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By Jafar Safarian, Merete Tangstad, Leiv Kolbeinsen

"Silicon and its binary alloys have several applications in metallurgical, chemical, photovoltaic and semiconductor industries. Silicon goes to its liquid state within its production, refining and when it is alloyed with other elements. Therefore, the characterization of silicon melts thermodynamics is important and useful. The liquidus and activities in several silicon binary systems have been recently calculated by the application of two liquidus constants, which were established using the experimentally determined liquidus data. In the present study, the thermodynamic properties of six silicon binary melts, which are simple eutectics, are calculated by analytical approaches. In this case, the changes in the partial and integral Gibbs free energies and enthalpies of mixing are calculated and compared with the experimental data in literature. The enthalpies are calculated by two methods and the calculation results are compared to the data from the literature. It is shown that thermodynamic properties of silicon binary melts can be accurately predicted without the use of complicated thermodynamic software.IntroductionSilicon and its alloys have several industrial applications. Silicon is used for making aluminium-silicon alloys to produce cast parts, mainly for automotive industry. Silicon in the form of ferro-silicon is used to deoxidize and alloy steel and cast iron. The photovoltaic (PV) industry has had a rapid growth in the recent years and silicon is the dominant material used for the fabrication of solar cells. Silicon is primarily produced through carbothermic reduction of quartz in electric arc furnaces and the produced metallurgical grade silicon (MG-Si) contains around 1 wt% impurities. It is further refined to produce solar grade silicon (SoG-Si) with above 99.9999 wt% Si to fulfil the chemical requirement for PV application. Since molten silicon is processed all along the metallurgical route, obtaining fundamental thermodynamics knowledge about silicon melts is valuable for the related industries."

Jan 1, 2012

By E. Krystad, G. Tranell

"The kinetics of boron removal from liquid silicon during slag refining, as a process step in the production of solar grade silicon, has been investigated by means of small scale mass transfer experimental series at 1600°C, using a graphite crucible. The slags were SiO2-CaO based, with or without addition of approx. 19 wt% MgO. Experiments were carried out at slag-metal ratios of 1 or 2, where the silicon initially contained approx. 250 ppm boron. The metal-slag mass transfer coefficients for boron were found to be in the order of 1-3 · 10-6 m/s and were largely influenced by slag composition. The mass transfer rate was higher for the MgO-containing slag than the slags without MgO. The final equilibrium distribution of boron between metal and slag, LB, was determined to be in the order of 2.3-3.3.I. INTRODUCTIONRecent years have seen a race in industry and research aimed at obtaining a reliable metallurgical route for production of silicon for solar cells (SoG-Si) from metallurgical grade (MG) silicon. Metallurgical routes can successfully challenge the traditional chemical routes for production of SoG-Si if they generate metal of sufficient purity while being less expensive in terms of production cost and energy consumption. Efficient removal of boron is one of the greatest obstacles in the refining of silicon by a metallurgical route, because the segregation coefficient of boron in silicon makes directional solidification unfeasible; in addition, the vapour pressure of boron is not high enough for removal by vacuum refining. However, the thermodynamic properties of boron makes removal from silicon by oxidation possible, and thus the process of slag refining of silicon has been receiving increasing attention as a method for boron removal."

Jan 1, 2012

By Zhou Jiemin

A mathematical model is developed to determine the economic thicknesses of refractories and insulations in rectangular furnaces, Both the heat loss cost and the lining investment are taken into account to achieve a minimum operation cost. For the sake of calculating the heat flux, the paper is particularly concerned with the simulation of the three-dimensional transient heat conduction processes in the lining and a Douglas-Rachford method is used to solve the finite difference equations, The model has been used to design an industrial electric resistance furnace operated periodically. the values of temperatures and power consumption measured from the furnace correspond with the model results.

Jan 1, 1991

By T. Mason, R. Macko

Electroless nickel (EN) coatings are widely used in the manufacture of automotive parts, providing uniform coating, corrosion protection, wear resistance and lubrication. In contrast to EN plating benefits, the disposal and treatment of waste solutions can cause many difficulties. The use of electrochemical treatment technology greatly improves _the operation of the main wastewater treatment process and reduces operation costs. A new, state-of-the-art job shop in the Chicago area, which provides EN plating for the automotive industry, has installed a large separated electrolytic cell for the treatment of spent EN solution (from dumps and wastewater). The waste/wastewater is handled by the separated electrolytic cell, batch treatment system, filter press and neutralization station. The implementation of modem electrolytic technology and auxilliary equipment provides an effective waste treatment process that meets environmental compliance criteria.

Jan 1, 2000

By K. D. Mondale

The chemical and physical properties of samples from ten sedimentary zeolite deposits. (representing chabazite, clinoptilolite, erionite and mordenite types), have been determined as a prelude to the development of a wet beneficiation process. The mineralogical composition of each deposit and such properties as morphology, size, apparent density, surface area, pore volume, relative hardness and zeta potential in solution have been determined. Some of these properties, especially apparent density and relative hardness, were found to differ significantly from textbook values. Based on differences in properties between the zeolites and their associated gangue minerals, a wet beneficiation process has been developed which makes use of selective grinding, sizing, sorting and gravity concentration. Additionally, an alternative upgrading process using flotation has been developed for one of the deposits.

Jan 1, 1988

By David Melgaard

A significant emerging recycling, waste minimization problem stems from legacy waste from the nuclear weapons program and from production of power using nuclear fuel. Premium quality metals used in nuclear plants become contaminated, making them unsuitable for reuse. Consequently, decontamination studies were conducted to evaluate the decontamination capacity and partitioning effeetiveness of Electroslag Remelting (ESR). Eight laboratory melts were conducted to evaluate the efficacy of using ESR to transport radionuclides from the liquid metal phase to the liquid flux or slag phase. To determine the decontamination effectiveness, several surrogate compounds for uranium, plutonium and other fission products were added to the melts. During the melts, the melting rate was varied, typical slag additives were used, and two different slag compositions were evaluated. The resultant post-test ingots and slag were then analyzed to determine the partitioning of the surrogates. ESR generally proved very effective in removing contaminates from the metal with a few noted exceptions. -

Jan 1, 2003

By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By Tianzu Yang, Weifeng Liu, Lin Chen, Wei Chen, DUCHAO ZHANG, HUI XIAO

Carbonaceous refractory materials are widely accepted in many reducing smelting processes such as iron and ferroalloys. Oxidizing processes such as copper concentrate smelting traditionally use magnesia and/or alumina/silica refractory materials. The main objection to the use of carbon-based refractories as the exposed working lining in oxidizing applications is the potential for free oxygen to react with the carbon at high temperature, which could rapidly degrade the refractory lining. In 2013, Outotec and GrafTech conducted joint trials of a thermally conductive, carbonaceous lining for smelting copper concentrates in the Outotec® pilot-scale top-submerged-lance (TSL) furnace in Dandenong, Australia. This testwork had two equally important goals; to demonstrate the ability of carbon refractories to withstand oxidizing process conditions, while ensuring that neither furnace operating conditions nor process stability were negatively affected by the refractory material. The paper discusses the input parameters of the trials, key observations during the testwork program, and the results and conclusions from both process and refractory design standpoints.

Jan 1, 2016

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, PSo, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of O2 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By Zhijing Zhang

Long-term thermal stability of ionic liquids is essential for reliable performance of ionic liquids in any engineering applications. TGA studies were carried out on a series of ionic liquids with different cations and anions such as 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-hexyl-3-methylimidazolium chloride ([C6mim]Cl), 1-hexyl-3¬methylimidazolium tetrafluoborate ([C6mim]BF4), 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6mim]PF6), 1-octyl-3-methylimidazolium hexafluorophosphate ([Csmim]PF6), and 1-butyl-3-methylimidazolium bis(trifluromethanesulflonyl)imide ([C4mim][Tf2N]). The short-term thermal stability of ionic liquids was evaluated by measuring the onset temperature of decomposition of ionic liquids, and the long-term thermal stability of ionic liquids was also evaluated by weight loss of ionic liquids over a long period of time at various temperatures. The experimental results showed that the long-term thermal stability of ionic liquids decreased with increasing temperature and was significantly lower than the onset temperature of decomposition of ionic liquids.

Jan 1, 2002

By S. P. Vanka, B. G. Thomas, S. Sivaramakrishnan

"During the continuous casting of steel, transient 'flow events can be very important to the generation of quality problems, such as shear entrainment, surface level fluctuations and bubble entrainment. These phenomena can be better predicted using Large Eddy Simulation (LES) models than the K-E models, which have been extensively studied. In this work the turbulent transient flow in a water model of a continuous caster has been both simulated using LES models and measured using Particle Image Velocimetry (PIV). The results of PIV and LES have been compared to validate the LES model and also to enhance the understanding of the prominent transient features of the flow field. The flow near the top surface in PIV was found to contain periods of 5-1 Os when the velocities were three to four times their mean values, which is of importance to the shear entrainment of the liquid flux. In both simulation and PIV the upper roll structure is found to change chaotically from a single large recirculation structure to a set of distinct vortices. The inlet swirl in PIV is seen to persist more than halfway across the mold, causing a characteristic staircase velocity vector pattern when viewed in a plane parallel to the wide faces. The lower rolls in PIV are significantly asymmetric for very long periods of time (- I-hour) and go through a repeating sequence of features. One of these features involving a short circuit between the upward and downward flow in the lower roll is also seen in the simulation and is of significance to bubble entrapment.IntroductionThe turbulent flow through the nozzle and in the mold of the continuous caster has been studied extensively using computational Reynolds Averaged Navier Stokes (RANS) models of turbulent flow [1,2]. Defects, such as internal inclusion of liquid fl4x through surface shear, pencil pipe defects due to bubble entrapment, surface defects due to level fluctuations are caused by transient flow phenomena oc'curring in the mold. These phenomena can be better predicted using transient Large Eddy Simulation [3] or ""LES"" models."

Jan 1, 2000

By Stavros A. Argyropoulos, Michael Trovant, Norman J. Goudie

"Two studies were carried out to estimate the thermal resistance of various interfaces using experimental and computational techniques. Three types of interfaces were examined. The first study investigated metal-mold interfaces, and the second study focused on metal-metal and metal-oxide interfaces.For the metal-mold interface, the air gap size was measured and subsequently correlated with the interface thermal resistance. The procedural details are outlined for the development of a correlation which predicts thermal resistance as a function of air gap size.Investigation of the metal-metal and metal-oxide interfaces employed data from a series of experiments as input into a model, which solved the inverse heat conduction problem in terms of a resistance estimate. These experiments, involved dipping a cold cylindrical metal into a liquid metal or liquid oxide, respectively. Under these conditions, a shell freezes around the cylindrical addition and a thermal resistance develops during the time period which shell exists . The Heat Transfer Coefficient (HTC) at the addition shell interface differs significantly among the various types of metals and oxides used. In the case of an oxide shell, the (HTC) is about an order of magnitude lower than the (HTC) of the metal shell.INTRODUCTIONIn many metals processing operations there is a need to estimate the thermal resistance at metal-metal, metal-oxide, metal-mold interfaces. This need was further intensified with the recent proliferation of mathematical models, which predict various transport phenomena events. There are many factors which can influence the magnitude of the interfacial thermal resistance. Some of the factors, among others, are as follows: contact temperature, metal thermal conductivity, apparent contact pressure, surface roughness, interstitial gas conductivity, and interstitial gas pressure.In this paper, two studies are reported on the estimation of thermal resistance. The first involves, the development of heat transfer coefficient-air gap relationships at the metal-mold interfaces. The second includes, estimations of thermal resistance at the addition-shell interface. The former case is encountered in the metals solidification and the latter during the melting and/or dissolution of additions to liquid metals or slags."

Jan 1, 1999

By Bao Xiancheng

Jinlong's copper flash smelting process started up in April 1997. In the early days of production, lots of equipment and process problems were encountered. But, through continuous improvements in equipment and operation, the designed productivity was reached two years later and the smelting operation has been greatly upgraded since then. After more than 4 yew of production, we have made great achievements, such as increasing the flash furnace availability, significant improvements in operation control, optimization of concentrate burner's structure and operation, and smooth operation of the whole smelter. This paper outlines Jinlong's operational achievements made after commissioning, and discusses problems that were encountered and their countermeasures. Operational experience is also summarized

Jan 1, 2002

By Amir Rehmat

The Institute of Gas Technology has developed a fluidized-bed process for recovering direct reduced iron from blast furnace flue dust a material currently considered to be a waste from the iron and steel industry. In the process, a portion of the carbon in the flue dust is combusted to supply energy for the endothermic reaction between carbon and steam. The reaction produces reducing gases comprised of carbon monoxide and hydrogen both of which react with iron oxides to produce reduced iron. Up to 95 percent of the iron oxides contained in the waste stream can be reduced to elemental iron. The vitiated reducing gases emanating from the process can be used as fuel in the plant. The yield of iron depends upon the quantity of iron oxide present in the flue dust and generally ranges from 20 to 30 percent of the waste stream. The investment cost estimated for a single processing train dedicated to one steel plant can be recovered in less than one year.

Jan 1, 1996

By Lei Wang, Xiancong Zhao, Hongxu Li, Lifeng Zhang

Recovery of Fe from red mud has been studied using statistically designed experiments. The effects of three factors, namely: reduction temperature, reduction time and proportion of additive on recovery of Fe have been investigated. Experiments have been carried out using orthogonal central composite design and factorial design methods. A model has been obtained through variance analysis at 92.5% confidence level.

Jan 1, 2015

By Vincent Canaguier

Methane is increasingly considered as a promising reductant for metal oxides, including chromite. To assess the possibilities of such reduction route, the gas-solid reactions between Ar–CH4–H2 gas mixtures and synthetic chromites are studied between 950 and 1050 °C. The influence of Mg and Al additions on the reduction-caburization of (Fe,Mg)(Cr,Al)2O4 solid solution is investigated thermodynamically, structurally and kinetically. The product phases are examined by x-ray diffraction (XRD), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). The reaction rate is derived from real-time exhaust gas measurements and post-reaction product analyses such as oxygen analysis. Kinetic models are proposed based on the product phase morphologies and confronted with the empirical data.

By R. G. Robins

Metal separations based on the selective precipitation of phosphates have a potential application in many hydrometallurgical processes. This paper reviews the literature on the solubility of a number of both divalent and trivalent metal phosphates and presents the result of some additional experimental measurements. The systems examined have been modelled to obtain free energy of formation data for the various species. Computer generated solubility diagrams which are described can be useful in predicting a variety of metal separations.

Jan 1, 1991

By Richard D. Hagni

Ore microscopy is a useful technique to detect and study the ore minerals that are associated with sediment-hosted and volcanic-hosted deposits of finely disseminated gold and silver. Ore microscopy can be used to determine the: 1) precious metal-bearing minerals in some ores, 2) associated ore minerals that may form geochemical exploration halos, 3) character of iron sulfide grains, 4) extent of sulfide oxidation, 5) character of oxidized iron minerals, 6) character of original sulfide grains from a study of the hypogene and supergene oxidized ores, 7) relative time of oxidation, 8) character of organic matter, 9) minerals that may consume excessive amounts of cyanide solution, 10) extent of silicification and silica encapsulation, and 11) possibility of salting.

Jan 1, 1987

By A. Perillo

The process, realized in. the Kivcet furnace, can convert continuously lead concentrates, residues and secondary lead bearing materials into a lead bullion free of sulphur and a discardable slag. The lead recovery can be up to 99%. The long experience of about three years at Portovesme demonstrates the capability of the furnace to smelt a very. high range of lead raws without interruption of the operation. The operating costs are very competitive in comparison to the traditional technology. The work place and environment are clean and new tight regulations for the? hygiene control are met. The Kivcet furnace can be considered as consisting of three parts (reaction shaft, waste gas shaft and electro-furnace) connected with a common hearth. The technical basis of the furnace construction is the application of a number of design elements .which have mostly been used before in designs of industrial furnaces, such as open hearth furnace, refining furnace and other furnaces dealing with liquid meta1s. Refractory wear in the reaction shaft with typical pattern from watercooling soon has been stabilized and since maintained. No deformation of the furnace shell and no leakage of metal or s:l:ag through the bottom is? appeared after three years' operations.

Jan 1, 1990

By Berger. P.

The accepted definition of the function of an edge protector fails to specify adequately the several tasks which it must perform to be functionally effective: detailed analysis of these tasks leads to the reasoned conclusion that they cannot satisfactorily be fulfilled by the conventional types of "edge-strips". The true cost of edge protector failure is cumulative: renewal costs are dwarfed by the increased operating expenses and production losses which result from but partial or incipient failure of the edge-strip; yet, the several supposedly improved types, for use with starter-blanks, generally were "built down to a price", prolonging the agony, as it were. Clearly, a fresh appraisal of the problem was overdue, and more especially so with the advent of "permanent" cathodes. As a result, new methods of edge .protection have been developed, including the so-called "EDGEWISE" system in which the present author as patentee *) has a vested interest-which he hereby declares. Due mention is made of recent progress in protecting the edges of aluminium "Jumbo" cathodes in zinc electrowinning operations, although the present Paper is more concerned with edge protection of starter-blanks and permanent cathodes in copper ER/EW processes, where most of the "old" problems now may justifiably be claimed to have been overcome, Mention is also made - albeit at this time necessarily only briefly, and confined to edge protection - of "rigidized" metal blanks and permanent cathodes: a most recent development**) which may prove to represent a "breakthrough": time will tell.

Jan 1, 1987