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By R. Boom, B. Kraaijveld, H. Kuntzel, Y. Meteleva-Fischer

"Alloying refining with rare earth elements followed by acid leaching was examined for the potential of upgrading of metallurgical grade silicon. Microstructure study of silicon alloyed with small additions of rare earths showed behavior relatively similar to the influence of calcium addition. After alloying with neodymium the phosphorus content was detected in various intermetallic silicides containing neodymium and iron. The content of lanthanum and neodymium in refined silicon was by several times lower than that of aluminium and calcium. Alloying with lanthanum and neodymium at smaller additions than calcium reduced the phosphorus content down to the same level. The efficiency of lanthanum and neodymium in removal of boron and phosphorus at the 1-2 wt% of their additions and their low solubility in silicon make the alloying with these metals followed by acid leaching an attractive option for the refining route of metallurgical grade silicon up to solar grade.IntroductionA striving for a cheap ""green"" energy directs the research interests in silicon solar cells towards new efficient refining routes for metallurgical grade silicon (MG-Si, -98% purity). The silicon price determines up to high extent the solar module's price, so that cheap and efficient metallurgical process is awaited. The research challenge is to fulfil the purity requirements of solar grade silicon (SoG-Si, 6N) by competing with the energy-consuming and environmentally unfriendly Siemens process. Most difficult impurities to remove are boron and phosphorus, so technologies dedicated to their efficient removal attract an attention of industry and academia.Alloying refining (also known as solvent refining) is one of the most promising refining options, which is based on a principle of solid-liquid extraction using limited solubility of impurity elements in solid silicon [ 1]. Various elements were proposed for alloying refining: aluminium [2], calcium [3], tin [4], iron [5], copper [6] etc. The attractiveness of the alloying refining is in decreasing a melting point of the metal mixture and an affinity of the alloying element to the most harmful impurities, especially to boron and phosphorus. However, the difficulties are still faced due to self-solubility of the alloying elements, their low affinity to boron and/or phosphorus, silicon losses and necessity of removal of the silicide impurity phases in an additional step, using acid leaching [7], fractional melting [ 8] etc."

Jan 1, 2013

By Yichi Lu, Haydn N. G. Wadley, Douglas T. Queheillalt

"Using a 3-D ray tracing methodology combined with laser ultrasonically measured elastic constant data near the melting point, ultrasonic propagation in cylindrical single crystal bodies containing either a convex or a concave solid-liquid interface have been simulated and used to design new sensing concepts. Ray paths, wavefronts and time-of-flight (TOF) of rays that travel from a source to an arbitrarily positioned receiver have been calculated. Experimentally measured TOF data have been collected using laser generated/detected ultrasound on model systems with independently known interface shapes. Both numerically simulated data and experimental results have shown that the solidification (interfacial) region can be identified from ultrasonic transmission TOF data. Since convex and concave solid-liquid interfaces result in distinctively different TOF data. When TOF data collected in the diametral plane are used in a nonlinear least squares algorithm, the interface curvature has been successfully reconstructed and ultrasonic velocities of both the solid and liquid obtained. The reconstruction errors were found to be less than 5%.IntroductionMany of today's single crystal semiconductors are grown by variants of a vertical Bridgman technique in which a cylindrical ampoule of a molten semiconductor is translated through a thermal gradient, resulting in directional solidification and the growth of a single crystal, Fig. 1.1 It has long been recognized that during crystal growth the velocity and the shape of the solid-liquid interface, together with the local temperature gradient, control the mechanism of solidification (i.e. planar, cellular or dendritic), the likelihood of secondary grain nucleation/ twin formation (i.e. the loss of single crystallinity), solute (dopant) segregation, dislocation generation, etc. They thus determine the crystals' resulting quality.2-4 The solidification rate and the solid-liquid interface shape are also sensitive functions of the internal temperature gradient (both axial and radial) during solidification.5•6 This in turn is governed by the heat flux distribution incident upon the ampoule, the latent heat release at the interface, and heat transport (by a combination of conduction, buoyancy and surface tension driven convection, and radiation) within the ampoule. The solid-liquid interface's instantaneous position, velocity and shape during crystal growth are therefore difficult to predict and uncontrolled during growth, especially for those semiconductor materials with low thermal conductivity (e.g. CdTe).4-6 The development of technologies to non-invasively sense the interface position and shape throughout the vertical Bridgman crystal growth process has therefore become a key step toward developing a better understanding of the growth process, for enabling sensor-based process control, and thus ultimately for improving the yield and quality of difficult to grow semiconductor materials like CdTe."

Jan 1, 1997

By Yi Tan, Kazuki Morita, Yaqiong Li

Molten Si-Al alloy, with the addition of Sn, was used for metallurgical grade Si purification by a low-temperature solidification method, with the aim of improving the recovery rate of Si. In this ternary melt, bulk Si was grown with a planar front by a directional solidification process under a well-controlled thermal gradient and growth rate conditions, thereby reducing the contamination of solvent metals. Effects of cooling rate, amount of Sn addition, and temperature gradient on the quality of bulk Si were determined. The criterion for constitutional supercooling for single-phase growth from multicomponent melts was employed to evaluate the growth process.

Jan 1, 2015

By Jan Dabrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures at each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 2D graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mu, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By Stig Petersson

Slag from the converting of copper matte is usually recirculated to the smelting furnace. This recirculation generally causes disadvantages as magnetite-build-up in the furnace, accumalation of impurities as antimony, lead, nickel etc in the process. The treatment of converter slag in a separate furnace in order to recover the copper and nickel content would be of advantage from several points of view. At the Mining and Metals Division, Boliden, testwork has been carried out to treat converter slag from the PS-converters in a separate furnace. The tests have been performed in laboratory and pilot plant scale. The pilot plant tests have been carried out in a TBRC with charges of 5 tons. Based on these tests a full scale TBRC has been projected in order to treat the slag from the PS-converters. This slag will be reduced with copper concentrates to give a matte and a final slag low in copper and nickel. The background and data from the testwork are presented. Also the lay out, technical data and flowsheets for the projected process are shown as well as some production data from the Rönnskär smelter.

Jan 1, 1976

By Tuula Mäkinen

One of the latest applications of the Outokumpu Flash Smelting Technology is the direct smelting ,of nickel concentrates to metallised low-iron nickel mattes. Compared to the conventional nickel smelting, the new DON process needs a lower number of smelting vessels resulting in considerable economic and environmental benefits. Fundamentals of smelting nickel concentrates in one stage to low-iron mattes are presented. Properties of nickel. smelting slags with an emphasis of the slag fluidity at high MgO-levels are also discussed. Conditions prevailing in DON mattes at high oxidation degrees are presented as well as their influence on the behaviour of such mattes in the settler and on tapping the furnace. Distributions of elements in the direct smelting are presented and compared with the conventional process. A further comparison is made with pilot-plant data and the industrial scale.

Jan 1, 1998

By J. K. Brimacombe

Plant trials have been conducted at the Tacoma Smelter of ASARCO to assess the effect on tuyere blockage and refractory erosion at the tuyere line, of increasing the injection pressure of air into a Peirce-Smith con¬verter. Four tuyeres each having an ID of 19.1 mm (3/4 in) were installed toward one end of the tuyere line of the No. 4 Converter. Air and oxygen-enriched air were injected at 414 kPag (60 psig) through these tuyeres and at the usual 83 kPag (12 psig) through the remainder of the tuyeres in an otherwise normal converter campaign. The test campaign consisted of 88 charges and lasted for 89 days. During this period, punching of the high-pressure tuyeres was found to-be unnecessary; and when, as a precaution, the tuyeres were cleaned by hand at the end of a charge, they were always open. Also it was observed that the flow of high-pressure air remained constant. Accretion formation around the tip of the high-pressure tuyeres varied from charge to charge and was influenced by the matte grade and the level of oxygen enrichment.

Jan 1, 1983

By John R. Goode

Barrick Gold Corporation operates gold mines in the United States, Chile, 'Peru, Canada, and in the near future, in l1anzania. Barrick meets environmental requirements and limits the potentially adverse effect of cyanide discharge to the environment using various cyanide destruction techniques. Barrick operations use, or have used, natural degradation, ferrous sulphate, hydrogen peroxide, Caro's acid, alkaline chlorination, and the SO/Air process for cyanide destruction. This paper presents a general discussion of the options for controlling cyanide in plant effluent and provides details of Barrick's operating experience including general notes on costs.

Jan 1, 1998

By P. N. Anyalebechi

"The effects of solidification rate, initial melt hydrogen concentration, and grain refining on porosity formation in aluminum alloy 2024 have been investigated with unidirectionally cooled laboratory-size ingots. The ingots were prepared from melts containing hydrogen concentration of 0.059-0.27 cm3/100 g and solidified at 0.2-37 °C/s. As expected, the amount of porosity, average pore size, and pore number density increased with increase in melt hydrogen concentration and decrease in solidification rate. However, the effect of solidification rate was greater at the very low melt hydrogen concentration (0.059 cm3/100 g). These results are consistent with reported effects of solidification rate and melt hydrogen content on porosity formation in other aluminum alloys. Interestingly, addition of grain refiner slightly increased the amount of porosity and the average pore size, especially at solidification rates above 1°C/s. IntroductionIn shaped castings and wrought products fabricated from ingots, billets, bars, or slabs of aluminum and its alloys porosity formation is a problem. This is because it compromises their tensile strength, fracture toughness, and fatigue properties [ 1-18]. The pores are usually the crack initiation and propagation sites [6,8,9] and the largest pores tend to dictate the fatigue life of the aluminum products [9,10,14]. Porous regions within an aluminum product probably yield first due to the reduced tensile load bearing capacity, causing the concentration of the strain near the voids which subsequently results in premature fracture. In aluminum alloy ingots, billets, bars and slabs porosity formation is particularly problematic because of its persistence through fabrication and potential for reappearance or exacerbation during subsequent thermal treatment processes before and/or after fabrication [19]. In fact, persistence of microporosity is a serious problem in large thick plates of wrought aluminum alloy products that must be rolled from correspondingly large direct-chill or electromagnetic cast ingots. Some of these thick plate products are machined into large aircraft components that are required in service to withstand multi-directional stresses and to possess high fatigue strength, fracture toughness, resistance to stress corrosion cracking, and strength in the short-transverse direction [1,20]."

Jan 1, 2011

By Shuqiang Guo, Xionggang Lu, Yuyang Bian, Weizhong Ding, Lan Jiang, Kai Tang, Changyuan Lu

For recovery of rare earth elements from the NdFeB based permanent magnet scraps, a high temperature process was used. Permanent magnets scraps were firstly oxidized in air. The optimal oxidation conditions under air are at temperature of 700oC holding for 30min. After the oxidation process, the oxides were reduced by graphite crucible at 1500oC under Ar atmosphere. By this way, the rare earth elements were recovered in the form of oxides, and Fe was separated to the metal phase. Boron distributed in both the rare earth oxides (REO) containing slag and the metal phase. In order to reduce the boron contents in the rare earth oxides, the carbon saturated iron bath and NdFeB added carbon saturated iron bath were used to refine the slag. By this process, the rare earth oxides with a comparatively high purity of 98.2% were gotten.

Jan 1, 2015

By J. W. Lyman

The U.S. Department of the Interior, Bureau of Mines, investigated methods to recover valuable rare-earth materials from NdFeB magnet scrap. Although several processing techniques were evaluated" the best separation of rare earths from the NdFeB magnet ,scrap was obtained by sulfuric acid dissolution followed by precipitation of recyclable rare-earth salts. Both sodium and ammonium intermediate double-salt precipitates' that can be converted to a variety of useful neodymium products were investigated. The sodium system showed a neodymium recovery of 98 pct, while the ammonium system yielded 70 pct during double-salt precipitation. The iron-rich effluent following the rare-earth recovery was treated to produce sodium and ammonium iron jarosites that can be disposed of or converted to hematite. By following this new procedure, many materials handling and economic disadvantages found with fluoride or oxalate direct precipitation were avoided.

Jan 1, 1992

By Rak-Jun Choi

Plasma-induced damage of InGaN/GaN multiple quantum well (MQW) light-emitting diodes (LEDs) has been studied in terms of forward turn-on and reverse breakdown voltages, together with etch rate and surface morphology. The physical degradation of sidewall along with rough surface morphology of n-GaN caused by increased ion scattering induced the deterioration of the forward and reverse voltages. It was found that the turn-on voltage is sensitive to the surface roughness of the etched n-GaN and the breakdown voltage is strongly affected by the sidewall contamination. Annealing under nitrogen after the mesa etching improved the electrical properties of the InGaN/GaN MQW LEOs. Efficient blue light-emitting diodes (LEOs) were fabricated using InGaN/GaN triangular MQWs. The LEOs with triangular QWs showed a lower operation voltage and 2.4 times higher light output power than those with the rectangular MQW LEOs at 20 rnA and 20 "C. The intensity of electroluminescence (EL) at 20 mA was almost independent of ambient temperature in the triangular QW LEO, but decreased substantially in the rectangular one.

Jan 1, 2003

By George E. Cook, Peter C. Levick, Francis M. Wells

"Relationships are established between the peak current of a pulsed, rectangular current waveform and the pulse current duty cycle under conditions of constant arc power. By appropriate choice of these interrelated parameters, it is shown that the arc pressure may be varied over a wide range even though the arc power is held constant. The methodology is suggested as a means of countering the effect of gravity in 5-G welding, while maintaining constant heat input to the weld. Combined with appropriate penetration sensors, the methodology is additionally suggested as a means of controlling penetration. IntroductionBoth low frequency pulsation (typically 0.1 - 20 Hz) and high frequency pulsation (> 100 Hz) are often used with GTA welding. Benefits derived from pulsing include improved weld quality and better process control.Advantages cited for low frequency pulsation include claims that the total heat input to the weld is reduced, the weld bead size is reduced, weld penetration is increased, grain size is reduced, porosity is reduced, weld distortion is reduced, thinner materials can be welded successfully, and the tolerance of the welding process to material and production variations is improved (1-16). With respect to the latter, pulsing aids control of weld bead penetration by increasing the tolerance to component dimensions and joint fit-up. It also reduces the sensitivity to disparities in heat sink, and it helps to reduce distortion in thin section material or distortion attributable to poor clamping. In certain materials it can reduce the sensitivity to surface oxides and to cast to cast compositional variations (16). Low frequency pulsation is also useful in welding thick materials mated by a prepared groove. In these applications the low frequency pulsation is used to obtain proper sidewall fusion as the tungsten electrode is weaved from one side of the groove to the other. In this case the weld current pulsation is synchronized with the cross seam weave pattern, such that the high current pulses occur at each sidewall. This type of low frequency pulsation has proven particularly useful in welding with narrow width groove designs (17-21). Finally, Ecer (22) has shown that the pulsed current arc is more stable against magnetic disturbances than an equivalent constant current arc."

Jan 1, 1986

By Youn-Bae Kang, Jong-Jin Pak, Min-Kyu Paek

The critical evaluation and thermodynamic optimization of Mn-Si-C and its sub-binary systems have been carried out over the whole composition range from room temperature to above the liquidus temperature. The solution properties of the liquid systems have not been clearly described because the liquid solution exhibits a high degree of short-range-ordering. In order to predict the thermodynamics of the liquid solution, the liquid phases were optimized by the modified quasichemical model. The model parameters of the solid phases were also optimized by the compound energy formalism to best reproduce the phase diagram and important thermodynamic properties in Mn-Si-C system. Using the model parameters, various thermodynamic calculations were carried out. The present database will be a part of larger thermodynamic database for the ferromanganese alloy database.

Jan 1, 2014

By Derek J. Fray

"A need exists for fast and accurate analysis of species in various phases at elevated temperatures. Although modern analytical techniques are very efficient, the equipment is usually situated some distance from the industrial operation and time is spent taking the sample and sending it to the analytical facility. Several minutes can easily lapse and, during this time, heat must be supplied in order to keep the system molten and, if the composition is changing rapidly due to a refining process or reaction with the environment, the information may only be of retrospective use. Perhaps more important reasons for the use of on-line sensors are that instantaneous analysis gives better control, process optimisation and the minimisation of energy losses and pollution. To date oxygen has been the only element which is measured widely using solid electrolytes. However, the analysis of many more elements is required and possible electrolytes for other species are discussed. For some elements, ~here is no suitable conducting electrolyte and, therefore, a different approach is adopted where the electrolyte, in which one species is mobile, comes to equilibrium with another species. IntroductionThere is an ever increasing demand for the development of sensors for on-line measurements in most areas of technology and, in particular, metal processing. This is especially relevant in situations where greater control can be achieved by monitoring the chemical composition of the melt during processing and where a minor constituent in the melt can have a major effect on the properties of the finished alloy. Although modern analytical techniques are fast and reliable, the equipment due to its complexity, is frequently situated away from the process area and valuable time may be spent in sampling and transportation. During this period, heat may have to be supplied to prevent solidification and the refining reactions may be continuing, and, therefore, the analytical information may not be of direct use."

Jan 1, 1988

By E. J. Peuraniemi

Primary copper production using suspension smelting techniques like Outokumpu Flash Smelting always causes some dust formation. Flue dust particles are formed when sulphide feed material reacts violently with oxygen inducing particle disintegration and total desulphurisation of fragments. In the process, flue dust follows the off-gases to the heat recovery boiler (HRB) where its sulphation takes place because of prevailing conditions. Sulphation releases heat and causes also a drop in particle melting temperature and, further, particle sticking to the walls and heat exchange tube banks. Sulphation of synthetic CU20 particles were examined using a laboratory scale fluid-bed reactor. This study aims to a better understanding of flue dust behaviour in a HRB and, thus, to a better operational practise and design of a HRB. The effect of PSO/PO2 -ratio and temperature on the sulphation kinetics were tested. Standard chemical analysis, light optical and scanning electron microscopy with energy dispersive spectroscopy were used to examine the samples.

Jan 1, 2001

By Suguru Kohno, Yoshihiro Momose, Masakazu Honma, Tokirou Kamosawa

Copper metal surfaces have been examined by an extremely sensitive surface analysis technique called temperature programmed photoelectron emission (TPPE). The surfaces were ultrasonically cleaned and subsequently abraded by a screw in organic solvents and water. The TPPE apparatus is composed of a Geiger counter with Q gas (He+ iso-C4H10). The curve of photoelectron emission (PE) intensity vs. wavelength from 300 to 170 nm, termed PE spectrum, was repeatedly measured at different temperatures in the temperature- increase process from 25 to 350°C. The number of emitted electrons in a PE spectrum (PE total count) increased, reached a maximum at-250°C, and decreased with increasing temperature. With the surfaces cleaned alone in the liquids the maximum PE total count decreased in the order C3H70H > (CH3) 2CHOH > C2HpH > CHPH > H2O. With the mechanically abraded surfaces in the liquids the maximum PE total count changed as a function of the abrasion period and the maximum tended to appear at higher temperature with increasing abrasion period; the maximum value at 10-min abrasion decreased in the order H2O > CHpH > C2HPH > (CH3) 2CHOH > n-C3HpH. It was suggested that the TPPE behavior can be related to the acid-base interaction between the alcohols and the abraded metal surfaces and the presence of a contaminant over layer on the surface. From the XPS analysis of the 01 s spectra it was suggested that the chemical change of the adsorbed oxygen to oxide oxygen with temperature plays a substantial role in the appearance of the maximum PE total count.

Jan 1, 2000

Equilibrium calculational software programs can be effectively utilized to illustrate the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation to students studying hydrometallurgy. The calculational program STABCAL will be demonstrated. illustrative examples for the creation of diagrams such as EH-pH, activity or concentration-pH and activity or concentration-EH will be presented to demonstrate the fundamentals of real hydrometallurgical systems. Speciation, titration and mixing will be used to simulate or predict operational processes. Applications will include treatment of Acid Mine Drainage (Berkeley Pitlake water and sediments), mass balance potential/pH diagrams, leaching and selective separation of metals from electroplating sludge, metal adsorption at femhydrite surfaces, and flowsheet development for treating mercury sulfide K106 sludge.

Jan 1, 2002

By Jing Zhan

The fibrous precursor can be obtained by coordination precipitation process, using oxalate, cobalt chloride and ammonia. The composition and morphology of fibrous precursor were characterized by XRD, IR, DTA/TGA and SEM analysis. The results show that XRD pattern and composition of the precursor with fibrous morphology precipitated at pH=9.0 were different from that of ß-CoC2O4?2H2O precipitated at pH=1.0. The mechanism on the thermal decomposition of fibrous precursor was addressed. The influences of various conditions in pyrolysis, including the temperature, time, atmosphere, and the morphology of the precursor, on the morphology, average size and specific surface area of the Co powders were investigated in detailed. At last, the final product, fibrous cobalt powders with diameter about 0.3~0.5µm in size and 40~60 in aspect ratio, were produced by thermal decomposition at 400~500? in the weak reducing atmosphere. The structure of pores in cobalt powders was capillary tube with open ports and the majority was mesoporous.

Jan 1, 2009

By Chao Lian, Hongxu Li, Hao Bai, Wei Wei

"Application of high-emissivity coating on inner walls in industrial furnaces increases the furnace thermal efficiency. The coating with high emissivity strengthens radiation heat transfer in the furnace, however, according to Wien's displacement law and Planck's radiation law, under heating temperature, the wavelengths of the radiation transfer are mostly between 1-5 µm, implying that increasing emissivity of the coating in near infrared band is more effective for higher thermal efficiency. In this paper, a new CuO-ZnO-based coating material sintered at 1600K was developed. The emissivity of the samples were measured and the result shows that, in near-infrared band, the emissivity of the sample reaches 0.98 at 773K with 13at.% of CuO doped in ZnO. In addition, the effects of CuO doping and use temperature on emissivity were also discussed. Furthermore, crystallization behaviors of ZnO-CuO sintering were investigated by DTA,XRD and SEM-EDS etc., which offered information for possible optimal design of the material.1. IntroductionIndustrial furnaces are widely used in various industrial heating. For example, the metal smelting furnace, ore sintering furnace in metallurgical industry; the distillation furnace, cracking furnace in petroleum industry etc,. The research on efficient energy saving technology has important significance. High emissivity coatings are widely used in many high temperature applications to effectively transfer the heat by radiation [ 1]. The theoretical calculation and experimental studies have shown that, coated high emissivity coating in the heating surface is an effective method to enlarge the infrared radiation power [2].At present, the infrared high emissivity coating has been widely used in China, and have been achieved remarkable energy saving effect. According to Wien' s displacement law and Planck' slaw, most energy of the black body at high temperature is radiated in the wavelength range of l-5µm; however it happens that many materials have the low emissivity within this range. Thus, it is important to improve the near-infrared band emissivity of materials [3]."

Jan 1, 2013