pu0.20)O1.98, and two compositions of MA-MOX with O/M of (U0.75Pu0.20Am0.03Np0.02)O1.98 and (U0.75Pu0.20Am0.03Np0.02)O1.95. The precursor powders, uranium oxide (depleted, DUO2 and highly enriched, HEUO2), neptunium oxide, NpO2, americium oxide, AmO2, and plutonium oxide, PuO2, were characterized using a FEG-SEM for particle morphology, size, and size distribution. The morphology of the actinide powders was studied in the areas of flowability and porosity in order to predict manufacturability. The MOX pellets were characterized using an EPMA in order to determine impurity levels and locations."

Jan 1, 2008

By J. H. Huang

In this investigation, the selective precipitation of cobalt and molybdenum from Co-Mo aqueous solutions was studied in order to recover efficiently valuable elements from industrial effluents generated from a novel electrodeposition of nanocrystalline Co-based alloys process and reduce the effluent impact on environment. It was found that the behavior of cobalt in aqueous solutions was substantially affected by the presence of molybdenum. When adding 11.6 to 46.6g/L molybdenum to a 50g/L cobalt solution, the co-precipitation of molybdenum and cobalt started to occur at pH value of 3-4. However, without the presence of molybdenum, cobalt could only be precipitated out of the solution at about pH 6. Most of the molybdenum was found in the solid phase when the solution pH reached 5. After further increasing pH to greater than 7, the molybdenum dissolved back into the solution. Cobalt kept precipitating as the pH increased. When the pH was greater than 7, most of the cobalt was present in the solid phase. The chemical and physical characteristics of the precipitated materials were investigated by SEM, XRD, AAS and EDX. It was revealed that the precipitate was initially present as cobalt molybdate oxide hydrate and subsequently transformed as sodium cobalt molybdenum oxide. With further increasing the solution pH, the precipitate was transformed into cobalt hydroxide. Further investigation implied that most of molybdenum was chemically tied to the precipitate produced at the low pH, yet at the same time, physically entrapped at the high pH. The paper also presents the influence of reaction temperature and time on the precipitation process and kinetics.

Jan 1, 2003

By Fernanda Margarido

Recovery of metals contained in the electrode materials of batteries was studied considering an integrated recycling process constituted by physical and chemical operations. The physical treatment included the shredding of the spent batteries, followed by a wet sieving operation of the fragmented material. The physical behavior of Ni-Cd and Zn-Mn based (alkaline and saline) system batteries was studied and compared. In that sense, shredding operation was performed and the sieving of shredded fractions was accomplished to evaluate the efficiency of the separation of electrodes and scrap. For Ni-Cd batteries the loss of electrode material with the supra fraction (scrap) after the shredding operation was lesser than the Zn-Mn batteries. Especially for saline-type batteries, the electrode attached to the scrap was substantial leading to important losses. This difference can be explained by the composition of the case materials and the internal physical constitution of the electrodes. The wet sieving studies carried out allowed optimizing the separation of the electrode fine fractions from the scrap materials through the analysis of selectivity Cd/Fe or Zn/Fe. For Ni-Cd batteries, maximum selectivity was achieved for the granulometry of 1.4 mm, while for alkaline and saline systems best selectivity were obtained at 2.8 mm and 5.6 mm, respectively. This process allowed the recovery of about 70% of electrodes for Ni-Cd and alkaline systems, and 50% for saline batteries, with less than 5% of scrap as contaminant. This physical step can be considered as a pre-treatment of this type of waste material envisaging its valorization by chemical treatment, as improves the concentration of the elements of interest and decreases the iron content.

Jan 1, 2006

By Dexter G. Mendoza

To analyze the behavior of minor elements in the copper smelting process, the phase relations and the activities of arsenic and antimony in the miscibility gap of Cu-Fe-S-X (X = As or Sb) system have been determined at 1473K by the quenching method and the double Knudsen cell- mass spectrometric method, respectively. The experiments have been conducted for the charges in the miscibility gap with different mass%Fe/mass%Cu ratios with varying arsenic or antimony content. The activity measurements indicate that the arsenic activities in both the metal and matte phases show extremely negative deviation from the ideal behavior. The Raoultian activity coefficients at infinite dilution in the metal and matte phases are found to be almost constant against the charges in the miscibility gap, and they are 4.3 x 10-3 and 5.5 x 10-2 for the metal and matte phases, respectively. Moreover, the activity measurements of antimony show an activity value larger than that of arsenic but it still deviates negatively from Raoult's law. The activity coefficients of antimony at infinite dilution are found to be 1.2 x and 2.2 x 10-1 for the metal and matte phases, respectively. The vapor pressures of the predominant As, AS2, AsS, Sb, Sb2, and SbS species in the gas phases of arsenic and antimony, respectively, equilibrated with the immiscible solutions have been calculated on the basis of the determined activity coefficients and they are very small at less than 1 Pa, even when their contents in the metal phase are increased up to 10 mass%.

Jan 1, 2002

By Wei-ling Wang, Ryosuke O. Suzuki, Xiang-ning Meng, Miao-yong Zhu

"A finite-element thermal-stress model of continuous casting mold is conducted to predict deformation of copper plates and its change with different cooling structure. The results show that deformation behavior of copper plates is mainly governed by cooling structure and thermal- mechanical conditions, deformation amount is related to structure geometry, and a small deformation mutation occurs in cooper-nickel boundary due to different properties. The maximum deformation of hot surface centricities of wide face locate at 100 mm below meniscus and that of narrow face locate at meniscus and terminal of water slots and significant curvature fluctuations on both sides of copper-nickel boundary. The maximum deformation of centricities is increased up to 0.05 mm with thickness increment 5 mm of copper plates, and maximum deformations are only depressed 0.01 mm and 0.02 mm with increments of 1 mm nickel layer thickness and 2 mm water slot depth respectively.IntroductionIn conventional continuous casting of steel, a large amount of sensible and latent heat of molten steel dissipate in primary cooling zone and make continuous casting mold under enormous heating load giving rise to thermal stress, deformation, high-temperature fatigue and creep not only depress mold life-span, but reduce casting stability [1] Many studies focused more on heat transfer, solidification and shrinkage of solidifying shell to provide inverse proposals for optimizing cooling system and even designing new taper of mold [2,3], but it is generally useless to those of having been manufactured or being put into production. Therefore, mold-related forward problems show necessity to be discussed deeply, and stress and deformation distributions based on special thermal conditions in mold should be analyzed in order to explore suitable cooling structure of mold directly. Samarasekera et al. [4] examined heat flow and distortion of two-dimensional longitudinal sections and investigated effect of cooling water velocity, copper plates thickness and carbon content on formation of rhomboidity and longitudinal comer cracks. O'Connor et al. [5] developed a three-dimensional mathematical model to compute thermo-mechanical state in thin-slab mold and calculated temperature and deformation of mold wall to assess roles of various process parameters on impacting mold life. Thomas et al. [6] predicted temperature, distortion and residual stress in mold and indicated increased distortion requires increased remachining, which reduces mold life and increased residual stress increases the probability of a catastrophic crack failure. Park et al. [7l determined heat-flux profiles in funnel-shaped and parallel thin-slab molds based on an inverse heat conduction model and thermocouple temperature measured in-plant and put them into three- dimensional finite-element thermal-stress model to predict temperature, distortion and residual stress of mold wall. Korie et al. [SJ focused on prediction of temperature, distortion and residual stress in mold and in particular to clarify that mold life is significantly affected by temperature and its rigidity, but little effect by mechanical including clamping force, bolt prestress, friction and ferrostatic pressure. Meng et al. [9l predicted temperature and thermal stress in a slab mold and analyzed effect by cooling system geometry and casting speed quantitatively. In present study, a three-dimensional finite-element thermo-mechanical model with type-switched element is transformed from previous heat-transfer finite-element model [9l, and mold deformation is simulated in order to shed light on thermo-mechanical behavior with special thermal conditions and different mold geometry at high casting speed."

Jan 1, 2013

By Brommerm Tracey, Britt Elin Gihleengen, Elsa Olivetti, Hans Ole Riddervold, Randolph Kirchain, Geir Øyen

"Compositional uncertainty in secondary materials and variable processing conditions inhibits secondary material utilization in the production of aluminum alloys. Efforts to implement optimization models that direct batch planning have limited industrial presence due to factors such as the insensitivity of these optimization models to dynamic plant circumstances. This paper describes a chance constrained model formulation that generates lower cost, robust batch plans with significant flexibility towards changes in processing conditions. The principal attribute of the chance constrained formulation is its inherent mitigation of risk by diversifying the batch plan. This paper compares aluminum remelter batch planning using the chance constrained formulation with a traditional deterministic model and a manual batch planner. With the expectation that volatile material prices, restricted scrap material availability, and pressure by consumers and legislation for increased recycled raw material input will continue in the future, batch planning tools that inherently diversify a production portfolio will become increasingly advantageous for industrial aluminum remelters.IntroductionAluminum remelters must develop strategies to incorporate lower cost secondary materials into finished alloys to remain competitive amidst increasingly demanding market and regulatory conditions. Determining the optimal combination of incoming raw materials to produce an alloy that meets compositional specifications presents remelters with a complex problem that has driven the development of computational tools commonly referred to as batch planning or blending algorithms. The ubiquity of the ingredient or raw material blending problem in production has motivated ongoing development of batch planning algorithms since the classic nut-mix problem in the 1950's [1]. The most common model formulation for industrial aluminum remelters are deterministic, linear optimization programs [2]. These blending problems determine the optimal combination of raw materials by minimizing cost subject to constraints around demand, availability, and compositional specification. Despite extensive research and moderate computational requirements, batch planning algorithms are inconsistently used in industry. Insufficient incorporation of the complexity of real world remelting conditions into these models provides an obstacle for their implementation [3]. For example, many batch planning algorithms do not explicitly incorporate the impact of compositional variation of the raw materials on overall batch cost. Additionally, they do not allow for endogenous specification of tolerance to error in batch planning, so provide little flexibility where a batch planner would like to incorporate materials of greater uncertainty. Incomplete accounting for quality variability undervalues secondary materials leading to overly conservative use [ 4, 5]."

Jan 1, 2011

By Norihiko Fukatsu, Takashi Iwamoto, Noriaki Kurita, Koji Katahira, Kunihiro Koide, Teruo Ohashi

"The galvanic cell-type hydrogen sensor employing CaZro.9Ino.t03-a. as the solid electrolyte was designed for the measurement of hydrogen activities in molten copper under industrial .conditions. The sensor probe consists of the cap-shaped solid electrolyte with porous platinum electrode on the inside and alumina refractory tube. The gas mixture of the composition 4%H2-0.5%02-Ar was made to flow on the inside electrode. The hydrogen sensor probe was inserted directly into molten copper and the melt was used as the outer electrode. The effect of oxygen activity gradient to EMF was eliminated theoretically by measuring the oxygen activity in the melt simultaneously with an oxygen sensor. The high stability of output and excellent response to the change of hydrogen activity were obtained over the wide range of industrial copper melting conditions.IntroductionIn the metal casting process, hydrogen easily dissolves in molten metals from water vapor in the surrounding atmosphere. Owing to the large difference in hydrogen solubility between liquid and solid metal, dissolved hydrogen becomes a cause of the defects of blowholes in castings or ingots. It is necessary to control the hydrogen content in the molten metals [l]. Using proton-conducting ceramics as a solid electrolyte, high temperature-type hydrogen sensor can be constructed [2]. SrCe03- and BaCe03-based perovskite-type oxides exhibit appreciable proton conduction under hydrogen containing atmosphere at high temperature [3-5]. A hydrogen sensor for molten aluminum using CaZro.91no.103-a. has been developed and widely used in the ·process control in the aluminum melting industry [6,7]. The same type of hydrogen sensor has also been expected in the copper melting industry. .. However, CaZro.91no.103-a shows ·not only proton but also oxide ion conduction in the high temperature and at low oxygen activies like the copper melting· conditions. Then we studied the oxide ion conduction in CaZro.91no.103-a. iit · detail [8]. From the consideration on the EMF of the galvanic cell employing this material as electrolyte, it was shown that the unknown hydrogen activity may be precisely determined from cell potential which is corrected for the effect of oxygen potential gradient And the hydrogen sensor based in this principle was constructed and tested in laboratory-scale [9,10]. We repeated the similar tests in factory-scale and developed the sensor system for practical uses [11, 12]. In this report, the structure and system of the hydrogen sensor for molten copper will be introduced first. The reliability of the sensor will then be demonstrated from the results of experiments for sensor probes carried out in TYK's laboratory."

Jan 1, 2000

By Honggang Zhong, Xin Cao, Qijie Zhai, Hongmei Song, Congsen Wu, Cheng Zhang, Jingzheng Ye

"The influence of superheat on the solidification structure and ferrite/austenite phase transformation of a novel lean duplex stainless steel (DSS) was investigated on a setup, which designed to thermally simulate the continuous casting process. The results showed that the macrostructure of the samples all exhibited chill zone, columnar zone and equiaxed zone. The distance from chill zone to position of columnar to equiaxed transition (CET) moved from 51.0 mm to 39.8 mm with an decrease of superheat from 70 °C to 10 °C, and that the grains in the chill zone tended to be finer. In equiaxed zone, the fme and uniform grains were observed when superheat higher than 40 °C; while, coarse grains were found in samples poured at low superheat. Generally, the volume fraction of ferrite increased along the dendritic growth direction, and stabilized in equiaxed zone. The high superheat decreased the volume fraction of ferrite in equiaxed zone, while it had indistinctive influence on chill zone and columnar zone.IntroductionDuplex stainless steel with approximately equal volume of ferrite and austenite, offering an attractive combination of corrosion resistance and mechanical properties. [ l]. The production of DSS, worldwide application in structural engineering[2] and petrochemical industry[3], have increase by more than 100% in the latest decade[4]. But due to the sharp prices increase of nickel and chromium, lean duplex stainless steels which have lower contents of alloy elements were developed. They perform well in both mechanical and corrosion resistance[S, 6] and even have TRlP(Transformation Induced Plasticity) effect[?]. Nonetheless , the mechanical properties of DSS was affected greatly by the solidification structure, such as columnar to equiaxed transition (CET), grain size and phase content[8]. So, the solidification behavior of stainless steel was investigated widely"

Jan 1, 2014

By M. A. Rabah, F. E. Farghaly, M. A. Motaleb

"Wastewater from industrial galvanization industry was reclaimed under current flow stream conditions. Results showed that the raw water contains 0.7 % by weight total suspended solids (TSS) causing turbidity amounting to 30. Measurements of Zeta potential as a function of pH revealed that solid separation takes place at pH 9. Addition of H2O2 to the polmer solution helps to oxdize ions of iron and zinc metals toinsoluble ferric oxide and zinc hydroxide to a higher state of oxidation. Addition of 5 mg/L of cationic magna flocculants polymeric solution helps the rapid separation of the turbidity. Separation of floccules so formed takes place by filtration. Addition of peroxide ions to the turbid wastewater confirms the physical stability of the flocs so formed. Impurity flocculation takes place in few seconds. Maximum temperature for safe solid removal was <30°C. The treated water was pure and safe for recycling or use in domestic purposes.IntroductionStocks and et. al. [1] show that the galvanizing process introduces spent pickling acid waste production, but its major constituent, could be used. Survey of the operational procedures adopted and the acid wastes produced by UK Galvanizers are reported. Various methods to recovery spent acid of suitable composition and to eliminate zinc contamination was considered. Application of the Kleingarn acid management system reduces waste volume, saves hydrochloric acid (HCl) and increases component throughput whilst, in conjunction with zinc elimination, could allow recycling of the majority of galvanizer’s acid wastes.Dahab [2]; Kerney [3] reported recycling of galvanizing products, including pickleliquor. Kerney suggested a mobile treatment plant for recycling pickling acids. Dahab found that pollution reduction could be achieved by relatively simple operational changes to the process that gave fairly short payback times.Rozenblat and et. al.[4] studied the extraction of zinc (II), iron(III) and iron(II) with Tributyl phosphate (TBP) from hydrochloric acid solutions containing high zinc(II) concentration. Two technological approaches for the separation are considered. Firstly, the selective extraction of iron(III) (iron(II) is oxidized to iron(III)) over zinc(II) with TBP deficiency. Secondly, iron(III) reduction to iron(II) followed by zinc(II) selective extraction with an excess of TBP. Prior stripping, the organic phase was washed with small amounts of water. Scrubbing of TBP solutions containing iron(III) contaminated with zinc(II) gives always a mixture of zinc(II) and iron(III) which must be recycled to the extraction step in continuous process. The following technological concept is proposed: reduction of iron(III) to iron(II), extraction of zinc(II) with 5-10 volume excess of TBP, washing of TBP phase contaminated with iron(II) with small volumes of water and recycling of the scrubbings and stripping of zinc with water."

Jan 1, 2008

By Yang Cui

The partition ratios of lead and antimony between liquid copper and MgO saturated Cu2O-CaO-SiO2 flux and their removal rate by using CuCl-based flux were measured between 1423 K and 1573 K. For Cu2O-CaO-MgOsatd. system, the partition ratio of Pb was not affected by the CaO content at 1573 K, while that of Sb increased with increasing CaO content. The maximum value was 160 at the CaO content of 15.4 mass%. For Cu2O-CaO-SiO2-MgOsatd. system, two liquid phases of calcium silicate rich phase and Cu2O rich phase were observed at 1573 K. The partition ratios of Pb and Sb between calcium silicate phase and liquid copper depended on the (mass%CaO)/(mass%SiO2) ratio. When the (mass%CaO)/(mass%SiO2) ratio increased, the partition ratio of Pb decreased and that of Sb increased. For CuCl flux, the removal of Pb from liquid copper at 1473 K was possible, and a relatively low concentration could be reached. Moreover, most of lead as metal chloride vaporized from flux. For the removal of antimony from liquid copper at 1423 K, it was difficult by CuCl flux, and the removal ratio was approximately 20% for 75 minutes. However, the addition of CaO or Na2CO3 to CuCl flux was relatively effective to remove antimony, and the concentration of antimony reached a relatively low value after 15 minutes by using CuCl-CaO or CuCl-Na2CO3fluxes. Moreover, a small part of antimony as chloride vaporized from flux.

Jan 1, 2006

By Nedam Abed

A fundamental study of the sonochemical leaching of chalcopyrite in ferric ion media has been performed to understand and quantify the effects of sonication and other parameters on leaching reactions. The study covers sulfate and chloride media. The main leaching reaction: CuFeS2(s) + 4Fe3+(aq) Cu2+(aq) + 5Fe2+(aq) + 2S(s) (1) was found to be dependent on temperature and initial particle size, but less dependent on ferric ion concentration. Leaching kinetics were not affected by ferrous ion concentration or the amount of chalcopyrite added. Leaching was performed under a variety of sonication and leaching conditions. Reaction stoichiometry was confirmed through detailed wet chemistry analysis and mass balance calculations. The use of ultrasound activation showed a clear improvement in leaching kinetics and amount of copper extracted, sonication having a catalytic-like effect on the leaching reaction. Compared to experiments without sonication, reaction rates were 2-3 times faster at the same temperature, and could be faster by a factor of 20 for the same initial particle size. Regardless of initial particle size, the amount of copper extracted was comparable under sonication, and could be twice that under chemical leaching, implying the avoidance of fine particle grinding. Sonochemical leaching was found to be only temperature dependent, where the best copper extraction was at 75C. Leaching was further enhanced by the use of a grinding aid. The leaching behavior of chalcopyrite particles remained similar with and without ultrasound activation, implying that the known passivation mechanism in the oxidative leaching was not eradicated. Sonication resulted in coarse particle breakage (ultrasonic milling). Sonication did not contribute to particle passivation, as affirmed from different leaching procedures and sonication in aqueous and organic media. Parabolic leaching kinetics were confirmed for leaching experiments.

Jan 1, 2003