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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 R. Nilsson

In the present work, an assessment of the sulphide capacities of a number of binary and ternary slag systems have been carried out in the light of a sulphide capacity model. The model is based on the expression: {CS- exp (-A G °/R T) ? ao2 / fs2-} where AGO is the standard Gibbs energy change for the above reaction, ao2 is the activity of oxygen ions and f, is the activity coefficient of the sulphide ion in the slag. In the present model, the ratio (ao2/fs2) is optimized for the experimental data available in literature. The systems assessed are the binaries MnO-SiO2, CaO-SiO2, Al2O3-CaO, as well as the ternaries CaO-Al2O3-SiO2 and CaO-MnO-SiO2. In the case of all these systems, the experimental data available in literature were complemented by measurements carried out at the Division of Theoretical Metallurgy. The sulphide capacities of some FeO- containing binary, ternary and quaternary slags are also examined. The potentiality of the model to estimate the sulphide capacities of complex slag systems from binary and ternary data is demonstrated.

Jan 1, 1996

By J. L. Holman

The Bureau of Mines is investigating recovery of Ni, Co, Cr, and other metals from mixed contaminated supera110y scrap. The scrap is melt-refined and cast into anodes for electrodeposition of recyclable Ni-Co alloy. Melt oxidation using roasted superalloy grinding sludge as oxygen source can divert the Cr to the slag but with excessive Ni-Co loss. Melt oxidation-carburization or direct melt carburization retains -95 pct of the Ni-Co in the anode alloy. With direct carburization, -90 pct or more of the Cr and other refractory metals report to the anode alloy, largely as carbide phases insoluble in electrolysis. Electrorefining data relate parameters such as controlled cathode potential, Fe and Cr impurities, pH, and compartmented cell use, to current efficiency and Ni-Co deposit quality. Recovery of -90 pct of the Ni-Co in the scrap can be achieved. Preliminary experiments to recover Cr, W, and other metals from the anode sludge and other byproducts are discussed. 347

Jan 1, 1987

By D. L. Yopps

Platinum-group metal (PGM) flotation .. concentrate from the Stillwater Complex, MT, was subjected to biooxidation using Thiobacillus ferrooxidans in an effort to break down the sulfide minerals and liberate the ? associated PGM's for subsequent chemical leaching. Bacterial treatment oxidized up to 94 pct of the sulfide present, destroyed the PGM-bearing pentlandite [ (Ni,Fe),9Ss) mineralization, and dissolved most of the nickel in the concentrate. Results showed that increased sulfide oxidation during the biological stage led to improved PGH recovery in the subsequent. chemical leaching stage. cyanidation at 80° c proved to be the best chemical leachant tested. It removed 7.6 pct of the palladium, 94 pct of the rhodium, 97 pct of the gold, but only 34 pct of the platinum from the biooxidized concentrate.

Jan 1, 1991

By M. C. Ruiz

In the present study, the size distribution, Fo(v), of organic drops produced in a continuous-mixing vessel has been determined experimentally for various conditions. The organic phase used was a 1: 1 mixture of a salicylaldoxime (LIX 860N-IC) and a ketoxime (LIX 64-IC) in an aliphatic diluent (Escaid 103). The aqueous phase was a copper sulfate solution. The results indicated that an increase in stirring speed, extractant concentration, and pH produced smaller drops. The effect of the stirring speed was the most significant, decreasing the average volume of drops by 57 % for a change from 300 to 400 rpm. On the contrary, an increase in the dispersed phase fraction, copper sulfate concentration, and retention time produced larger drops. Changes in temperature from 23 to 30°C did not affect significantly the drop sizes. In all cases, the experimental drop size distributions could be accurately represented by a lognormal distribution.

Jan 1, 2001

By M. M. Monte

A method for removing metallic mercury from contaminated tailing, using the flotation process, is described. In order to define some relevant parameters for the mercury flotation system, microflotation and electrophoretic mobility tests were carried out on (pure) metallic mercury in the presence of several surfactants. Based on the results obtained from fundamental studies a series of bench scale flotation experiments with mercury containing tailings from two wetland sites in Brasil were done. The results of microflotation tests with mercury showed that by using cetyl trimethyl ammonium bromide, an increase in mercury flotability is observed in the acid pH range, whereas in the presence of potassium oleate the highest mercury flotability was found in the alkaline pH region. The mercury flotability using potassium amyl xanthate was improved by the addition at sodium dithionate as an activator. The bench scale flotation tests with contaminated tailings from Poconé (brazilian wetland site) showed a recovery of 70% when sodium dithionate was used as activator and potassium amyl xanthate as collector. The resulting coefficient of separation is around 60%. However, the results of the flotation experiments with fine fractions from amalgamation tailings from Peixoto de Azevedo (brazilian wetland site) showed a low mercury recovery (32%).The results from this work suggest that since in the Poconé site tailings, the metallic mercury is not completely associated to the finer particles, the flotation process to recover the metallic mercury seems very promisor.

Jan 1, 1996

By Dietmar Eifler, Benjamin Jost, Marcus Klein

This paper focuses on the ductile cast iron EN-GJS-600 which is often used for components of combustion engines. Under service conditions, those components are mechanically loaded at different temperatures. Therefore, this investigation targets at the fatigue behavior of EN-GJS-600 at ambient and elevated temperatures. Light and scanning electron microscopic investigations were done to characterize the sphericity of the graphite as well as the ferrite, pearlite and graphite fraction. At elevated temperatures, the consideration of dynamic strain ageing effects is of major importance. In total strain increase, temperature increase and constant total strain amplitude tests, the plastic strain amplitude, the stress amplitude, the change in temperature and the change in electrical resistance were measured. The measured values depend on plastic deformation processes in the bulk of the specimens and at the interfaces between matrix and graphite. The fatigue behavior of EN-GJS-600 is dominated by cyclic hardening processes. The physically based fatigue life calculation “PHYBALSIT” (SIT = strain increase test) was developed for total strain controlled fatigue tests. Only one temperature increase test is necessary to determine the temperature interval of pronounced dynamic strain ageing effects

Jan 1, 2015

By Y. Yang, S. Peelman, J. Sietsma, Z. H. I. Sun

The rare earth elements (REEs) present in the Kiruna iron ore mine tailings are being considered as a new REE resource for the EU. These tailings, after beneficiation, contain approximately 5000 ppm of rare earths, concentrated in apatite and monazite minerals. To economically extract the REEs from these tailings the phosphorous contained within the apatite must also be extracted and the waste production of the process should be minimal. To achieve the extraction of REEs and phosphorous HCl and HNO3 were investigated as possible leaching agents. Based on the results a leaching process using HNO3 is proposed. This process produces H3PO4 from the apatite while simultaneously dissolving the REEs. The resulting leach liquor is then cooled to remove the unwanted Ca as Ca(NO3)2. Analysis of the leach liquor reveals extraction ratios of between 75% and 100% for the heavy REE (e.g. Y, Eu, Dy, …) and below 40% from the light REEs (i.e. Ce, La). Full phosphorous extraction was also achieved.

Jan 1, 2016

By J. G. Zafiratos

The leaching of a Greek low-grade manganese dioxide ore, not amenable to conventional mineral processing operations, was studied using a mixed culture of Thiobacillus sp. bacteria. The experiments were carried out in specially designed continuously aerated and stirred tank reactors arranged in two-tank series. The first tank of each series was loaded with an elemental sulfur culture suspension while the second was loaded with a manganese ore high density slurry. The bacterial culture had been previously adapted to grow on elemental sulfur and also in the presence of manganese ore and dissolved manganous ion. A two level full factorial design was constructed in order to study the effects of the ferric ion concentration in the leach solution, the "elemental sulfu weight to ore weight" ratio, the ore pulp density and the composition of the dispersed gas. The responses which were investigated included percentage manganese recovery, co-dissolution of iron and manganese dissolution rate. Parameters with constant values throughout the experiments were the leach solution pH, the nutrient medium composition, the dilution rate and the ore and sulfur grain sizes. It was found that the ferric ion concentration was the most significant factor and had a positive effect on the final percentage extraction of manganese from the ore and also on the rate of manganese solubilization from the ore. The effects of the other factors studied are discussed in detail.

Jan 1, 1997

By Hassan Saalman, Mahmoud Mahmoud, Omneya El Hussaini

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

Jan 1, 2014

By D. C. Azubike

Wolframite (FeWO4) usually having cassiterite (SnO2) as a major impurity is a primary source of tungsten. Its direct reduction/carburisation with carbon in the temperature range 1000-1400°C, and with hydrogen at 600-900°C followed by carburisation with CO at 900°C are described. Depending on the conditions and reactants employed, Fe, Fe2W, B-Sn,WC, W2C, Fe3W3C and Fe6W6C are the products. Tin was found to inhibit the overall reduction and carburisation reactions significantly. The potential for either efficient separation of iron and tungsten or a one-stage production of an iron-based metal carbide composite is discussed.

Jan 1, 1992

By Chan. C. L., Zehr. R., M. M. Chen, J. Mazumder

"Two three-dimensional models of a surface tension gradient driven flow during laser surface heating are developed. The first model is based on a perturbation solution. The basic solution corresponds to the stationary axisynwnetric case and perturbation is based on a small scanning velocity. The advantage of seeking a perturbation solution, as it turns out, is that the three-dimensional flow is modeled by two sets of two-dimensional equations which are presumably much more tractable than the original three-dimensional equations. Numerical solutions are obtained and discussed. The second model is a full three-dimensional numerical solution of the Navier-Stokes equations, using a point-by-point partially vectorized iteration scheme. Surface shape is also determined in a self-consistent manner. The effect of the presence of convection on pool geometry, cooling rate and solute redistribution is presented and discussed.IntroductionThe existence of fluid flow and convection and their effects were first reported in the fifties (1,2). The role of convection in controlling pool geometry such as pool shape, undercut and ripples, and defects such as variable penetration, porosity and lack of fusion and weld properties such as weld homogeneity and bead formation is studied by a number of researchers and is reviewed by the authors in a recent paper (3).Recently, surface tension gradient driven flow has been identified as one of the forces responsible for convection within the molten pool (4,5). It is postulated that surface tension gradient driven flow is responsible for the surface ripple formation in the weld pool (6-8). Oreper, et al. (9) developed a two-dimensional convection model. Buoyancy, electromagnetic and surface tension gradient forces were considered. The formulation was based on a specified pool profile. It was found that the surface tension gradient is the dominant force in most cases. However, the solid-liquid interface is not known a priori. In fact, the solid-liquid interface, i.e. the pool shape, is a piece of information that the model should be able to predict. A two-dimensional transient self-consistent (i.e. the solid-liquid interface is solved as part of the solution] model for laser surface melted pool was first developed by Chan, Mazumder, and Chen (3)). This model predicted a non-uniform cooling rate, hence non-uniform microstructure. Depending on the Prandtl number (i.e. material) and surface tension number, the shape of the molten region as well as the cooling rate changes. It was also predicted that the recirculating velocity is of one or two order of magnitude higher than that of the scanning velocity. This model provides the detail of the flow field and heat transfer on a plane perpendicular to the scanning direction. However, the front-to-back motion and its effect on heat transfer also play important roles in the physical process, especially for the fact that the recirculating velocity is so much higher than the scanning velocity. Such a motion cannot be obtained from two-dimensional models."

Jan 1, 1986

By Aïda Espinola

Decontamination of synthetic solutions containing cadmium ions using coconut fibers in natura was investigated in laboratory scale. Cadmium ions, a serious pollutant of water ways, where it is detrimental to the environment, may be absorbed by fish and mollusk used as food, which will, eventually, poison humans; these ions are usually present in minero-metallurgical and electroplating industrial effluents. Usually employed for the aqueous effluents treatment are chemical precipitation, adsorption and electrolytic processes. Precipitation is not effective for cadmium removal, because of the high KpS of the cadmium hydroxide, which requires high pH; only sulfide would be efficient in cases of very small amounts. Some vegetal refuses have shown to be practical for absorption processes of several metallic ions. We have applied coconut (Cocos nucifera) shells, which are extremely abundant over most of the extensive Brazilian coast, in the removal of cadmium: it has been verified, in our laboratory, that the surface of the fiber of this coconut is rich in chemical compounds which are active scavengers for Cd2+. For the optimization of the process, hydrosoluble components existing on the surface of the fiber, which may be deleterious, were previously washed out by water, and variables, such as the pH and the proportion of mass of fiber to volume of solution, were adjusted. As much as 99% of the initial contaminant metallic ion has been eliminated, resulting a solution to be discarded which contains ca. 0.1 ppm; this attends to the maximum impurity legally admitted by the environmental control agency of Rio de Janeiro, FEEMA, for cadmium ions in aqueous effluents to be disposed in rivers and in the Guanabara Bay area.

Jan 1, 1998

By Keiji Toyabe

Several purifying techniques have been developed for controlling the impurity levels in the copper electrolyte at Niihama Copper Refinery. These have been carried out as follows; i ) the study of the reaction in liberation made it possible to raise the current efficiency for arsenic removal by more than 50% and to decrease generation of arsine sharply. By applying this method, a good performance was attained at commercial operation. li) the antimony in the electrolyte can be successfully removed by contacting it with activated carbon. This procedure is applicable particularly when there is a large amount of antimony in the copper anode. lli) for the nickel sulphate recovery from the electrolyte, an electric evaporating system was developed. The characteristics of this process are, capability of continuous operation with less manpower, the high recovery ratio of nickel sulphate (more than 85% as nickel) and no black acid formation in the treated solution.

Jan 1, 1987

By Broggi Andrea

Condensates produced by SiO(g) and CO(g) have a crucial importance in silicon production. Condensation will follow the reactions 3 SiOðgÞ+COðgÞ→ 2 SiO2 + SiC and 2 SiO ðgÞ→Si+SiO2. Solid compounds generated during silicon production contain Si, SiO2 and SiC in different microstructures and amounts. In industrial systems, condensates limit the SiO(g) escape to the off-gas system. On the other hand, they can block the gas flowing from the high temperature zone, hence the necessity of studying an optimized condensation process. This review discusses SiO(g) condensation and its interaction with CO(g). The report gives an overview of the condensates found both at laboratory and at industrial scale. The two main compounds are the Si–SiO2 and the SiOx–SiC mixtures. The hypothesis on the mechanism of formation of SiC–SiOx condensates is presented through a wide selection of performed works. The advantages and disadvantages of the former experimental procedures are discussed.

By T. R. A. Davey

A simple model for metal solution behaviour may be derived, on the basis of dilute solution solubilities (where? log concentration of solute varies linearly with reciprocal temperature) and not-so-dilute region solubilities (where the log of the alpha-function at saturation frequently varies linearly with reciprocal temperature) and assuming activity to vary according to the quadratic formalism in between. Matte binary systems usually exhibit regular .solution behaviour when the constituent species are chosen appropriately. In many recent papers, metal solubilities in .slags are expressed as the sum of several different and supposedly independant molecular species (e.g. oxides, sulfides, chlorides), Such a view is untenable because of the now proven ionic nature of slags. Some possible reasons for the great effect of sulfur on copper solubilities in slags are discussed.

Jan 1, 1985

By Animesh Jha

"Fine ceramic powders (<500 nm) exhibit exceptional physical and mechanical properties in engineered structural ceramics. The production of fine powders, in particular the non-oxide ceramics, via a cheaper route than the organic solvent route has been rather elusive. This paper examines the physical chemistry of sub-oxide vapour-phase reduction reaction for the nucleation of non-oxide ceramic phase. Well known vapour species eg SiO and BO in the production of technical ceramic powders (SiC, BN) are particularly discussed for understanding the nucleation process of SiC and BN ceramic phases respectively. The regimes of partial pressures and temperatures are particularly 'identified. The calculated nucleation rate as a function of the temperature is compared with the experimental results on powder morphology. The production of amorphous and nanocrystalline h-BN powders is discussed in the context of substrate structure and thermodynamic parameters.IntroductionThe physical and mechanical properties of ceramic components are strongly dependent on the powder particle size and morphology used for their fabrication. For example the strength (Os) of the structural ceramic components increases with decreasing average grain-size (d) in accordance with the Hall-Petch relationship: Os = 0""0 + k/(d)1/2. Here k is an empirical constant which can be established from the graphical relationship. However as the particle size approaches submicrometer-size range, the dependence of strength on the particle size becomes more complex [1]. The design of ceramic components based on nanometer-size particles have recently become an important field which can offer ceramic materials with properties comparable to their metal counterparts. Several materials based on these concepts have been developed and reported by Niihara [2]. For example, the Al2O 3-SiC nanocomposite, having average B-SiC grain size 0.3-2um with intragranular SiC particulates of 5-10 nm has unusually high strengths (1100 MN/m2) at low and elevated temperatures combined with enhanced fracture toughness (> 4 MN-ml.5) which is an unusual combination in structural ceramics. Besides mechanical properties, as the particle size of ceramic powders approaches the nanometer-size range, the charge transport properties also improve by many times. The effect of particle size on the electrical conductivity of Si3N4-TiN composites has been well documented [3.4]. The size of ceramic particulates without doubt plays a pivotal role in determining the properties of ceramic components."

Jan 1, 1996

By Masanori Abe, Yoshitaka Kitamoto, Kazuhiro Nishimura

"Ferrite plating is a chemical processing which utilizes Fe2+ - Fe3+ oxidation to synthesizing polycrystalline films of ferromagnetic spinels (MFe20 4, M = Fe, Co, Ni, Zn, Al, Cr, TI, etc:) directly from an aqueous solution at 24 - 100°C. This low temperature process allows us to fabricate new ferrite film devices on · substrates of such non-heat-resistant materials as plastics, GaAs integrated circuits, and biomaterials. Synthesized from an aqueous solution the ferrite plated ·films are highly biocompatible. Thus various magnetic device and biomedical applications have been proposed and realized using ferrite-plated films. Ferrite-encapsulated polymer microspheres are applied to antibody carries for enzyme immunoassay, and also to toners/carriers for photocopying. Perpendicular magnetic recording media utilizing plated CoNi ferrite films are proposed. The low-temperature synthesized films of NiZn and Co ferrites are potentially used as soft-magnetic and/or insulating layers, respectively at high/microwave frequencies.IntroductionFerrite plating is a processing which facilitates the formation of crystalline spinel ferrite films with various compositions, (Fe, M)30 4 (M = Fe, Co, Ni, Zn, Al, Cr, TI, etc.), directly from an aqueous solution at 60 - 100°C [1]. This opened the door to fabricating novel ferrite-film devices using substrates of such non-heat-resistant materials as plastics and GaAs integrated circuits [2-4]; conventional ferrite film preparation techniques such as sputtering, vacuum evaporation, MBE, LPE, etc., require high temperatures(> -600°C) for crystallization of ferrites, which deteriorates the non-heat-resistant substrates. Recently we extended ferrite plating to be preformed at room temperature [5, 6]. This enables us to use as substrates such organic materials as biomaterials (e.g. enzymes) having very low heat-resistance."

Jan 1, 2000

By Balladares V. Eduardo

Most of the arsenic contained in copper concentrates is removed in the gas phase during the smelting and converting processes and, according to recent environmental regulations, it is required to fix it in a solid stable form. In this regards, ferric arsenate has been reported as thermal and aqueous stable compound. Therefore, various alternatives for treating gas containing arsenic were considered in this work. From data obtained at laboratory scale on fixation of arsenic using iron oxide, a new process to treat copper concentrates containing arsenic was evaluated. The effect of temperature, oxygen potential and the sample porosity on the fixation of arsenic contained in a gaseous stream was studied, and the iron oxide converted into ferric arsenate was up to 10%. The obtained results suggest a new alternative for gas treatment with an interesting and attractive technical development. The arsenic was retained as ferric arsenate with thermal and aqueous stability, and it allows a safe disposal keeping the environmental restrictions. The kinetics parameters are used to scale up laboratory results to higher processing rates.

Jan 1, 2005

By Larry G. Twidwell, Jannette L. Chorney, Bryce D. Ruffier, Katelyn M. Lyons, Daniel W. Gaede, Ryan J. Foy, Jerome P. Downey

The Army Research Laboratory (ARL) has an interest in the recovery and processing of rare earth elements. At Montana Tech, elevated temperature chlorination of rare earth oxides is presently being investigated as a potential methods leading to the selective separation and recovery of rare earth elements from mineral ores and concentrates. After preliminary evaluation, ytterbium oxide was selected as a representative surrogate material for more extensive chlorination studies. Methods used to determine the conversion and recovery include X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis. These data have been used to establish and confirm process conditions that consistently yield high conversion efficiencies. Based on the promising results, further experimentation is underway to ascertain the metallurgical response of other rare earth oxides and carbonates to the roasting process. The end goal is to create a robust process for industrial application that has greater efficiency and reduced costs as compared to current practice.

Jan 1, 2015