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By Greg Dowling, Jun Ge, George Shannon, Shufeng Yang, Yongfeng Chen, Lifeng Zhang

"Inclusions in 316L stainless steel ingots poured using two different upgate designs – a traditional upgate and a swirl upgate - were investigated using SEM and ASPEX automated inclusion analysis. The main inclusions were high SiO2 inclusions, MnS inclusions and SiO2-Al2O3-CaO inclusions. More inclusions were detected at the top of the ingot than other places in vertical direction, and more inclusions were at the edge of the ingot than other place in the radial direction. With swirling upgate there were more K- and Na- bearing inclusions than that with the traditional upgate indicating possible more serious flux entrainment with the swirl upgate.IntroductionIngot casting still is very important for production of special steel grades including high carbon chromium bearing steel, thick plate, seamless tube, forgings, bars, and wire rods [1] . During the bottom teeming process, molten steel enters the trumpet and passes through the spider into the runners. Molten steel then enters the ingot mold through an upgate near the end of the runner. In the early stages of filling a mold, a mold flux bag hung in the mold were burnt and the mold flux will cover the top of the rising steel to protect the steel from being reoxidized, acting as well as act as a thermal insulator. So far, some efforts on studying inclusions characteristics in the ingot have been reported. A review paper on the control of inclusions during steel ingot casting was published by Zhang et al. [2] Zhang also studied Inclusions in bottom-teemed ingots of plain carbon steel and found that the >20µm inclusions originated from either the entrainment of mold flux of the reoxidation during teeming process. [3] The results of Nagendra and Du showed that there were more inclusions in the centre part of the ingot [4]. Eriksson et al reported that the composition of inclusions was more complex in the mold samples in comparison to the ladle samples, and more inclusions in the mold were found than in ladle because of the reaction between the mold flux and the molten steel [5]. It was reported that SiO2-CaO-Al2O3 inclusions originating from mold powder with reoxidation product Al2O3 as a part, and there were more inclusions close to the side wall than the center of the ingot in the radial direction. [6]. A more recent investigation showed that four main types of inclusions in runner samples were classified: oxides, sulfides, complex and carbon-nitrides. [7] The flow pattern in the mold during filling has been found to be an important factor regarding inclusions in the ingot. In the early stages offilling a mold, steel enters the mold through the entry nozzle at a high velocity. The effect of the resulting turbulence on the meniscus can lead to the entrainment of mold flux. Efforts have been paid over the years to find methods to reduce the velocity of the molten steel entering the mold, such as using opening angle of the inlet nozzle [8], using swirl blade at the runner [9], using a divergent nozzle combined with a swirling flow generated in the nozzle [10-11]."

Jan 1, 2012

By E. I. Gedgagov, A. V. Tarasov, V. M. Paretsky, A. D. Besser

"Hydrometallurgical technology and equipment have been developed in the Gintsvetmet Institute (Moscow, Russia) for processing of rhenium-containing alloys waste to produce commercial- grade metal products with recovery of all valuable components. The technology is based on waste treatment with hydrofluoric acid with subsequent decomposition with nitric acid at pH = 1 to 1.5 to ensure maximum degree of rhenium conversion to the liquid phase of pulp. Some experimental lots of ammonium rhenate and ammonium molybdate were produced at a pilot plant. The following main techno-economic performance values have been achieved when processing grinding residues (balance-based tests were conducted with a lot of SP-2 alloy waste) to produce ammonium rhenate of high purity, as well as tantalum-niobium, nickel-cobalt and tungsten-molybdenum concentrates: rhenium recovery of 92.3% into a commercial product from grinding waste; production cost of 170-210 US Dollars per 1 kg of rhenium in commercial-grade ammonium perrhenate taking into account its recovery; tantalum and niobium recovery of 75- 77% into bulk concentrate; nickel and cobalt recovery of 88-89% into a mixed concentrate; tungsten and molybdenum recovery of 88% to 91% into concentrate. Introduction During the recent years the use of rhenium has been increasing at a fast pace worldwide [1]. The growing prices for this refractory metal are an essential factor encouraging collection and processing of rhenium-containing wastes. Double-component waste, such as molybdenum- rhenium or tungsten-rhenium alloys can be readily decomposed and the process of rhenium recovery does not cause, therefore, any difficulties. The main separation of metals takes place at the stage of waste digestion with acid, because molybdenum and especially tungsten remain in precipitate in the form of hydrated oxides and rhenium reports in the liquid phase, from which it can be easily extracted by solid ion-exchange or solvent extraction techniques. However, most of rhenium is contained in super-alloy waste [2]. Such waste has different contents of valuable components, such as tantalum, niobium, molybdenum, tungsten, cobalt, nickel, chromium and other metals. The basis of all such super-alloy waste is nickel. Refractory metals in the super- alloy composition are in the form of metallized target-oriented eutectics, and due to this reason hydrometallurgical decomposition of such alloys is a difficult technological task."

Jan 1, 2008

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

By Maria Cristina Ruiz

The removal of iron from the leaching circuits is a common problem in the hydrometallurgical processing of non ferrous metals. Among the currently available processes, hematite precipitation is the most recommendable from an environmental point of view. This paper is concerned with the batch precipitation of hematite from ferrous sulfate solutions. One of the main objectives of the study was to determine the effect of the experimental conditions on the extent of iron precipitation as well as the purity and the particle size distribution of the precipitates. The main variables studied were temperature (180 to 220 ºC), concentration of sulfuric acid (1 to 10 gpl), initial iron concentration (1 to 15 gpl) and partial pressure of oxygen (3 to 7 atm). The results showed that increasing the oxygen partial pressure from 3 to 7 atm produced a very small increase on the rate of hematite precipitation indicating that a large partial pressure of oxygen is not needed for an effective ferrous to ferric oxidation. An increase in the temperature produced finer precipitates with lower sulfur contents. On the other hand, an increase in sulfuric acid concentration and initial iron concentration produced precipitates with larger particle sizes and higher sulfur contents.

Jan 1, 2006

By Xiping Chen, Wangxing Li

"Spent potlining is unavoidable solid waste from aluminum smelters. About thirty kilograms spent potlining is discharged in China to produce per ton primary aluminum. Spent potlining has high level soluble fluorides and cyanides so that it brings heavy pollution to environment. It is prohibited to keep a large amount of spent potlining in open air because it will lead concentrated pollution to local soil and water source due to hydrated reactions between spent potlining and rain water/moisture in air. Landfill may solve pollution of spent potlining provisionally, but it is difficult to be accepted by aluminum smelters because of its high investment, troublesome monitoring and perennial maintenance. Detoxifying of spent potlining not only can remove deleterious fluorides and cyanides in SPL, but also can make fluorides in SPL recycle and return to aluminum electrolysis cells, at the same time benign SPL solid residue can be recycled and ready for cement production.IntroductionChina became the largest primary aluminum manufacturer in 2001. In the past few years, its aluminum output increased by twentyfive percent every year and reached 12.56 million metric tons in 2007. The whole world was very surprised and focused attention upon Chinese aluminum industry. It is more and more important to keep sustainable and steady development with the rapid development of Chinese economy. Aluminum industry is an important base industry and does a great contribution to Chinese economy. But aluminum industry is high energy-consumption and heavy-pollution industry. The government has paid more attention to aluminum industry in recent years. Nowadays the bothersome problem which counterworks Chinese aluminum industry is pollution from solid wastes. Main Solid wastes from aluminum industry are red mud from alumina refineries and spent potlining (short as SPL) from aluminum smelters. Spent potlining are waste lining materials from aluminum electrolysis cells. During production of aluminum, due to reactions between melted electrolyzer and pot lining as well as penetrating of fluorides into pot lining, newly-formed compounds inlayed in pot lining, destroyed the lining structure and brought pot lining cracking. Melt rushed out of lining cracks, cells have to be stopped running and ready for heavy repair. Cell life generally varies from 1500 to 2000 days. Spent potling is an unavoidable solid waste from aluminum industry."

Jan 1, 2008

Accretions of dust on the walls of the offtakes from furnaces and in the waste heat boiler are a cause of significant operating and maintenance problems in non-ferrous smelters. The dust originates from entrained solids in the gas stream and vaporised species that condense during gas cooling. Control of dust formation is very important for minimising the formation of accretions and reducing the severity of environmental problems caused by toxic species, such as those containing arsenic, in the dust. The present paper discusses the formation of accretions and the condensation of dust in copper smelting from a thermodynamic viewpoint. Changes, in gas composition and the amounts and identities of the condensed species in the dust are calculated using computational thermodynamics. Interactions between dust species to form accretions are considered in the light of appropriate phase equilibria. The results show that the nature of the dust formed varies greatly, depending on the temperature and the amount of oxygen present during cooling. Control of the amount of oxygen is required if offtake and waste heat boiler accretion problems are to be minimised.

Jan 1, 2002

By P. Stantke

In recent years the CollaMat process has been used successfully worldwide in a number of copper electrorefining tankhouses as an instrument for measuring the glue concentration and optimizing cathode quality. Owing to its measuring principles the CollaMat can be used not just for measuring the concentration of active glue but also the activity of other substances, which have an impact similar to glue on the copper deposition. In SX-EW plants guar is frequently used instead of glue as a levelling additive. In our laboratory the effect (activity) and the decomposition rate of guar in copper electrolyte was examined. As expected, the results show that guar has an effect similar to glue on the copper deposition. However, at the same temperature, a greater quantity of guar is required to achieve the same results. As with glue, the decomposition rate (due to hydrolysis) of guar is strongly dependent on the temperature. Therefore, in practice, its on-line monitoring is necessary to guarantee the same guar activity at any time.

Jan 1, 1999

By Jeffrey W. Fergus, Shiqiang Hui

"Aluminum is an important alloying addition to the zinc used in the hot-dip galvanization of sheet steel to control the properties and appearance of the resulting coating. Optimization of the galvanization process requires control of the alloy concentration which can be improved through the use of chemical sensors. Aluminum sensors based on molten electrolytes are commercially available but are not widely used because of their high cost. One approach to reducing the cost is to use a solid electrolyte which can simplify the sensor design and thus reduce the cost of fabrication. In this paper, the development of an aluminum sensor based on a solid fluoride electrolyte, specifically magnesium fluoride, will be described.IntroductionThe concentration of the zinc bath used in hot-dip galvanization affects the galvanization process as well as the properties of the resulting coating. Thus, accurate in situ measurement of the alloy composition can be used to improve process control. This paper describes a solid-electrolyte-based aluminum sensor for monitoring the bath composition during hot-dip galvanization."

Jan 1, 1997

By K. Pagalthivarthi, P. V. Desai

"During solidification of alloys, many inter-related physical processes, such as melt convection, mass diffusion, heat transport, macrosegregation and melt-undercooling occur. Several research workers have studied one or more of these effects separately. To answer important questions on solidification behavior, an overall approach interrelating the processes is necessaryAs a first step toward accomplishing the overall modeling, the freezing of a binary liquid metal is examined. The various stages during freezing of the alloy are critically described to build a continuum model for the entire process. Diffusive mixture theory is used to write the conservation equations for the liquid and the mushy zones. The concept of local thermodynamic equilibrium in the presence of curvature effects is used to restrict the number of degrees of freedom within the mushy zone. Constitutive equations relating flux quantities and affinities, the governing differential equations and boundary conditions are discussed briefly for the freezing process.IntroductionA solidification study encompasses such facets as solifidication time, microstructure, macrosegregation of the solute, shrinkage effects and soundness of the casting. Influence of one or more of the coupled heat and mass transfer phenomena such as local solute redistribution, thermosolutal convection, melt undercooling at dendrite tips and heat dissipation to the ambient have all been previously examined [1-3J. Several studies have examined the individual facets of alloy solidification as isolated processses. In fact, the transport processes occur simultaneously and a comprehensive model should include their inter-relationships. In particular, some of the existing studies of the mushy zone [4-6J do not emphasize thermodynamic completeness. This work represents an attempt to develop a thermodynamically consistent model of the entire solidification process on physical grounds."

Jan 1, 1986

By Ibrahim Yusufoglu, Cem Kahruman, Sedat Ilhan, Ahmet Orkun Kalpakhi

"Scheelite is the main raw material in tungsten production. In hydrometallurgical processes, extraction of tungstate ions into solution is very important. During the leaching of scheelite in oxalic acid solutions, tungsten dissolves as a chelate complex. Scheelite includes impurities along with calcium tungstate. Determination of the dissolution of these impurities is important in the subsequent tungsten production stages. In this study, scheelite was dissolved in oxalic acid solutions and the dissolution of impurities was investigated. The quantities of dissolved impurities were determined by ICP - OES and characterization of the undissolved impurities in the leach residues was carried out by SEM - EDS analysisIntroductionScheelite and wolframite ores are used for the industrial production of tungsten. Both ores are dissolved in acidic or basic solutions, and ammonium paratungstate is obtained as an intermediate product. Prior to crystallisation of ammonium paratungstate, all the impurities must be removed. Among these, Fe, Si, P, Mn, Mg and Mo are classified as ""harmful"" elements and different methods are used for their removal [1]. During purification, solvent extraction, ion exchange, etc. methods are used.Potashnikov et al. [2] studied the dissolution of scheelite in acidic solutions and the effects of stirring speed, temperature and oxalic acid concentration on the dissolution kinetics.There are no works in the literature about the removal of impurities from scheelite ores in oxalic acid solutions. Therefore, the aim of this work was to investigate the dissolution mechanisms of impurities during the leaching of scheelite in oxalic acid solutions. The effects of temperature and oxalic acid concentration on the dissolution were also investigated. In addition, the characterization of the impurities which were not dissolved was studied."

Jan 1, 2012

By Michael L. Sorokin

The various methods of converter slag cleaning operation are analysed from the thermodynamk point of view: cleaning using coal, cleaning using combustion products of natural gas and cleaning in presence of matte. All calculations were done, applying the developing computer procedure based on the free energy minimisation algorithm. Three-suffix Margules equations were used to calculate thermodynamic properties of melts; The calculations resulted in recommendations for the practical appliance.

Jan 1, 1995

By Seshadri Seetharuman

The present paper summarises a series of measurements of the interaction parameter of oxygen in liquid copper with respect to a third element, e(M)o, where M is Mn, Zn, As, Se or Te which are common impurities in the liquid metal. The technique employed was the solid electrolyte galvanic cell method. The cell used may be represented as Pt, W or cermet / Cu-O-M // ZrO2 - CaO // AO, A /PT where AO/A represents a suitable oxide/metal reference. The measurements indicate that Mn and Zn interact very strongly with oxygen in liquid copper while, in the case of arsenic the interaction parameter is nearly zero. The behaviour of the elements Se and Te is unique with respect to oxygen interactions in copper bath. At oxygen levels, xo= 10-4 ? 10-5, the apparent interaction parameters are negative, comparable to that for sulphur. On the other hand, at lower oxygen levels, the results indicate that the interaction parameter values are positive. The results are discussed in the light of some of the theoretical models for solute interactions in liquid metals.

Jan 1, 1993

By Luis G. S. Sobral, Gabrielle N. Bard

Copper sulphides Concentrates, from the flotation process of copper primary ore; contain, commonly, small amounts of precious metals, such as gold and silver. During the smelting process of those concentrate all gold and silver are practically in the blister copper, which is cast into anodes. Those copper anodes are electrorefined in an electrolytic system, where the electrolyte is an acid copper sulphate solution, where a high purity electrolytic copper is produced (>999,9/1000). The slime when submitted to an oxidative leaching process, using sodium hypochlorite and hydrogen peroxide as oxidizing agents, turn those metals into solution. This research practical work, apart from concentrating effort on the digestion of the anode slime, aims at evaluating the efficiency of the cementation process of the metals of interest for the separation of them to take place. 141

Jan 1, 2008

By V. Kamavaram

Ionic liquids are novel salts used as potential non-aqueous electrolytes for aluminum electrolysis at low temperatures. In the current research di-alkylimidazolium chloride ionic liquids such as 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) and 1-hexyl-3-methylimidazolium chloride ([HMIM]Cl) were investigated for aluminum electrolysis. Melt formed by mixing ionic liquid with AlCl3 is termed as chloroaluminate and is composed of several polymeric chloroaluminate anions. Ionic liquids are studied as electrolytes for aluminum electrowinning and electrorefining of aluminum based materials (A356, A360, & Al-MMC) at low temperatures. Mechanism of aluminum electrodeposition in these chloroaluminate ionic liquid electrolytes was investigated using electroanalytical techniques such as cyclic-voltammetry and chronoamperometry. Aluminum electrodeposition on pure copper substrate in AlCl3-[BMIM]Cl (1.5:1.0) electrolyte at 30°C melts was found to be quasi-reversible process with a charge transfer coefficient ( of 0.40. Chronoamperograms obtained at different voltages in the range (-0.1 to -1.0 V) revealed that the initial stages of aluminum deposition in AlCl3-[BMIM]Cl melts was instantaneous nucleation followed by diffusion controlled growth of three-dimensional aluminum nuclei. The diffusion coefficient of electroactive species Al2Cl7¯ in AlCl3-[BMIM]Cl melts was found to be 6.5×10-7 cm2 s-1 from Cottrell?s equation and 3.9×10-7 cm2 s-1 from the dimensionless current-time transients.

Jan 1, 2006

By Jian Li

Corrosion resistance of materials is highly dependent on the microstructure of the specific material. Apart from general corrosion rate measurement using techniques like linear polarization and A.C. impedance, microstructural investigations are frequently needed to identify the root cause of corrosion. Advanced techniques, including scanning electron microscopy (SEM) and transmission electron microscopy (TEM), have been well integrated into routine characterization studies. Other microscopy techniques, including electron probe micro-analyzer (EPMA), Auger, X-ray photon spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS), can provide detailed chemistry information on corrosion products. In recent years, focused-ion beam (FIB) microscopes have evolved into an important microstructural characterization instrument. In this study, corrosion of rebar encased in concrete was studied in great detail using advanced microscopy techniques. Corrosion product on the rebar surface was identified as ferrous oxide with relatively large crystal size. The morphology of this passive layer was thoroughly analyzed, and its formation mechanism is proposed.

Jan 1, 2009

By Tam Tran

Most new gold mines in Australia are required to treat tailings to reduce cyanide levels before they are discharged to storage ponds to meet the stringent environmental management guidelines set by government statutory authorities. In New South Wales, the average level of weak acid dissociable cyanide allowed in open tailings dams is now limited to 20 ppm, As stringent environmental guidelines continue to be enforced in Australia as well as in other parts of the world, the management of cyanide wastes has emerged as a key issue for the gold mining industry. This paper provides a critical evaluation on technical aspects related to the use of ion exchange resins and affiliated processes in cyanide management and tailing treatment. Particular attention is given to the use of ion exchange resin technologies in the processing of mixed gold-copper ores, where cyanide usage is the highest. Information presented in this paper is heavily drawn from the experience on the application of ion exchange resin processes at May Day mine, in New South Wales, Australia and associated pilot plant test programs. Issues related to the management of thiocyanate, especially with respect to the recovery of cyanide from thiocyanate are also discussed.

Jan 1, 1998

By C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

By D. Van Dooren

The final goal of the research project is to develop a 3D FEM model that is able to predict the kinetics and micro-structural evolution during the bainitic transformation. The input parameters consist of thermodynamic and atomic mobility data obtained from the ThermoCalc and mCTRA databases combined with structural mechanics data extracted from the stress-strain curves of the fcc and bee phases. In this paper the general principles of the model are outlined and some interesting preliminary results are shown and commented. The full implementation of the model has presently not been achieved yet. In the model the bainitic transformation is considered as a sequence of martensitic (re)nucleation and growth of a ferritic subunit followed by the carbon rejection into the surrounding austenite. The (re)nucleation of the subunits will be described through a non-classical martensitic nucleation criterion. Once a nucleus has been activated at a specific location in the material, a full-sized subunit is instantaneously formed through a displacive mechanism. The stress state in the system that arises due to the transformation strain can be calculated by a 3D FEM programming code. Immediately after the formation of the subunit, another 3D FEM programming code calculates the carbon diffusion from the supersaturated ferrite into the surrounding austenite. The resulting stress state and carbon profiles will be used to determine where and when a new subunit will nucleate based on a renucleation criterion. Keywords: Bainitic Transformation, Modeling, Eshelby, Carbon Diffusion

Jan 1, 2003

By Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa

"Thermodynamic properties of impurities in molten silicon are of prime importance in developing economical production methods of solar grade silicon. In the present research work, thermodynamic properties of boron, the most difficult element to remove from molten silicon, were measured by chemical equilibration techniques at 1723 and 1773 K. Activity coefficients and self-interaction parameters of boron in molten silicon were determined by equilibrating the melt with solid BN under controlled nitrogen partial pressures. Interaction parameters between boron and nitrogen in molten silicon were also determined by equilibrating the molten Si-B alloys with solid Si3N4• Based on the data obtained, the stability diagram of the Si-B-N system was established.IntroductionPhotovoltaic power generation using a silicon solar cell is expected to be the most promising energy source, because it is inexhaustible, cleaner and more safety than conventional energy sources, such as thermal or atomic power generation. At present, expensive off-grade silicon for semiconductor (SEG-Si) is used for a solar cell production. However, if a large-scale photovoltaic energy conversion using silicon solar cell comes into wide use in the near future, silicon will be sure to be in short supply for the cell. Therefore, a development of a new large scale process for solar grade silicon (SOG-Si) production is definitely necessary, which can remove contained impurities from silicon.Among the impurities contained in silicon, boron is one of the most difficult ones to remove by a zone melting or an unidirectional solidification, because its segregation coefficient in silicon is close to unity (0.8). In addition, boron behaves as a p-type silicon semiconductor dopant and, therefore, its content in SOG-Si must be severely controlled. Although some attempts to remove boron by various metallurgical methods have been carried out [I -4], quantitative analysis has not been made due to lack in the information on the thermodynamic properties of boron in molten silicon. From this view point, the activity of boron in molten silicon was determined in the present study by chemical equilibration techniques at 1723 and 1773 K."

Jan 1, 1998

By Gökhan Demirci, Ishak Karakaya

"Energy consumption in electrolytic magnesium cells is well above the theoretical values. However, the mechanism of the back reaction, the main cause of the current losses, has not been fully understood yet. Magnesium dissolution into the melt is generally regarded as the limiting step for the back reaction. Accordingly, present cell designs are made with priority given to fast magnesium removal from the cell. However, experimental data and modeling results in this study indicate that the limiting step for the back reaction between magnesium and chlorine is the chlorine dissolution into the electrolyte when physical contact between electrolysis products was eliminated. Effects of chlorine bubbles on the current efficiency and the cell potential were investigated. Results show that the extent of back reaction is proportional to the chlorine surface area in contact with the electrolyte per unit time, and the cell potential increases with the amount of chlorine bubbles inside the electrolyte.1. IntroductionMagnesium is less dense than the electrolyte in electrolytic magnesium production. Therefore, both electrode products, magnesium and the chlorine gas, move upwards inside the molten salt electrolyte during electrolysis. The upward motion of electrode products promotes the most important current loss mechanism, the ""back reaction"". Separation of the highly reactive species; liquid magnesium and the chlorine gas in the cell, to prevent their recombination is one of the main concerns in cell designs. The employment of large inter-electrode distance or a separation wall in early cell designs; decreased the extent of recombination, but increased the cell voltage and energy consumption. Recent cell designs, on the other hand, make use of lifting action of chlorine gas [1,2] by utilizing smaller inter electrode distances to separate the magnesium and chlorine gas faster. Although energy consumption was reduced, but more physical interactions between electrode products make electrolytic magnesium cells still highly inefficient when energy consumptions are compared with the theoretical values. Today, the most efficient industrial cells utilizing high purity feed operate at 10.5-11.5 kWh kg-1 Mg [3-5] and it is considerably higher than the theoretically attainable value of about 6.0 kWh kg-1 [6]. This large gap demonstrates the necessity of more research on physics and chemistry of magnesium cell electrolysis."

Jan 1, 2011