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By Donald R. Sadoway

"Molten salt electrolysis is a proven technology for the extraction of metals -- all· the world's primary aluminum is produced in this manner. The unique properties of molten salts also make them excellent media in which to treat a variety of forms of waste. Of special note in this regard is electrolysis in molten oxides, a concept put forward by the author, initially as a ""clean technology"" for producing primary metal. However, in the context of waste treatment, electrolysis in molten oxides is a process offering the prospect of changing the-valence of dissolved heavy metals while making pure oxygen gas as the main by-product. Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3, SiO2; CaO, and MgO have confirmed electrochemical production of oxygen on a carbon-free anode. IntroductionMolten salt electrolysis is the electrolytic decomposition of a compound dissolved in an ionic melt. The prime example of this process can be found in the production of aluminum. The compound, alumina (Al2O3)' derived from the mineral bauxite, is dissolved in an ionic melt comprising a multicomponent solution of cryolite (Na3AlF6)' aluminum fluoride (AlF3)' and calcium fluoride (CaF2,). The products of electrolysis are molten aluminum and carbon dioxide, the latter due to the attendant consumption of the carbon anode. Primary aluminum is produced in a reactor known as the Hall cell.' Alternatively, the compound undergoing electrolytic decomposition can be derived from waste. Processing in molten salts, with their capacity to dissolve materials to very high concentrations compared to those attainable in aqueous solutions, can be rather advantageous. High solubilities lead to high limiting current densities, and this, in tum, results in high productivities: For a primer on molten salt electrolysis and a review of the basic literature in the field of molten salts the reader is directed to an earlier publication of the author (1)."

Jan 1, 1996

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothermic reduction, hydro metallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By Donald R. Sadoway

Molten salt electrolysis is a proven technology for the extraction of metals -- all the world's primary aluminum is produced in this manner. The unique properties of molten salts, also make them excellent media in which to treat a variety of forms of waste. Of special .note in this regard is electrolysis in molten oxides, a .concept put forward by. the author, initially as a ."clean technology" for producing primary metal. However, in the context of waste treatment, electroly-sis in molten oxides is a process offering the prospect of changing the. valence of dissolved heavy metals while making pure oxygen gas as the main by-product .Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3 and MgO have confirmed electrochemical production of oxygen on a carbon-free anode.

Jan 1, 1996

By J. L. Johnson

The U.S. Department of the Interior, Bureau of Mines, investigated recovery of concentrates containing tin, tantalum, and niobium from the Kougarok deposit on the Seward Peninsula, AK. To date, 25 million lb of tin has been delineated in occurrences containing 0.36 to 1.32 pct Sn, and the resource potential is estimated to be as high as 25 million short tons at average grades of 0.75 pct Sn, 0.025 pct Ta, and 0,025 pct Nb. Deslimed ore was concentrated to 54 pct Sn, 0.3 pct Ta, and 0.3 pct Nb, with recoveries of 74 pct Sn and 44 pct Ta/Nb using a Humphrey's* spiral followed by a Deister shaking table. Tin values in the slimes were upgraded to a 5-pct-Sn concentrate using a Bartles-Mozley separator followed by flotation. The 5- pct-Sn was further upgraded by fuming to give a concentrate containing approximately 60 pct Sn. The recovery of the two products combined was 80 pct Sn and 46 pct Ta/Nb, A flowsheet with mill-design parameters resulted from the metallurgical testing. An economic analysis was made based on the proposed process.

Jan 1, 1990

By Adam Powell

A Cahn-Hilliard phase field model is formulated to describe transport-limited electrochemical reactions coupled with fluid flow in a metal reduction cell. When the reaction is limited by mass transfer of metal ions from the electrolyte to the cathode, the metal-electrolyte interface at the cathode exhibits a Mullins-Sekerka instability, leading to the growth of dendrite-like "streamers" of liquid metal into the electrolyte, which in turn significantly enhance the apparent mass transfer coefficient there. Model results for iron reduction from ferrous oxide in slag show formation of these streamers. Although the double-layer is not included in this model, the related phenomenon of electrocapillarity can be represented by a gradient penalty term which includes the electric potential gradient, such that interfacial energy is a function of the electric field normal to the interface.

Jan 1, 2003

By Toshiyuki Kozuka

CdTe metal composite semi-conducting material has high potential in good performance of energy conversion efficiency for solar cell and there is much room for improvement of the performance by developing a process of making a thin CdTe film. In this paper, the imposition of intense magnetic field on CdTe electro-depositing surface is proposed, which is one of the possibilities for improving the energy conversion efficiency. In the experiment, cryogen-free super-conducting magnet up to 5T was used and CdTe film was deposited electrically in -o.nv vs. SHE The electrolyte was Cd and Te ammonia alkali solution with controlled temperature in the acrylic cell of 70mm diameter. Electro-deposition behavior of CdTe has affected by the imposition of the intense magnetic field due to microscopic convection in the vicinity of the depositing surface. Electro-deposited surface of CdTe becomes smooth due to microscopic convection around the surface, and the crystallization behavior is also affected, where crystallization temperature and the grain size is changed by the imposition of intense magnetic field.

Jan 1, 2003

By James W. Evans, Brian R. Wildey

"Carbon has been the principal reducing agent in producing metals for centuries. Carbon is an inexpensive reducing agent, but also an effective one, as any undergraduate who knows her Ellingham diagrams is aware. Even in the production of aluminum, an electrolytic process, carbon consumed at the anodes serves to reduce the voltage of the Hall-Héroult cell. The interest in reducing the amount of anthropogenic CO2 has led to this examination of whether a switch to hydrogen as a major reductant is feasible and economic. The main source of hydrogen is natural gas and its production entails the generation of CO2; however, that CO2 is more easily captured than, say, the CO2 leaving an iron blast furnace. Calculations and speculations lead to conclusions about whether there is significant benefit to be obtained from such a radical change in our way of producing metals and the approximate cost of such change.IntroductionThe 1991 paper by Forrest and Szekely1 was one of the first to examine the impact of CO2 emissions from the primary metals industries on global climate change. These authors compared data from 1968 and 1985 and reported a drop in carbon emissions from 115.8 million tons to 65.6Mt over this period, the latter figure representing approximately 1% of the world’s greenhouse gas emissions. Much of this reduction was due to a drop in steel output (with carbon emissions increasing within the aluminum and copper industries in this period) but some were due to technological changes such as increased use of continuous casting. A more recent paper on CO2 emissions, focused on the steel industry in Japan, is that of Ariyama and Sato2. These authors report CO2 emissions of 182.4Mt from the Japanese steel, industry in 2003, down from 194.8Mt in 1990. The former represents 14% of the GHG emissions for Japan in 2003. Much of this emission is from ironmaking and the authors break these emissions down into"

Jan 1, 2008

By S. Eckert, G. Gerbeth, K. Timmel, B. Willers, T. Wondrak, N. Shevchenko, M. Röder

The quality of the produced steel in the continuous casting process is significantly governed by the melt flow in the mold. However, direct flow measurements in liquid metals are still rather scarce. In order to investigate these flow phenomena, three experimental facilities operating with low melting liquid metals were installed at Helmholtz-Zentrum Dresden-Rossendorf (HZDR). The melt flow in the models is measured by the Ultrasonic Doppler Velocimetry (UDV) or the Contactless Inductive Flow Tomography (CIFT), multi-phase flows can be visualized by X-ray imaging. The obtained measurement results are primarily used for validation of numerical models. In this paper we will investigate the fluid flow in the mold and the behavior of the surface of the liquid metal using flow measurements by UDV and surface profile measurement by a laser scanner, respectively. Strong fluctuations and deviations of the free surface were observed in case of a static magnetic field

Jan 1, 2016

By Kimio Itagaki

The distribution behaviours of the VA elements between the gas, slag and matte phases in copper smelting were evaluated on the basis of the thermodynamic data, most of which were determined by the authors. The distribution is basically dependent on the process factors such as temperature, the content of the element in charge, the amount of the waste gas and degree of vapour saturation with the elements. The thermodynamic quantities such as the activity coefficients of the VA elements in matte, the activities of iron and copper, SO2 or 02 potential and the distribution ratio of the elements between the slag and matte phases seriously affect the distribution, and the behaviours in various smelters could be explained systematically and reasonably by considering the changes in these quantities, In oxidation smelting at PSO2= 0.1 to 1 atm, the proportion of arsenic and bismuth in gas is predomi22t for the arsenic and bismuth distributions in both smelting and converting stages. The degree of vapour saturation has serious effect on the distribution, and sufficient contact between gas and matte phases is desirable for transferring arsenic and bismuth into gas phase.The elimination of antimony by means of vaporization is not significant. In reduction smelting at po2 = 10-11 atm, the proportions of arsenic and antimony in the gas phase are quite small, but the proportion of bismuth does not change significantly.

Jan 1, 1983

By Hassan Saalman, Mahmoud Mahmoud, Omneya El Hussaini

The Ferruginous sandstone ore was obtained from Ramlet Hemeyir area, Southwestern Sinai, Egypt, was found to contain 10% rare earth elements (REE). A representative sample has been subjected to sulfuric acid agitation leaching. About 93% of the REE content was released by mixing the ground sample to -100 mesh with concentrated H2SO4 at solid/liquid (S/L) ratio of 1/2 for 5h at a temperature ranged from 250 to 300o C. The REE was precipitated from the prepared sulfate leach liquor of pH 1.0 by adding 35% oxalic acid at 25o C. The precipitation yielded 98% REE. For selective separation of yttrium, the rare earth cake was leached with 31.5% nitric acid. Next, the aqueous solution was contacted with di-(2-ethylhexyl) phosphoric acid (D2EHPA) where 98% yttrium extraction was achieved. Stripping was done with hot H2O (80o C). Finally, a precipitation with oxalic acid was done followed by ignition at 950o C. A yield of 95% yttrium oxide was produced.

Jan 1, 2014

By Ray Y. Lin, Randall A. Blue

"Joining of silicon carbide with infrared using a mixture of Si-30wt.%C as the brazing material has been investigated. Joining was performed at a temperature of 1500 °C in a flowing argon atmosphere for processing times ranging from 5 to 60 seconds. The joining filler materials include thin film silicon obtained by thinning down silicon wafers to about 70 /!m and graphite powder of a 15 /!m average particle size. Joint strengths were determined with a specially designed shear-in-compression jig for testing shear strengths of brittle materials. Cross section examinations of the joined specimens with optical microscopy, scanning electron microscopy and transmission electron microscopy have shown that all joints are essentially void free with excellent wetting between the base SiC and the brazing material. Silicon carbide in the B form has been identified as the reaction product in the joining zone with a transmission electron microscope (TEM) and selected area diffiaction (SAD) analysis. At 1500 °C with a joining time of 60 seconds, the joint has consisted of primarily SiC. With such a high SiC content in the joint, the joint strength is comparable to those by other joining techniques, such as diffusion bonding, as reported in the literature. A kinetic model for the formation of SiC from liquid silicon and carbon is proposed to explain the observed joint microstructural evolution.IntroductionSilicon carbide is of great interest for high temperature structural applications because of its excellent high temperature strength, wear resistance and anticorrosive characteristics [1]. Even though the interest in SiC is high, the use of the material has been limited by the high cost and difficulties involved in forming components of complicated shapes [2]. It is these limitations that necessitate the development of effective joining techniques that are cost effective and able to provide strong joints."

Jan 1, 1996

By T. Shibasaki

Purification of copper electrolyte at Naoshima is carried out by two stage liberation to completely depress copper and impurity ions followed by concentration of the solution to produce crude nikel sulfate as by-product. A new nickel recovering process has been developed and pilot tested recently. It consists of the following process steps.; neutralization of spent electrolyte from liberation section to remove free acid and most part of remaining impurity ions, refining and nickel concentration by solvent extraction, and crystallization of pure nickel sulfate from concentrated strip solution. This paper describes the results of laboratory and pilot plant tests, then briefly discusses feasibility of the proposed process.

Jan 1, 1987

By Elliot Schwartz, Julian Szekely

"In this paper we describe an experiment that was recently performed on the IML-2 Space Shuttle mission in which the thermophysical properties of molten metals were measured using electromagnetic levitation. In the planning of these experiments calculations had to be performed to predict the levitation and stirring forces, heating rates, sample deformation, and internal flows within the sample. These predictive calculations were essential for both the planning of the experiments and for the re-planning of experimental runs during the actual Space Shuttle mission.Introduction""Materials Processing in the Computer Age"" involves the use of mathematical modeling to obtain a quantitative understanding of the phenomena that govern materials processing operations. Microgravity, or space shuttle experimentation represents a specific case in point here; the very high cost of the space shuttle flights, the very limited flight opportunities that are available, and the tight resources aboard a shuttle clearly mandate that these experiments be very precisely planned and that all possible opportunities for mathematical modeling be fully exploited.The purpose of this paper is to present the results of calculations performed for the planning of a space shuttle experiment involving electromagnetic levitation and wherever possible present a comparison of the computational predictions with both experimental measurements and asymptotic analyses. Finally we shall seek to discuss the practical implications of both the computational methodologies and the potential experimental findings."

Jan 1, 1994

By Jinrong Zhang

Major components of soil were tested for their ability to attenuate cyanide. Feldspar, kaolinite, plagioclase and bauxite are found to degrade cyanide at an appreciable amount mainly through adsorption. A soil near a mining site in northern Nevada was studied in detail using a tall column. Many species of cyanide were anlyzed to determine the mechanisms of the reactions of cyanide with soil. Volatilization, adsorption, oxidation, precipitation and complexing were quantitatively identified, being 5 to 10, 11.7, 4.2, 7.3 and 4 per cent of the total cyanide added, respectively. It is found that the oxidation of cyanide to cyanate is due to the catalytic effect of nickel and copper leached from the soil. Precipitation of metal-cyanide complexes occurred at low pH values.

Jan 1, 1991

By M. Neises, M. Roeb, C. Sattler, S. Stenger

"A two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split carbon dioxide as well as water molecules by extracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source, a promising method exists to produce synthesis gas from water and CO2. An easy way of operation is gained by the combination of a ceramic substrate as the absorber structure, which can be heated to high temperatures with concentrated solar radiation, and of a metal oxide coating which is capable to carry out the redox reactions. The performance and kinetics of a ferrite based redox material coated on ceramic substrates were investigated in a laboratory set-up. CO2 could be reduced with significant conversions. In addition, several side reactions were observed like the formation of carbon and like the Boudouard reaction.IntroductionThe search for alternative energy carriers and for processes able to reuse carbon dioxide stimulates the research for sustainable routes of alternative fuel production. In the scope of this search thermo-chemical processes combined with sources of concentrated solar energy have become more and more attractive. Ideally, the only raw materials for such processes are water (H2O) and carbon dioxide (CO2) enabling not only a process free of emissions, but also allow to reduce emissions of other processes by reusing CO2 to provide synthesis gas, which itself can be applied to produce chemical commodities or even better synthetic fuels like methanol or petrol.In contrast to the direct splitting of those raw materials, thermochemical cycles split water and CO2 in several steps and enable hydrogen (H2) and carbon monoxide (CO) generation at temperatures controllable by today’s technical equipment. One of the most interesting thermochemical cycles is a two-step process using metal oxide based redox systems. During the first step of this cycle (the regeneration step) the metal oxide is reduced setting some of its lattice oxygen free according to reaction (1). In the next step (the splitting) the reduced and activated material is oxidised by withdrawing oxygen from water and CO2 and at the same time hydrogen and CO is set free according to reactions (2a) and (2b) respectively."

Jan 1, 2011

By Tadashi Aiura, Yasuhiro Miura

"A small amount(0.2mass%) of Scandium(Sc) was added to the 7.NOl and 5083 Al alloys as a refiner and stabilizer of microstructure, and the resulting microstructures were discussed in comparison with the effects of the conventional additives. The followings are summarized: 1) in the as-solidified structure, a ·decreased tendency of constitutional supercooling and increased solubility of Mg were recognized for the Sc-added 5083 alloy. Sc is a -better microstructure refiner for the 7N01 alloy than Zr, in a sense that it does not suppress the favorable effect of· coexisting Ti. 2) Sc effectively suppresses recrystallization both in the 5083 and 7N01 alloys. 3) The rod like primary Al3Sc crystals formed during solidification, as well as the fine dispersion of Al3Sc precipitates formed by subsequent heat treatment, can act as a strong recrystallization suppresser. IntroductionThe 7N01 and 5083 alloys are the most popular industrial Al alloys and they are widely' used for various structures because of their superior properties. Fine macro and micro structures of the materials are required for obtaining acceptable sec resistance,consistent appearance of anodized surface and good weldability, as well as good mechanical properties. In order to produce fine grain structures, transition metals, such as Cr, Zr, and Mn, have been conventionally added.It has been reported that Sc is an efficient refiner [l, 2] and can be an alternative for the conventional and also suppresses recrystallization in Al alloys [3,4]. Scandium is the lightest transition element and forms an equilibrium intermetallic phase. The equilibrium phase, Ll2-Al3Sc, is coherent with the matrix, and of _spherical shape. A fine dispersion of the spherical precipitates is obtained by quenching and aging after solutionizing annealing. The authors have already reported a part of the experimental results on the effect of Sc on the as homogenized microstructure of the 5083 alloy [5]. In the present study, the effects of Sc on the macro and micro structures of the industrial high strength Al alloys(7N01 and 5083) for extrusion are investigated, and the superior role of Sc as a grain refiner is shown"

Jan 1, 2000

By Kazuhiro Nisizono, Takashi Kuroki, Nobuyuki Mori, Keisaku Ogi

"The improvement of critical current density and mechanical property is essential to the practical application of the superconductive oxides. A solidification technique is developed in this study for the growth of columnar or single Y123 crystal with finely dispersed Y211 and Ag particles through a monotecto-peritectic reaction of Li.(Ba-Cu-Ag-0 rich liquid)+ Y211-+ Y123+Lz(Ag rich liquid). The large solidification rate and temperature gradient can refine the Ag and Y211 particles. But Ag-free region is widely formed along the crystal growth direction in the central part of the Y123 cell. Since this phenomenon occurs because of the cellular growth, it is necessary to narrow Y123 cell width or to grow Y123 crystal with flat freezing interface. By controlling crystal growth direction using a seed crystal, Y123 columnar or single crystal with uniformly dispersed fine Ag particles are obtained. The· behavior of Ag and Y211 particles during the solidification of Y123 crystal is simulated by the peritectic growth model of faceted Y123 crystals.IntroductionY-Ba-Cu-0 superconducting oxide (YBCO) with high critical temperature also has excellent superconducting characteristic under the high magnetic field. The critical current density (Jc) has been enhanced by ·using unidirectional-solidification technique, which can overcome the weak-link problem at grain boundaries and control the crystal orientation and the distribution of Y211 particles which give effective magnetic flux pinning centers in the Yl23 matrix [1-4].In addition to improving superconducting properties, it is necessary to improve mechanical property for the practical application. The silver addition to the melt-textured YBCO superconducting oxide has been reported as the effective method to improve mechanical properties without degrading superconducting properties. Since the material properties are considered to be largely affected by silver particle size, form, dispersion state etc. in the Y123 phase, it is important to control Ag distribution in YBCO/Ag composites. Besides, it is also reported that the silver addition improve the corrosion resistance to the water and CO2 [5,6]. Nishizono et al. [7-9] have reported that the silver distribution in the YBCO/Ag composites is largely affected by the solidification condition, but yet some unclear points are also remained. YBCO has been also fabricated by the zone melting method [10-12], and Furuya et al. [5] and Hirano et al. [13] have reported the fabrication of silver added YBCO composites, but the distribution and behavior of Ag are not investigated in detail"

Jan 1, 2000

By Chen Song

In the experiments of purifying the solution of chlorine leaching from nickel concentrate with N235, the effects of organic phase composition on purifying efficiency have been studied. From the results obtained, the optimal organic phase composition is found to be 25%N235+12%isomerous alcohol +63%sulfonic kerosene (VIV) and the saturated content of cobalt in organic phase is7.95 g*dm3. And then the serial experiment is carried out. The results show that at the given organic phase composition, the purified solution contains p(Ni) >200 gm dm3, p(Ni)l p(Co) >50000 and the contents of Cu, Fe, Mn, Zn meet the technical criterion of standard nickel electrolyte. The cobalt chloride solution contains p(Co) >I10 g L-1, p(Co) lp(Ni)>50000 and the enrichment of cobalt has been achieved.

Jan 1, 2006

By Deepak Gupta, R. Kageyamat, J. W. Evans

"In electromagnetic casting, a liquid metal pool is partly supported by electromagnetic forces resulting from the interaction between induced currents and an alternating magnetic field. Stability of the metal surface is of paramount importance if the cast ingot is to be free from surface defects. Prior work by Garnier and Moreau had suggested that the magnetic field has no influence on the surface stability, but a more complete analysis at Berkeley suggested that surface perturbations are destabilized by the magnetic field once a critical magnetic field is exceeded. More recently we have employed a modified version of the software SOLA to compute the behaviour of a melt surface in the presence of an alternating field. The computed results support the theoretical analysis in predicting an unstable surface. Experimental work is now in progress to examine the stability of a mercury pool in the presence of an alternating field. Introduction and Previous InvestigationsElectromagnetic casting (EMC) is a technique widely employed in the aluminum industry to produce ingot for subsequent rolling. It is a ""continuous"" casting technique (illustrated in Fig. 1) producing ingots several meters high (and perhaps 1m by 2m in horizontal dimensions) at a casting speed of one or two mm. per second. The technology has gained acceptance because the metal is solidified without contact with a mold. Consequently the surface finish of the ingot is usually smooth and the ingot can be fed directly to rolling without machining, the surface (""scalping""). Scalping is necessary with alternative technologies (e.g., DC casting) where a mold is used. Consequently any disturbances that result in surface imperfections of EMC ingot are a serious matter. One type of imperfection is waviness on the surface of the ingot; a line drawn along the crest of a wave would run horizontally around the ingot. This imperfection may be caused by waves on the surface of the metal pool. As the waves reach the solidification line at the periphery of the metal they cause alternate outward and inward bowing of the meniscus at that point with attendant small (but significant) changes in ingot width. Elimination of building vibrations and similar disturbances minimize the occurrence of these surface waves but it is interesting to speculate whether there are disturbances of the metal pool that arise from the electromagnetic forces supporting the liquid metal. These forces are generated by the interaction of currents induced in the melt and the magnetic field produced by the current imposed on the inductor surrounding the melt. The present investigation has been concerned with whether the alternating magnetic field destabilizes the melt surface."

Jan 1, 1994

By Z. Yang

The flotation behavior of the. green algae Chlorella vulgaris and a wild Chlamydomonas spp. was studied in the presence of Zn(II) using dodecylammonium chloride as collector. At about pH 6. both organisms readily float as amine concentration approaches lx10-3 kmol/m3. In addition, electrokinetic measurements were made on the organisms as a function of pH in both the presence and absence of Zn(II). It was found that the Zn(II) has a considerably greater effect on the zeta potential of C. vulgaris than on Chlamydomonas. Zn(II) adsorption studies also indicated that C. vulgaris is able to accumulate more Zn from solution than the Chlamydomonas.

Jan 1, 1991