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By S. P. Marsh, M. E. Glicksman

"The effect of capillarity-driven diffusion on the recalescence of mushy zones is studied in pure materials. The solid-liquid mixture is formed by rapid partial solidification of an initially undercooled melt, and the ratio of the two phases is subsequently maintained constant by an externally imposed adiabatic constraint. A novel technique has been developed that permits tracking of the kinetics of the diffusion-controlled evolution process in situ using precision temperature measurements averaged on a length scale larger than that of the microstructure.The mean ""temperature of a mushy zone is slightly below the bulk equilibrium melting point, and is related to a characteristic length scale of the microstructure through an appropriate statistical average of the GibbsThomson equation. Theoretical considerations indicate that the diffusion controlled recalescence will progress as t- l / 3, where t is time. This behavior is experimentally verified for both succinonitrile (SCN) and ethylene carbonate (ETC), which have markedly different morphologies. The kinetic rate constant is observed to increase monotonically with increasing volume fraction of solid in the two-phase mixtures, although a firm theoretical foundation for this result has not been developed.INTRODUCTIONA dispersed multiphase system seeking equilibrium will generally contain variations in the local .free energy density. These density variations arise from such factors as variations in the bulk free energies of the phases and the distribution of interfacial energies. In this study, we examine the kinetics of diffusion-controlled recalescence in 1 solid-liquid mixture of a pure substance at its melting point. This type of two-phase system is particularly convenient to analyze because of the well-characterized physical properties of pure phases (crystals and their melts) and their interfacial energies, and the absence of any solutal effects."

Jan 1, 1986

By Hiroaki Kawamura, Takeshi Yoshikawa, Kazuki Morita, Yutaka Yanaba

"To develop an alternative metallurgical process for phosphorus removal in the production of solar-grade silicon (SOG-Si), slag treatment of metallurgical-grade silicon (MG-Si) was conducted, followed by acid leaching. Phosphorus-doped silicon alloy or MG-Si containing certain amounts of phosphorus and calcium was reacted at 1723 K and 1773 K with CaO--CaF2 of several compositions. Phosphorus removal from the molten silicon into the slag phase was confirmed by reduction to phosphide ions, P3-, and phosphate ions, P3-. These ions were separately determined using a wet chemical analysis method developed by ourselves. The highest phosphorus distribution ratio obtained was 2. 7 after reaction for 18 h with 17.5 mass% CaO--CaF2 slag. We then conducted acid leaching of the silicon and achieved removal of a large fraction (over 90 % ) of the phosphorus, which was much higher than that obtained by ordinary oxidizing slag treatment.IntroductionIn recent years, the production of solar cells has been increasing rapidly. Because of this, the demand for solar-grade silicon (SOG-Si) has also been growing rapidly. The development of lower-cost mass production processes is therefore needed to provide silicon feedstock. Phosphorus is one of the impurities in metallurgical-grade silicon (MG-Si). Because of its large segregation coefficient (kp = 0.35) [l ], it is difficult to remove phosphorus using a solidification refining process. Vacuum melting is considered to be a promising method for removing phosphorous from MG-Si [2], but the issues of high cost and large energy consumption have still to be resolved.Slag treatment is often used to remove impurity elements by oxidizing reactions during general oxidation refining processes. For example, phosphorus in molten steel is removed into a slag phase as phosphate ions, PO4 3-l-, by the following reaction:"

Jan 1, 2013

By Takashi Miyamoto, Hideo Nakae, Hideki Yamaura, Takeshi Yanagihara

"For the production of partially composed metal matrix composites, namely discontinuous MMCs, using a casting· process, the interpenetrated phase composites with SiC particles were fabricated by pressureless iDfiltration using molten Al-Si alloys. This process is based on a wetting phenomenon, therefore, we discussed the technique based on the reactive wetting. The SiC particles coated by diluted water glass were sintered in a mullite Tammann tube and simultaneously infiltrated with molten Al-Si alloys in air at 1173~1573K. As for the improvement of the wettability between the SiC and the liquid aluminum alloy, Fe3O 4 powder was mixed with the water glass due to the thermit reaction between Fe3O4 and molten aluminum alloy. In some experiments, pure aluminum powder was placed on the sintered SiC to increase the interfacial area and the chemical reaction between the sintered Sic. and the melt. By combining these conditions, we succeeded in the complete infiltration without pressure at 1173K.IntroductionAs is well known, the mechanical properties of metal matrix composites (abbreviated MMCs) are superior than that of ordinary metals. However, their use has not been widely accepted because the production cost is very high due to their poor machinability. Therefore, the production of partially composed, namely discontinuous MMCs, by as the Lanxide process [l,2] has been investigated for many years. The Lanxide process, it takes a long time, sometimes up to 10h, in a nitrogen atmosphere for the infiltration. Therefore, the cost will be higher for common use. On the other hand, a high 'pressure process has been adopted for the production of discontinuous MMCs by the Toyota Motor Corp.[3]."

Jan 1, 2000

By R. N. O'Brien, E. Peters

"It has been discovered that copper concentrates can be leached in strong (40-60%) sulfuric acid with nitric acid, or with oxygen if nitric acid is present as a catalyst. Chalcopyrite is rapidly decomposed at temperatures well below the boiling temperature of the lixiviant (-150 C.) and the resulting copper and ferric salts are precipitated as CuS04.H20 and FeH(S04)z.4H20. Other metal sulfides such as zinc, lead, nickel, etc. are also converted to sulfates that are nearly insoluble. Sulfur is partially converted to elemental and partially to sulfuric acid. Reduction products of nitric acid can be recovered from the distillate with good recovery. Conversion of as-received copper concentrates is largely complete in about 1 hour. Introduction9 molar sulfuric acid is an unusual hydrometallurgical lixiviant: it has a boiling point of about 150 C. and a low solubility for base metal sulfates. Below about 6 molar acid, the boiling point falls below 120 C. and yields much higher sulfate salt solubility, while above 12 or 13 molar acid and at higher temperature sulfuric acid becomes an oxidizing agent, yielding gaseous S02' Thus, sulfuric acid within this range of concentration is capable of acting well above the temperature of boiling water without requiring autoclave conditions, and if typical oxidative leaching conditions are applied to suspended mineral sulfide concentrates, it is possible to obtain a conversion of these sulfides into 'crystalline sulfates. Thereafter, the sulfates can be separated by filtration or by solid - bowl centrifuge and the solution can be recirculated to the reactor vessel. Meanwhile, the solid sulfates can be treated in a typical hydrometallurgical circuit, i.e., dissolved in a return stream that is essentially water, separated from each other by, for example, solvent extraction, and recovered as metals by electrowinning."

Jan 1, 1997

By Erwin Flender, Preben N. Hansen, Peter R. Sahm

"Until now FDM-Techniques have been widely used for Modeling Solidification Processes in Castings. Often a rigid, regular type of enmeshment (cubes, , --) have been used. This has the advantage of low CPU-costs, but the disadvantage of a zig-zag presentation of the interface between the casting and the mold. The last point is the reason why FEM-Techniques, giving the possibility of a true presentation of the shape in the enmeshment, are increasingly used. The disadvantage is the high CPU-costs. In this paper, a technique is presented, which uses the FDM-Mesh with the zig-zag presentation of shape and ADI-Algorithms to calculate temperatures and gradients. The new idea is that the calculated parameters are not presented related to the mesh in which they are calculated, but displayed using the true shape of the casting. Such an advantage of both low CPU-costs and shape correct presentation of the calculated results are achieved. IntroductionThe main reason for using a regular type of enmeshment is that it gives the possibility, via ADI-Algorithms, of obtaining a very fast FDM-Technique. The technique presented by P.R. Sahm and P. N. Hansen (1984), and also used by E. Flender (1985), is numerically so stable that average time steps, at least 200 times larger than the limit given by the explicit FDM-Technique, can be applied. To obtain reasonably good results, average time steps in the range of 20 to 50 times the explicit limit seems to be applicable. It should be pointed out,however, that FDM-Techniques can be used on arbitrary nets, the disadvantages being the same as for the FEM-Techniques. This has, among others, been discussed by P.R. Sahm and P.N. Hansen (1984)."

Jan 1, 1986

By D. T. Smith, L. M. Hsiung, J. J. Schmitt, J. W. Golz, R. L. Lankey, H. N. G. Wadley, J. Z. Zhang, B. L. Halpern

"The microstructure and mechanical properties of Al/AI2O 3 metal-oxide nanolaminates fabricated by' a novel Jet Vapor Deposition (JVD) process at substrate temperatures of ~25° and -250°C have been investigated using transmission electron microscopy (TEM) and nanoindentation methods. The thickness of the oxide layer was held constant between 2 and 5 nm, whilst the Al layer thickness was systematically varied from -3 to -50 nm. Continuity of the Al layers was significantly improved when the nanolaminates were deposited at an elevated substrate temperature (-250°C). The yield strength of the nanolamintes with Al layers greater than -25 nm follows a Hall-Petch type relationship, whereas that of the nanolaminates with Al layers less than -25 nm is better predicted by a Koehler-Lehoczky strengthening model. IntroductionAluminum-aluminum oxide (presumably A12O3) nanolaminates have been recently fabricated using a novel Jet Vapor Deposition (ND) process developed and patented by Jet Process Corporation [1-4]. ND uses sonic, high purity helium (He) gas jets to entrain atomically dispersed vapor and deposit films. It is of interest here because it can deposit multilayered structures (laminates) inexpensively at high rates. Materials with a thin, multilayer structure are of interest because they potentially offer novel mechanical and physical properties [5]. Koehler in 1970 used an image force model to investigate the strength of laminated materials and proposed the use of alternating layers of high and low shear modulus metals to produce high strength composite materials [6]. He predicted that dislocations would have to overcome a large repulsive image force in order to move from metal layer B of lower shear modulus (uB) into metal layer A of higher shear modulus (uA)' The image force (F) is given by the relation:"

Jan 1, 1994

By Xuyang Liu, Xuewei Lv, Chenguang Bai, Meilong Hu

"The electro-deoxidation process for ilmenite concentrate in molten salt was studied by cyclic voltammetry and AC impedance spectroscopy. The results from cyclic voltammetry are consistent with those of AC impedance spectroscopy. The results showed that the electro-deoxidation process for ilmenite concentrate consists of two steps. In the first step, Fe is reduced from the ilmenite concentrate. The second reaction is the decomposition of TiCh. CaTiCh is an intermediate product. At low voltage, the electrochemical reaction is the main step. With the increasing potential, the diffusion of ion is the main rate controlling step for the electro-deoxidation of FeTiO3.IntroductionTitania and titanium-rich products are mainly prepared from ilmenite concentrates (FeTi03), which contain about 40%-60% T1O2 after ore dressing and other physical or chemical processes [1]. At present, the main methods to prepare titania are the sulfuric acid process and the chloride process, but the sulfuric acid process consumes a large amount of sulfuric acid and the materials requirements for the chloride process are strict [2], Since the Electro-Deoxidization in Molten Salt (FFC) method was put forward in 2000, many researchers have successfully extracted the metal and alloys by this method, such as Ti, Cr, Tb, Si, Al-Si, TiV, FeTi, etc. [3-7], FeTi alloy is a typical hydrogen storage material, and because of its favorable properties, the preparation of FeTi alloy has become a hot research topic [7-9]. However, the mechanism of electro-deoxidization has not been studied thoroughly [10-11]. Therefore, in this study, the electro-deoxidation process for titanium concentrate was investigated by electrochemical methods, and the study makes a contribution to improving the current efficiency of the electrolysis."

Jan 1, 2012

By Marko Suput

Titanium is a high-strength, low-density metal nearly immune to corrosion, but limited in use by its high price. The high price is due to the cost of smelting and processing the ore. The research on titanium production using the Solid Oxide Membrane (SOM) process aims to consolidate most of the processing steps required for conventional titanium production into a single step making it an energy-efficient and cost-effective method for producing CP billet and ingot and possibly also powders used to make titanium alloys. In the SOM process experiment, a steel crucible contains MgF2-CaF2-TiO2 flux; an inert metal/carbon rod serves as the cathode; an oxygen-ion-conducting yttrium-stabilized-zirconia (YSZ) membrane in the form of a one-end-closed tube contains either a liquid metal that acts as the anode or liquid MgF2-CaF2 ionic flux that connects the YSZ membrane to an anode. During electrolysis, when the voltage between anode and cathode is higher than the reduction potential of titanium oxide, titanium ions are reduced at the cathode and the oxygen ions pass through the YSZ membrane and are oxidized at the anode. The oxygen ions are oxidized at the anode by a reducing agent, hydrogen gas or carbon, forming steam or CO(g), respectively. To date, a suitable MgF2-CaF2-TiO2 flux has been selected and the operating temperature for the SOM process has been determined. Several electrolysis experiments have been performed. As expected, lower valence deposits of titanium oxides have been witnessed at the cathode prior to depositing pure titanium. Continuing work will aim to extend the electrolysis time in order to pass enough charge to produce a significant amount (100 g) of titanium at the cathode.

Jan 1, 2006

By Mari Naess, Jan Erik Olsen, Gabriella Tranell

"Fume, also known as dust, is produced during metal refining. Exposure to fume is damaging to the health of plant operators. A mathematical model has been developed to study the different factors governing the fuming mechanism. It is shown that natural convection is the main driving force of the phenomenon, and that the fuming rate is highly sensitive to the area of the exposed metal surface. A new feature introduced in the modeling concept is the ability to include a gas flux of unconsumed process gas flowing up through the metal surface. This reduces the fuming rate, and should normally not be neglected.IntroductionFormation of fume from the ladle in which metal is refined into its final specifications is an environmental issue of importance for the working environment in the production plant. In layman-term fume is often known as dust. It is formed when metal reacts with oxygen. As an example of a fuming process, we will focus on ladle refining of silicon. Note that many of the principles and conclusions will apply to other metal refining processes. For silicon production, silica fume (S1O2) is produced when silicon metal (Si) reacts with oxygen (O2).Silicon is produced in a submerged arc furnace. The metal is tapped from the furnace into a ladle for refining. The refining is conducted by injecting a mixture of air and pure oxygen at the bottom of the ladle. The oxygen reacts with the metal and the impurities, and the amount of impurities is reduced according to product specification. At the ladle surface, metal also reacts with oxygen present in the air surrounding the ladle. This reaction produces silica fume as illustrated in Figure 1."

Jan 1, 2012

By Kazuyoshi Sato, Keizo Uematsu, Nozomu Uchida

"Confocal fluorescence scanning laser microscope was applied to characterize the surface flaw of ceramics in great detail. A high potential -of the characterization technique is presented first. Then the technique was applied to clarify the relationship between the flexural strength of ceramics and the surface flaw. This kind of direct information of surface flaw should be essential for the fundamental study in this area, but has been lacking. The examination revealed that large defects are present on the machined surface of ceramics. Their size is consistent to the flexural strength measured on the material. The characterization tool was also applied to examine the formation of surface flaw in machining of ceramics.IntroductionClarification of fracture origin should be the starting point in the study on strength in ceramics. However, this task has been extremely difficult in some ceramics, such as an alumina ceramics. It may break from both internal and surface flaws. The former should reflect the quality of production process and the latter the machining. Examination of surface flaws should be very important for developing a better machining method for ceramics. The knowledge may valuable for establishing a better production process also.ExperimentAlumina Referceram (JFCC) was used as samples. They are cut to size of 3x4x40mm, and the surfaces were ground to meet the requirements of testing method for flexural strength of fine ceramics, JIS R 1601. They were soaked in an aqueous solution of fluorescence dye and evacuated with an aspirator for an hour to allow the solution penetrate into surface flaws. After excessive solution remained on the surface was removed by gentle washing, the specimens were dried at 120°C for 48 hours. The 4 point bending mode was applied to measure the fracture strength."

Jan 1, 2000

By Huaming Yang

The vanadium-doped SnO2 nanoparticle was synthesized by the co-precipitation reaction and subsequent calcination from the vanadium(III) chloride and tin(IV) chloride. The crystal size, pore size distribution, micrograph and properties of the nanocrystalline powders were examined by differential thermal analysis (DTA). thermogravimetric analysis (TGA). X-ray diffraction (XRD), desorption isotherm (Barrett-Joyner-Halenda method) and transmission electron microscopy (TEM). Thermal treatment of the precipitate powder at 600'C led to the formation of crystal0nmincrystal size. Most of the pores in the narmparticle are about 5~15nm in diameter. Effect of doped vanadium on the crystal size of the nanoparticle was discussed.

Jan 1, 2003

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 Ashish D. Patel, Ramesh S. Minisandram

"Vacuum Arc Remelting (VAR) is the final and, hence, critical melting step for the production of a sound, segregation-free ingot for the manufacture of alloys used in rotating components in aircraft engines. A mathematical model for this process has been developed by the Specialty Metal Processing Consortium (SMPC). The model predicts temperature distribution in the solidifying ingot, flow in the molten metal pool, and the electromagnetic field in the ingot. These predictions may be used to estimate the effect of melting parameters on the pool profile in the ingot. In this paper, typical pool shapes and flow fields during VAR of Alloy 718 and Ti-6Al-4V are presented. The differences in the pool profile are primarily due to vastly different melting conditions. The model predictions are compared to the observed pool shapes from industrial-size VAR ingots.1. IntroductionVacuum Arc Remelting (VAR) is a process in which an electrode is melted in vacuum by the heat from a DC electric arc. Metal droplets from the electrode fall into the molten metal pool, which solidifies in a water-cooled copper crucible to form the ingot, as shown in Figure I. The ingot obtained from VAR is sound, and has superior cleanliness and chemical homogeneity. Hence, the process is the final melting process for most nickel-base superalloys and titanium alloys used in the manufacture of critical rotating components (discs & blades) of aircraft engines. Modeling of this process provides an insight into the effect of melting parameters on the molten metal pool in the solidifying ingot, which is a key first step in process optimization and defect prevention. In this paper, typical pool shapes, both measured and predicted, for VAR of Alloy 718 and Ti-6Al-4Vare presented. Alloy 718 is the most common VAR-processed nickel-base superalloy; whereas Ti-6Al-4V is the ''workhorse"" alloy for titanium-based alloys."

Jan 1, 2004

By Julie M. Melluish

The metallurgical response of the Point Leamington deposit has been studied. Two series of bench tests were conducted and various ore samples and flotation products were examined using image analysis techniques. The majority of sphalerite and chalcopyrite grains in this texturally complex ore were found to be smaller than 10 micrometres. Copper recoveries were low with losses mainly as fine inclusions in pyrite. Sphalerite recoveries were somewhat better due to a generally coarser habit. Gold and silver recoveries were also low and only solid solution silver was identified in the ore. The deposit shows poor economic prospects unless additional tonnage of high grade zinc ore can be delineated.

Jan 1, 1989

By J. W. Matousek

In the flash smelting of copper sulfide concentrates, the course of reactions from the burner tip, through flame "burn-out" (the point of oxygen depletion), to settled matte and slag is of particular interest in understanding the mechanisms of the process. Numerous reaction sets can be proposed to describe the chemical changes that might be taking place, but from outside the furnace no one set offers an obvious advantage in explaining the actual processes involved. Only a combination of mathematical modeling and flame and bath sampling can achieve this result. This paper shows that flash smelting, while still reasonably orderly, is a more complex process than suggested by the technical literature.

Jan 1, 1993

By Dongping Duan, Hongliang Han, Li Zhong, Siming Chen, E Zhou

In this study, physical, chemical and microscopic characteristics of Celestine were investigated firstly. Based on which, the thermodynamic analysis of Celestine reduction was discussed. And the experiments of Celestine carbon-containing pellets used in rotary hearth furnace process were studied. The results showed that it is feasible to deal with Celestine by rotary hearth furnace direct reduction process. When the temperature is 1200°C, C/O ratio is 0.8 and holding times is 20min, the conversion rate of SrSO4 in Celestine is above 95%, the utilization rate of Celestine is nearly 100%. This study can provide theoretical and technical basis on economical and rational use of Celestine.

Jan 1, 2016

By James A. Sommers

Combustion of niobium nitride powder in a stream of oxygen results in several niobium oxide phases, depending upon reaction parameters. Under rapid oxygen flow, the oxidation produces a molten mass which coalesces into droplets of ca. 2 mm dimension and effectively quenches to leave NbO2 and other lower oxides of niobium, despite the ambient atmosphere of oxygen. A preliminary survey of reaction parameters which govern the split between reduced and oxidized products is presented. This technique offers novel synthesis means for binary oxides when mixtures of NbN and other materials are combusted together, since the niobium moiety is generated in a molten state.

Jan 1, 1995

By Olga Slavkina

A new technology of bacterial leaching by means of the Thiobacillus ferrooxidance bacteria is proposed. The equations of reactions that describe of the first and the second stage of bacterial leaching of sulfide raw materials containing non-ferrous metals are given. The theory is analyzed and the technology of processing of some complicated substandard concentrate containing copper and zinc is proposed. The main technological operations including a two-stage bacterial leaching and stages of copper and zinc recovery in the form of marketable product are described. The results of the experimental validation of the main technological parameters of the first stage are given. The main possibilities of a more complete zinc and copper recovery at the second stage of bacterial leaching are discussed in comparison with single-stage leaching process.

Jan 1, 2003

By Vladimir Mindin

Simulation of complex equilibria is usually done in the P-T-X coordinates, where "Xu is the amount of individual chemical components in the system. This approach is not productive in some very important cases: (i) investigation of "open" systems, (ii) determination of coordinates (trajectories) of mono-variant points, among others. To solve these and some other problems, we use the idea of chemical potentials of elements (CPE) of the system. A system of different coordinates axes (CPE-axes ) leads to a new strategy of simulation, observing the results of the simulation, and to efficient technology of compressing and storage the data of the simulation.

Jan 1, 1994

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