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By C. K. Gupta

Electrometallurgical processes have a definite place in the extraction technology of rare earth metals and alloys. Some of the advantages of the molten-salt electrometallurgical processes include fast electrode reaction, providing accurately controlled large amount of energy to a relatively small reactor volume, negligible over voltage, simplicity of operation, and possibility of accomplishing continuous or semicontinuoue operations. This paper provides a vivid account of the theoretical and practical aspects of electrometallurgical processes for the production and processing of some of the rare earth metals and alloys. Reference has been drawn to the work reported on electrometallurgical processes as applied to the preparation of lanthanum, cerium and misch metal from author's laboratory.

Jan 1, 1992

By Fathi Habashi

"Davy, Faraday, and Bunsen laid the foundation of electrometallurgy which had a· great impact on other areas of metallurgy. Electrometallurgy is presently dominated by the production of aluminum, the electrorefining of copper, and the electrowinning of zinc. It has also been successful in the electrowinning of copper from solutions obtained by leaching-solvent extraction. Electrowinning processes, however, are capital intensive. Improvement of the present technology should be intensely investigated especially when it is expected that such processes will increase greatly as a result of a shift from certain pyrometallurgical processes to pressure hydro metallurgy.INTRODUCTIONPyrometallurgy was used for thousands of years to produce copper and iron from their oxide ores!). Today it is still the only route to produce iron and steel and it is certain that it will remain so for many decades to come because pyrometallurgy is most suitable for the treatment of high grade oxide ores. Even when high grade iron ores are exhausted, it is possible to beneficiate the low-grade ores and produce pellets suitable for reduction in the blast furnace, which is a very efficient reactor, being a heat exchanger as well. Hydrometallurgy on the other hand can be traced to the time of alchemists in the Middle Ages when they were seeking to transmute base metals into gold, and thus were able to prepare many acids and bases which are the essential leaching agents."

Jan 1, 1997

By Vadim J. Jabotinski

Electron beam processing is potentially very attractive for the high temperature treatment of hazardous materials. The very high power efficiency of the electron beam energy source (80- 90% of the power from the electric power line is converted to useable energy) is one of the positive features of this technique. This paper will consider advanced electron beam concepts for solid, liquid, and gaseous waste treatment such as stabilization of radioactive solid and liquid hazardous streams. Fundamental aspects and applications including an analysis of the economic potential of electron beam processing of waste treatment will be presented.

Jan 1, 2000

By Yuri Bychkov

The Electron Beam Melting is the most efficient technology for metals and alloys refining. For ,secondary metals processing the Electron Beam Skull Melting (EBSM) with the electromagnetic stirnng (EMS) of melt in the crucible was shown to be the most appropriate. The copper produced by EBSM with EMS possesses higher density and electric conductivity in comparison with other refining methods. The details for high power electrical machines were cast of the copper waste refined by EBSM technology.

Jan 1, 1995

By Osamu Takai, Yoshiki Sato, Nobuhiro Tajima, Hiroyuki Sugimura

"Amorphous carbon thin films doped with nitrogen ( a-C:N) have been synthesized by means of shielded arc ion plating (SAIP). Their electron field emission properties, that is, threshold field strengths for electron emission and maximum emission current densities, were evaluated and compared with those of pure amorphous carbon (a-C) films prepared by the same SAIP apparatus. Among all of the fabricated a-C:N films, the a-C:N films with a N concentration of 23 %, which prepared using Nz arc plasm at a pressure of 1 Pa with applying a sample bias voltage of -100 V, showed the lowest threshold filed of 13.4 V/µm and the highest emission current density of 1.87 µAfcm2 at a field of20 V/µm. These field emission properties of the a-C:N film were much better than those of the a-C films. The best results obtained on the a-C film in this study were the lowest threshold filed of 15.5 V/µm and the highest emission current density of 0.052 µA/cm2 at a field of 20 V /µm. Nitrogen doping to aC was found to be effective for lowering threshold voltage for field emission and for increasing emission current density. The electron field emission characteristics of the a-C:N films depended not only on N concentration but also on chemical bonding state of nitrogen in the a-C:N films. The presence of the ~-C3N4-like phase, which contributes to improve wear resistance of a-C:N as well, distinguished by the NlsXPS peak at 400.5 eV is proved to be crucial in order to enhance field emission properties of a-C:N.IntroductionThere has been much interest in electron field emission from a cold cathode due to its potential applications in vacuum microelectronic devices including field emission displays which are expected as flat panel displays in next generation [l]. It is well known that efficient emission can be rather readily realized using tip-like shape cathodes, e.g., microfabricated three-dimensional electrodes [2], carbon nanotubes [3-5], etc. However, electron emission from planar surfaces is of particular importance since such a type of cathode is· simply fabricated and assembled into microelectronic circuits. Currently, amorphous carbon thin films doped with nitrogen (a-C:N) prepared by plasma processes have attracted attention because their threshold voltages of field emission are relatively low [6]. Among various methods for preparing a-C:N films, the process using arc plasma is of special interest since, in arc plasma, nitrogen is highly activated and new types of carbon nitride phase are expected to be synthesized. However, field emission properties of a-C:N prepared by arc plasma have been studied in less detail compared with that prepared by the other methods such as sputtering."

Jan 1, 2000

By O. E. Omotoso

This study is part of an ongoing investigation to understand the mechanism of stabilization/solidification of hazardous chromium wastes in ordinary Portland cement (OPC). Tricalcium silicate (C3S*),a major component of OPC is mixed with reagent grade Cr(lll) and Cr(VI) solutions, to simulate complex cementiCr waste systems. Scanning electron microscopy (SEM) and energy disperse spectrometry (EDS) were employed to provide microstructural and chemical information. Transmission electron microscopy (TEMlEDS), apart from complimenting the SEM, was used to probe the distribution of Cr in the hydration products of C3S and to provide crystallographic information. 29Si MAS NMR (magic angle spinning - nuclear magnetic resonance) Was used to characterize the influence of Cr on the hydrated silicate structure.

Jan 1, 1995

"Mechanical alloying (MA) synthesizing technology and thennohydrogen processing (THP) were utilized to produce nanocrystalline Ti-MMC's reinforced by TiB intermetallic compound by using TiH2-B powder mixtures. Powders MA'ed up to 8 hours were examined by X-ray diffraction and SEM study. All MA'ed powders afterwards were HIP'ed at 700, 800 and 950EC for 1 hour. Detailed XRD, SEM and TEM study of the samples were carried out to determine the structure and micrography of the Ti-TiB MMC material processed by MA+THP approach followed by HIP'ing at high temperatures.IntroductionThe fiber reinforced titanium base composites [1,2] which possess a great resistance to high temperature have been investigated. In these studies fibers of C and SiC were used as reinforcing materials. However, these fibers react with Ti-matrix at elevated temperature resulting in product formation at the interface between the matrix and the fiber. Because of the chemical reactions, strength of the product MMC material diminishes.In conventional techniques of whisker reinforced composite material production, the mixtures of matrix metal powders and dispersed fibers are consolidated by hot pressing, HIP and/or hot extrusion. These techniques, however, have some shortcomings. Hard and brittle fibers could be broken during mixing cycle of the processing. Consolidation techniques could also be the cause for fiber breakdown. Attaining of the uniform dispersion of fibers into the metal matrix is not an easy process. The chemical reactions at elevated temperature exposures in the interface between the matrix material and fiber reinforcement cause product formations leading to poor mechanical properties."

Jan 1, 1998

By H. L. Ludtke

Microlaminate composites were fabricated by electron-beam physical vapor deposition. The microlaminates consisted of five layers, each 2 to 4 pm thick, and were composed of either pure metal layers (Cu-Ag), or alternated between metal and intermetallic layers (Nb(Al)- Nb3Al). The microlaminates were heat treated in an Ar atmosphere for 2 to 12 hours, at temperatures of 600°C for the Cu-Ag and 1000°C to 1200°C for the Nb(Al)-NbsAl. Microlaminates were examined after deposition and after heat treatment by scanning electron microscopy and energy dispersive x-ray spectrometry. The effects of heat treatment on the morphological stability of these composites will be described.

Jan 1, 1999

By A. G. Jackson, Mark D. Benedict, Steven R. LeClair, Yang Cao, David M. Conrad

"Electronic Prototyping (EP) represents a new and powerful medium that many in science and technology view as the research paradigm of the future. Actually, EP has many handles, sometimes referred to as simulation-based design involving more long term objectives such as virtual reality, but regardless of the 'spin', the direction of EP is an enhanced visual paradigm to enable a new set of tools for engineers and scientists alike. Tools to not only automate, visualize and compute otherwise intractable problems but to enable augmentations of our ability to perceive that which is interesting and new -""a virtual version of a process"" [1] prodding us on the pathways of materials and process discovery.IntroductionActually there are many reasons to apply sensors to materials, such as smart or adaptive materials/structures, and new materials synthesis/processing [1], only some of which are motivated by improved product quality and/or productivity. Although U.S. Air Force applications of sensors to materials processing represent but one of many perspectives, hopefully it is a perspective which will engender new ideas and insights in addressing future challenges in materials research. To provide context and establish need for future sensor applications in materials processing, we will utilize on one of several Air Force vistas or '21st-Century' objectives."

Jan 1, 1997

By Uday Pal

In direct reduction processes for iron and steel making, significant amounts of Fe-C alloy droplets are generated and these remain suspended in relatively low FeO (around 5%) containing slags. Earlier workers have found that when the FeO content in the slag is <5%, the decarburization reaction becomes extremely slow (virtually ceases to occur) even though the alloy droplet contains a significant amount of carbons (2-3%). Understanding this rate controlling kinetic phenomena is crucial to designing an&apos; optimum direct steel making process. We studied decarburization of Fe-C particles by low FeO (<5%) containing CaO-SiO2A12O3 slags and found that by putting both the droplet and the slag in direct contact with an inert electronically conductive member that extends deep inside the slag bulk were able to quickly and completely decarburize the droplets. A detailed description and an explanation of the process will be presented.

Jan 1, 1995

By S. Goto, S. Yamashita, K. Hata

"The average consumption of zinc dust for purification of zinc leaching solution is more than 25 kg per tonne of electrolytic zinc. Authors proposed to remove impurities in zinc leaching solution by electrolysis instead of cementation by zinc dust. The effects of copper and arsenic on electrodeposition of cobalt in zinc sulfate solution were examined fundamentally using a potentiostat. It is observed that cobalt is easily deposited on a cathode at potentials under -480mV with arsenic. Mesh cathodes of stainless steel and lead anodes were used in a small electrolytic cell and the electrolyte was circulated through 'the electrodes during the electrolysis. The effect of electrolyte circulating rate , pH, cell temperature, current density, and concentration of copper and arsenious ions on removal of cobalt were studied. Removal of Cd and Ni are also examined.IntroductionCobalt is difficult to remove from a zinc leaching solution by a simple cementation reaction using zinc dust. However, it is easily precipitated by zinc dust with co-addition of arsenious or stibinous oxide and copper ion in practical operations(I), (2), (3). The consumption of zinc dust for purification is 16-152 kg per tonne of electrolytic zinc and 65% of this zinc dust consumption is used for cobalt purification. The average retention time for purification of cobalt is 4.5 hours (1). A more economical process for purification is desired instead of zinc dust. The mechanism of this acceleration effect of copper and arsenious oxide on removal of cobalt are explained by the authorsas follows; a galvanic cell is formed between zinc dust and copper which is precipitated firstly, and cobalt is reduced on copper as Co-As alloy by this galvanic current(2). This assumption was confirmed in experiments using a galvanic cell with a membrane( 4). The following galvanic reactions occur between zinc dust and copper precipitate; on copper cathode,2H+ + 2e -= Hz(g)2Coz+ + 2HAs02 + 6H ++ 10e -= 2CoAs + 4HzOand on zinc anode,Zn = Zn = 2+ 2e –This galvanic current becomes almost zero in a zinc sulfate solution which includes only cobalt and no arsenious oxide, and cobalt is weakly deposited on a copper cathode. Cobalt deposition requiers a high degree of cathodic polarization. However, the galvanic current flows almost constantly in an electrolyte, which includes arsenious oxide, and the cathode potential is kept at about -500mV. Cobalt is precipitated as Co-As on the cathode.The authors assumed that cobalt may be removed by electrolysis at a very low current density instead of zinc dust and the following experiments were carried out. In the first part of this paper, the fundamental experiments using a potentiostat on the behaviour of cobalt in zinc sulfate solution are described. In the second part, the results of the electrolysis are reported. Cobalt is removed by a new type of an electrolytic cell, which was desigoed to <Iccelerate the rate of deposition of cobalt. The removal of cadmium and nickel in a solution which includes cobalt and arsenic are also examined."

Jan 1, 1997

By Roland Kammel

In combination with various physical and chemical methods also electrochemical techniques are most frequently used to improve the recovery of metals from aqueous dilute process streams or effluents e.g. in electroplating, metal finishing, mining and metallurgical plants. To insure cathodic metal recoveries with favorable current efficiency and high throughputs per unit of cell volume seve¬ral types of electrolysis cells have been developed comprising extended electrode surface areas and/or intensive electrolyte. agitation. The practical experiences with these units indicate especially for the electrolytic recovery of metals whose values are high, that the treatment cost permits profitable operations with relativly short payback periods for the units. Anodic reactions can be utilized for the removal of undesired anion contents or buildups of impurities. Appropriate combinations of these recovery methods are used to improve the versatility and the overall economy. Industrial applications reveal their potentional as addidtive techniques for existing processes to reduce the metal content of effluents to values that meet the guide lines of environmental legislation whereas integrated in-operation recovery methods are nowadays increasingly introduced to approach nearly close-loop operations.

Jan 1, 1992

By Olli Hyvärinen

The capacity of Outokumpu Pori Copper Refinery has been increased by 50 % to 70 000 t/a in the last five years by adopting periodic current reversal, reducing spacing and installing some new cells in the old tank house building. Five years operation of PCR has proved that it is possible to achieve additional capacity with PCR and yet produce high quality cathodes. The impurity level in anodes has considerably increased, and recently, arsenic, antimony and sometimes bismuth have displaced nickel as the most critical impurity.

Jan 1, 1987

By V. V. Satya Prasad, A. Sambasiva Rao

Electroslag melting technologies have recently been developed for recycling light scrap of valuable metals and alloys such as superalloys and oxygen free high conductivity (OFHC) copper at Defence Metallurgical Research Laboratory (DMRL), Hyderabad. Conventionally, electroslag melting processes use consumable electrodes. Because of the difficulty in compaction of scrap into a consumable electrode of satisfactory quality, non-consumable electrodes such as graphite and water-cooled copper have been designed. Electroslag remelting using a water-cooled non-consumable electrode was developed to melt scrap of a nickel base superalloy. Sound ingots with smooth surface finish and properties comparable to vacuum melted superalloys could. be obtained from scrap using this process. A modified electroslag crucible melting process using graphite crucible and graphite electrode was developed for recycling OFHC copper scrap. Copper ingots with less than 10 ppm oxygen and electrical conductivity"" 100% IACS could be produced. The same process was also utilized to produce copper-based alloys such as copper-chromium and copper-titanium starting from copper scrap.

Jan 1, 2000

By Ralph H. Nafziger

The Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory, has electroslag melted a V-5Ti-5Cr alloy using a fused CaF2, flux. The alloy is a candidate for use in future fusion reactors. One objective of this research was to evaluate the feasibility of the electroslag melting process in separating simulated radioactive isotopes from the V alloy to demonstrate recyclability. Small amounts of Ca, Y, and Mn were added as surrogates for radioactive isotopes. Results showed that this vanadium alloy can be electroslag melted satisfactorily. The impurities added intentionally were removed or decreased successfully. Among the major alloying constituents, Cr was retained but there were some Ti losses. The latter may be controlled with process refinements. This research suggests that the electroslag melting process could be a suitable method for recycling V alloys after use in future fusion reactors, or for processing other reactive metal alloys with more immediate applications.

Jan 1, 1996

By J. E. Murphy

Neodymium was electrowon into a Mg-Cd molten cathode at 650 °C from NdC1,-KC1 electrolyte. With the chloride system, neodymium was deposited into the molten alloy cathode until the neodymium concentration reached 20 wt pct. The alloy was then vacuum melted to remove the Mg and Cd. The current efficiency exceeded 80 pct under optimum conditions and the purity of the metal was 99.9 pct after vacuum melting. As an alternative approach, neodymium was electrowon at 1,030 °C from Nd,O, dissolved in a molten fluoride eleotrolyte. With the oxide-fluoride electrolyte, the metal was electrowon in a molten state with current efficiencies up to 60 pct. The purity of the metal was 99.8 pct with oxygen and carbon as major impurities. A number of problems were encountered including anode effect, low oxide solubility in the electrolyte, high neodymium metal solubility in the electrolyte, and reactivity of the metal with the cell materials. Approaches to improved cell, operation and prospects for commercial adoption of the electrolytic production of neodymium metal are discussed.

Jan 1, 1995

By M. Olper, M. Maccagni, C. J. N. Buisman, C. E. Schultz

The key point of the CX-EWS process is the conversion of lead compounds, contained in the active mass of spent batteries, into lead sulphide. The obtained lead sulphide is leached with ferric fluoborate electrolyte to dissolve lead and oxidize the sulphur from sulphide to the elemental form. The lead-rich solution is fed into a diaphragm electrolytic cell depositing lead and regenerating ferric fluoborate. The introduction of sulphate reducing bacteria technology in the sulphidization step of the battery paste improves dramatically the economics of the CXEWS process, reducing the costs of chemicals, avoiding gypsum disposal and minimising the unit operations of the process. This paper describes in detail this technology change with reference to the economics of the process.

Jan 1, 2000

By Zhongliang Tian, Yun Cheng, Yexiang Liu, Ming Jia, Yanqing Lai

"A fundamental electrochemical study of Si ions in Na3AlF6-LiF melts and electrolysis using liquid cathodes was conducted. Cyclic voltammograms (CVs) clearly showed the depolarization of silicon deposition on liquid cathode by forming chemical complexes with the liquid solvent metals. Besides, co-deposition of Al and Si is possible when Si ions are insufficient in the molten salt. Based on the electrochemical results, silicon diffusion into liquid cathode is modelled and evolution of Si activity with concentration is deduced by a mathematic approach. Electrochemical study using liquid metals as working electrodes, can be used as an alternative approach for the acquisition of basic data on alloy behavior. Galvanostatic electrolysis showed that liquid cathodes are appropriate to collect the deposited solid silicon and the highest collection efficiency is almost 85%.IntroductionRecent years have witnessed an increasing demand for solar-grade silicon (Si) by the photovoltaic industry [1-4]. The preparation of high-purity metals through electrolysis and electrorefining offer many advantages such as low cost, low-energy consumption, and environment-friendly process, and thus has been widely used worldwide. From the perspective of electrochemistry [5-7], by utilizing the electronegativity difference between the impurities and Si and controlling the relevant process parameters, it is possible in principle to electrodeposit monatomic Si from a Si4+-containing compound melt. Moreover, because the carbon content of the high-purity Si obtained through electrolysis can be effectively controlled and used as a very ideal raw material in the preparation of electronic-grade and solar-grade Si, the preparation of high-purity Si through electrolysis has received widespread attention [8,9]. Monnier et al. [9] used a graphite electrode to obtain high-purity Si (99.9 %-99.99 %) from Si02/Na3AlF6 system through electrolysis; however, because the Si was precipitated in a solid form and showed poor conductivity, the deposition rate was too slow. Olsen et al. [10] obtained high-purity Si films via electrodeposition in K2SiF6/KF-LiF system by selecting electrode materials with high surface quality (such as Ag and graphite). However, in order to ensure the film quality, the deposition current density must be relatively low (10-50 mA/cm2), resulting in a low current efficiency and low deposition rate, which are not conducive to reducing energy consumption and applying to practical use"

Jan 1, 2014

By Toshihide Takenaka, Takashi Matsui, Nao Murakami, Masahiro Kawakami

"Electrowinning of Ti have been investigated in a LiF-NaF-KF melt including K2TiF6 at 773-923K by applying electrochemical oxidation ofH2 gas as an anodic reaction. The cathodic behavior of titanium and the anodic behavior of H2 gas were studied by voltammetry in detail to clarify the electrolytic condition for the process. The electrowinning of Ti was carried out by potentiostatic _electrolysis. Steady electrolysis was achieved under the suitable electrolytic condition without breaking out the anode effect. Titanium metal was electrodeposited on a Ti cathode though the deposits were usually powdery. It is concluded that this process is potential if the morphology of the deposit can be improved.IntroductionTitanium has such good properties as high specific strength and high corrosion resistance. However, the availability of Ti has been limited because the price of Ti is much higher than those of other common metals, such as Fe and Al. The production process of Ti ingot from its ore is rather intricate so that the production cost is high. If the simpler process is developed, the production cost should be retrenched. Titanium metal is usually produced by the Kroll process, which consists of the electrowinning of Mg metal in molten salt and the chemical reduction of TiCl.i by Mg metal. The Kroll process is very elabrate, but not simple. Because the chemical reduction ofTiCl4 by Mg metal is highly exothermic, a considerable amount of energy is wasted.Titanium metal can be electrowon in molten salt bath in principle. A simpler and more effective process than the Kroll process may be realized by the direct electrowinning so that the electrowinning of Ti metal has been studied widely[ 1]. Some researchs progressed to a pilot plant stages [2], but the electrowinning of Ti has not been industrialized yet."

Jan 1, 2000

By James R. Craig

The slags generated during gasification of petroleum coke are heterogeneous and con-sist of many different phases. These phases are important because their physical properties affect the operability of gasifiers and because they concentrate many elements that are present in the petroleum coke feed in only minor to trace quantities. An understanding of the chemistry and physical nature of these slag phases is necessary to predict behavior in the gasifier and in considering the ultimate use or disposal of the materials. Slags typically consist of silicate glasses, calcium-silicates, free iron-nickel metallic phases, iron sulfides, and aluminum oxide spinels enriched in iron, chromium, and vanadium. The partitioning of elements among these phases has been analyzed and will be discussed.

Jan 1, 1989