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By I. Ewart, E. Roux

Skorpion Zinc operates a solvent extraction/electrowinning zinc plant producing over 150 000 t/a of special high grade (SHG) zinc (>99.995% Zn). In the current flow sheet copper and cadmium are cemented from the neutral leach solution using zinc powder, to prevent galvanic corrosion of plant equipment and build-up of copper in plant solutions. This process is effective but unfortunately consumes expensive zinc dust and produces a low value copper product. The EMEW® (Electrometals electrowinning) technology of Electrometals Technologies Ltd. uses a rapid flow of electrolyte through a cylindrical cell to deposit copper or other metals from dilute solution (less than 1 g/L) [1]. The copper can be deposited as powder or may be harvested as a tubular cathode product. The advantage of the use of EMEW® technology at Skorpion Zinc will be to eliminate the use of expensive zinc dust and to produce a high value copper product for sale. Following extensive bench test work, a piloting campaign was carried out at Skorpion Zinc. The tests demonstrated the ability of the EMEW® cell to effectively remove copper from solution through direct electrowinning at lower operating cost than cementation. Keywords: Skorpion Zinc, copper, cementation, direct electrowinning, EMEW®

Jan 1, 2007

By S. Ata, Y. Pan, S. Gautam, G. Bournival

Bubbles play a vital role in flotation, and their properties directly affect the flotation performance. Xanthates are one of the major collectors used in sulphide mineral flotation. It is often believed that their main function is to render the desired mineral surface hydrophobic, which is essential for the mineral particles to attach to air bubbles. This paper takes a systematic approach to assess the influence of potassium amyl xanthate (PAX) at the air–liquid phase and its interaction with the frother in the concentration of range 10–5×104 ppm. Bubble size was measured in a laboratory flotation cell using a photographic technique and the stability of bubbles was quantified in terms of coalescence time -, the time required for a bubble pair produced at adjacent capillaries to merge into a single bubble. Bubble size reduction of up to 26% was observed with increasing PAX concentration in the cell. The bubble coalescence experiments using PAX only showed that the bubbles coalesced quickly at lower concentrations (10–50 ppm), but they stayed extremely stable at higher concentrations (1×102–1×104 ppm). Further experiments were carried out where the concentration of PAX was fixed at 1 ppm and 4- Methyl-2-pentanol (MIBC) concentration was varied. The synergetic action of PAX and MIBC significantly improved the stability of bubbles in the mixed system, and is even compatible with a stronger frother. The results strongly suggest that the role of PAX at the air–liquid phase should be considered in the practice of sulphide flotation. Keywords: Bubble size, bubble coalescence, PAX, bubble stability

Jan 1, 2020

By C. Righi, R. Carli

In modern steel continuous casting technologies mould fluxes are well-known to assure lubrication required by tribological system of mould-solidifying strand shell, and to provide crystalline phase solid film, contributing to control heat extraction between strand and mould wall. Actual cooling rates during normal continuous casting mould operations are far higher than critical cooling rate of the liquid slag. Indeed, DTA measurements point out that even relatively small cooling rates of 30?50 K/min are high enough to give exiguous formation of crystals. In this paper, contribution of devitrification in defining crystalline phase formation of industrial basic mould slag, used in continuous casting of crack-sensitive steel grades, has been investigated by means of non-isothermal experiments study. Devitrification has proved to play a major role in mould flux crystallization in a working environment explaining the higher amount of crystalline phase formed in plant sample in comparison with lab sample from DTA analysis with typical cooling rate of 5?20 K/min. The amount of crystalline phases formed ranks as follow: Cuspidine > Combeite > Gehlenite. Kinetic analysis of DTA non-isothermal experiments has provided kinetic parameters through Kissinger and Ozawa methods, as Avrami constant resulting to be n ?2 and activation energy of Cuspidine crystallization resulting to be EC= 315 kJ/mole. The effect of addition to the parent material of oxides as MnO, TiO2, ZrO2, Al2O3 and Fe2O3near to saturation point has proved to affect, in certain cases, crystallization behaviour of mold flux. In particular, MnO, TiO2, ZrO2oxides produce a relevant dump of crystallization of Combeite and Gehlenite phases, while Al2O3and Fe2O3do not appreciably affect crystallization. Key words: Mould flux, crystallization, devetrification, DTA non-isothermal analysis, Kissinger and Ozawa methods.

Jan 1, 2004

In ilmenite smelting, the FeO content of the feed material (nominally FeO.TiO2) is decreased by reduction with carbon. In a parallel reaction, a significant amount of the TiO2is reduced to Ti2O3.One of the striking features of these reactions is a consistent relationship between the extents of FeO and TiO2reduction; this relationship is independent of furnace size. It was recently proposed that this relationship follows from the solidification behaviour of the slag, where the final slag composition corresponds to the minimum melting point (?eutectic groove?) in the FeO-TiO2-Ti2O3phase system; the hypothesis is that solidification equilibrium with the freeze lining stabilizes the slag composition. If this is the case, the system of slag and freeze lining must be capable of correcting two types of disturbances: thermal and compositional. Thermal disturbances result from incorrect power input, for the feed rates of ilmenite and reductant. For example, excessive power input will tend to overheat the slag, causing the freeze lining to melt partially, establishing a new steady-state heat loss from the furnace. Compositional disturbances result from an incorrect reductant input for the given power and ilmenite input. In this work, the dynamic response of the slag and freeze lining to different inputs (flow rates of ilmenite and reductant, and power input) is modelled. The model is based on solidification equilibria, and quantified heat loss through the freeze lining. The conclusion is that the solidification equilibrium cannot constrain the composition to the eutectic groove for typical operating conditions. Keywords: ilmenite smelting, freeze lining, solidification, high-titanium slag

Jan 1, 2004

By M. -O. Suk, S. -K. Jo, S. -C. Shim, J. T. Kim, S. -H. Kim, C. -W. Seo, J. -S. Kim

An equilibrium study was carried out at 1873 K to ascertain the effect of carbon in CaO-SiO2-Al2O3-MgO-MnO-FetO slag systems on their FetO and MnO activity coefficients, representing the slag?s thermodynamic potential for steel reoxidation. Both ?FetOand ?MnO showed not only a sharp increment, but also a simultaneous slow decrement by increasing carbon content in slag, suggesting opposite roles of the carbon according to its stable forms. XPS (X-ray photoelectron spectroscopy) was introduced to clarify the stable forms of carbon in slag. XPS results prove that carbon dissolves in slag as carbonate, and carbide ions under oxidizing and reducing atmospheres, respectively. It was concluded that carbonate ions increase ?FetOand ?MnO, and that carbide decreases them. This paper suggests an application method of the present results to actual ladle refining processes, in order to enhance steel cleanliness without decreasing (FetO + MnO) content in slag. Keywords: carbon, slag, activity coefficient, FetO, MnO, carbonate, carbide, XPS, reoxidation, cleanliness

Jan 1, 2004

By S. Witzke, J. Lehmann, H. Gaye

The modelling work presented here concerns Ni-bearing steels produced by Imphy Ugine Précision. In such grades, the contents of elements such as silicon or titanium must be precisely controlled by slag/metal treatments. The slag phase is described by IRSID slag model that has been slightly revised in order to better fit recent SiO2activity measurements in the low SiO2content domain of the CaO-Al2O3-CaO system. The metallic alloys are described by the unified interaction parameter model (UIPM). In this formalism, the interaction coefficients, giving the effect of nickel on Al, Si, Mn and Ti activities, have been determined by electrochemical measurements and/or extracted from industrial data on slag/metal treatments concerning a wide range of alloy compositions: [ ] Keywords: slag, Ni alloyed steels, activities, interaction coefficient

Jan 1, 2004

By P. Fredriksson, S. Seetharaman

In the ladle refining process, the ?FeO?-content of the ladle slag is of great importance in the chemistry as well as the energetics of the process. An optimization of the process requires an accurate knowledge of the thermodynamic activities of ?FeO? in the ladle slags. Due to the discrepancies in the existing data, renewed attempts are being made at the Royal Institute of Technology to generate reliable data for binary, ternary and multi component slags containing ?FeO? at steelmaking temperatures. In order to measure the activities of ?FeO? in the slags, a gas equilibration technique was employed in the present work. The slags, kept in Pt-crucibles, were equilibrated with a CO-CO2-Ar gas mixture and quenched after equilibration. The chemical composition of the slag was analyszed. From a knowledge of the thermodynamics of Fe-Pt system, the ?FeO? activities in the slag could be evaluated. The results of the present studies, together with other literature values, were optimized in the slag software, THERMOSLAG® developed in the Royal Institute of Technology, Sweden. The results of the optimization are presented. Model calculations were performed with the KTH slag software, THERMOSLAG®, by using plant data from OVAKO Steel, Hofors, Sweden. It was found that oxygen estimations in the metal from the ?FeO? analyses of slags, obtained by conventional sampling and analysis methods, where less reliable. Estimation of the oxygen levels utilizing the sulphur partition between the slag and the metal were carried out using the THERMOSLAG® software. Reasonable estimations of the oxygen contents in the metal confirmed that this could be a very useful tool for the plant operator. Keywords: ladle, thermodynamics, slags, ?FeO?, experimentation, modelling, sulphur partition

Jan 1, 2004

By O. I. Ostrovski, D. K. Belashchenko

The aim of this paper is the construction of models of systems with ionic and ionic-covalent bonds (molten salts) using experimental diffraction data and the calculation of their structure and thermodynamic and transport properties. Modelling was performed using algorithm BELION, in which the non-coulomb part of interaction potential between ions in the model was determined by the method of iterative simulation which targeted agreement between calculated and experimental partial pair correlation functions (PPCFs). The ionic charges in salts, which can be fractional, were determined by minimization of internal energy. In this paper, the algorithm BELION is applied for chlorides of alkaline-earth metals. Pair potentials, PPCFs, atomization energies, self-diffusion coefficients and electric conductivity are calculated. The charge of alkaline-earth metals was in the range of 2.0-2.1, slightly increasing from Mg to Ba. Partial pair correlation functions and atomization energies of models agree well with experimental data for MgCl2, SrCl2and BaCl2. Keywords: molten salt, molecular dynamics, partial pair correlation function, ionic charge, atomization energy, diffusion.

Jan 1, 2004

By T. Tamura

It is known that the CaO-FetO-P2O5slag system has a wide liquid miscibility gap at steelmaking temperatures and this two-liquid slag phase has many advantages such as high activities of both FetO and CaO and high amount of P2O5. The phosphorus distribution ratio between the two-liquid slag and molten steel was confirmed to be higher than that between CaOsat.-FetO-P2O5slag and molten steel. The two-liquid slag may be useful for dephosphorization of molten steel and reduction of slag volume. Furthermore, the phase equilibrium of two-liquid CaO-FetO-P2O5slagsaturated with MgO was measured to determine the applicability of the two-liquid slag to dephosphorization in steelmaking process. Keywords: slag, refractories, solid solution, two-liquid phase, dephosphorization, steelmaking, phase equilibrium.

Jan 1, 2004

By J. Eriksson

Slag from stainless steelmaking is known to disintegrate, which is an environmental problem and prevents the cooled slag from being utilized. This disintegration is due to the transformation from the ßto the ? polymorph of di-calcium silicate. The transformation is accompanied by an increase in volume of about 11% and a total disintegration of the slag. AOD slag from stainless steelmaking was re-melted in a laboratory induction furnace, together with olivine and calcinated dolomite, to investigate the prevention of disintegration by increased MgO content of the slag with small changes in CaO to SiO2ratio. The modified slag was examined with X-ray diffraction and scanning electron microscopy. The trials showed that an increased MgO content can change the mineral composition towards formation of more Merwinite and Bredigite, which prevents disintegration of the slag. Keywords: slag, disintegration, di-calcium silicate

Jan 1, 2004

By M. Sanchez, C. Morales, J. Palacios

The slag produced in the Peirce Smith converters at the Ilo smelter of Southern Peru Copper Corporation has shown a wide range of magnetite content, which introduces an additional problem in the smelting units due to materials? recirculation. However, the operation data analysis and the application of thermodynamic concepts have made it possible to produce slag with magnetite content between 18 and 20%. The results have suggested that matte grade enhances magnetite formation while silica controls its precipitation, and they are also influenced by the increasing temperature of the slag. Thus, in order to obtain the required magnetite content in the slag, matte grade is gradually enriched in equilibrium with slag containing from 25 to 32% silica.

Jan 1, 2004

By A. B. Fox, R. P. Thackray, K. C. Mills

The role of mould fluxes in continuous casting is reviewed. The main functions of the flux are described and the importance of the flux in providing lubrication and the right level of heat transfer between the shell and the mould is described. The major problems of longitudinal, transverse and star cracking, gas and slag entrapment and deep oscillation marks in the steel product and ?sticker breakouts? are analysed. The important physical properties of the flux in combating these various problems are identified. Physical property data for the fluxes are given.

Jan 1, 2004

By M. D. Dolan

In this study, the development of a new method for investigating the diffusion of metal cations in multi-component slag systems, using microprobe analysis is discussed. This method allows the analysis of the diffusion of multiple species within a single system. This project has focused on the diffusion characteristics of manganese, iron, calcium and silicon in silicate slags, in order to simulate industrial steel and ferromanganese production. The diffusion behaviour of transition metals is of particular interest because of the effects of their variable valence. This study identified the variation in diffusivity of slag components with changes in composition and temperature of multi-component slag systems. The molecular structure of the experimental calcium-aluminosilicate slags was investigated to determine the chemical and physical properties that influence diffusion behaviour. This experimental data was used to develop predictive models for diffusivity. These models enable the estimation of the diffusivity of many slag components in complex slags, over a range of compositions.

Jan 1, 2004

By E. Kapilashrami, S. Seetharaman

Refractory/metal interactions and associated reactions are significant during casting as they can lead to inclusion formation. High-temperature interactions between aluminosilicate refractories and molten steel were studied in the present investigation using the sessile drop method. The changes in the contact angles between molten iron with well-defined oxygen levels and substrates of silica, mullite (3Al2O3?2SiO2) as well as commercial refractories were measured in the dynamic mode. In all cases, the reaction led to slag formation. The experiments were performed under isothermal conditions at 1823 and 1873 K. A known and constant oxygen partial pressure was imposed above the iron drop, through appropriate CO-CO2-Ar mixtures. For all substrates, the contact angles started decreasing due to the lowering of the surface tension of iron, as oxygen was imposed on to the system. When a critical level of oxygen was reached, slag started forming at the drop/substrate interface and at this stage, the contact angle dropped suddenly. Subsequent behaviour of silica and mullite was observed to be different, with SiO2showing a non-wetting behaviour. In the case of SiO2substrate, there were also deep erosions along the periphery of the drops and there was slag accumulation at the sides of the metal drop, probably due to Marangoni flow and/or SiO(g) formation. SEM and EDS analysis of the substrates revealed that the formed slag was fayalite. The thermodynamic criteria for slag formation and possible mechanisms of the reaction are discussed in the light of the experiments. Key words: silica, mullite, fayalite, corundum, slag formation, sessile drop.

Jan 1, 2004

By E. Chen, M. Barati, K. Coley

The reaction between carbon and slags is of significant importance in direct smelting of iron ores, EAF slag foaming and copper slag cleaning processes. This reaction is known to occur via gaseous intermediates and it is important to have fundamental data to understand the relative importance of each reaction step. In this study, the rate of CO2dissociation on different slag surfaces is measured using an isotope exchange technique. It was found that increasing iron oxide content up to 30 wt per cent does not have a significant effect on the rate constant while increasing from this limit, increases the rate constant dramatically. Activation energy of CO2dissociation on slags of unit basicity and different iron oxide contents is in the range of 180±40 kJ/mol. It is found that rate constant dependence on oxygen potential in the slag phase is increasing with iron oxide concentration. In the case of copper making slags, the influence of copper oxide is found to increase the magnitude of apparent rate constant, while decreasing the activation energy considerably. Key words: Gas-slag reaction, CO2dissociation, copper slag, kinetics, isotope exchange

Jan 1, 2004

By A. Hiltunen, R. Hiltunen

The utilization of blast furnace and BOF slags has long traditions and well-known applications in the building and road construction industries and in soil conditioning. The starting point for product development has been the basic physico-chemical properties of slags. This development has led to the almost 100% utilization of blast furnace slags and also considerable amounts of steel slags. While new methods and applications are continuously being looked for and developed in order to recycle and utilize all types of slag, there is at the same time an increasing debate over the exact nature of the slags, whether they are products or waste material, and whether they should be considered substances or preparations. These questions have emerged as a consequence of the environmental effects of the slags and current environmental legislation. The environmental effects of slags can be seen to be both beneficial and less beneficial. There is no doubt about their benefits in the road construction industry, as they allow significant savings in terms of natural materials and in transportation. It is also a known fact that using slags as fertilizers and in the cement industry leads to reduction in CO2emissions. The less favourable effects are the possible harmful emissions into the soil and groundwater. In this paper we describe the properties of slag products and their environmental effects according to investigations carried out in Finland. Keywords: utilization, blast furnace slag, steel slag, properties, solubility, environment

Jan 1, 2004

By G. van Aswegen

Large structures in mines (faults, dykes, pillars, abutments) fail when the load exceeds the strength. If the loading system stiffness (LSS, also referred to as the ‘local mine stiffness’) is lower than the stiffness of the structure the failure will be unstable. The greater the difference between these stiffnesses, the greater the energy release during unstable failure. A method has been formulated by which the LSS is established through cost-effective numerical modelling while insight into the structure stiffness (source stiffness - SS) is provided by apparent stiffness, a parameter based on the empirical relation between seismic moment and radiated seismic energy of small seismic events from the area/volume of interest. By plotting LSS vs SS a ‘stiffness diagram’ is constructed that is useful for seismic hazard ranking of different structures. A comparative back-analysis of the Dagbreek fault in Welkom, South Africa, (source of the 1990 Matjhabeng earthquake) and two other nearby faults confirm the applicability of the method. An extension of the method, where ‘hazard magnitude’ is used as a measure of the LSS, allows a ‘stiffness diagram’ to be constructed using seismic data only. Les larges structures dans les exploitations minières (failles, dikes, piliers, culées) s’écroulent lorsque la charge dépasse la résistance. Si la raideur du système de chargement (LSS, aussi appelé la « raideur de la mine locale ») est plus basse que la raideur de la structure, l’éboulement sera instable. Plus la différence est grande entre ces deux raideurs, plus l’énergie dégagée pendant l’éboulement instable est grande. Une méthode a été formulée selon laquelle le LSS est établi par modélisation numérique rentable, tandis que la raideur de la structure (SS – raideur de la source) est établie par la raideur apparente, un paramètre basé sur la relation empirique entre le moment sismique et l’énergie sismique radiée de petits moments sismiques dans l’aire/volume en question. On trace le « diagramme de raideur » en relevant les deux mesures (LSS et SS), ce qui est utile pour classer les risques sismiques de structures différentes. On vérifie l’applicabilité de la méthode en comparant la faille de Welkom, Afrique du Sud (foyer du séisme de Matjhabeng en 1990) avec deux autres failles proches. Une extension de cette méthode, dans laquelle on utilise la « magnitude du risque » comme mesure du LSS, permet de construire le « diagramme de raideur » avec des données sismiques seulement. Große Strukturen in den Gruben (Verwerfungen, Dämme, Pfeiler, Auflager) scheitern, wenn die Last die Stärke übersteigt. Wenn die Steifheit des Ladesystems (LSS, auch bezeichnet als `lokale Grubensteifheit’) niedriger ist als die Steifheit der Struktur wird der Bruch instabil. Je grösser der Unterschied zwischen diesen Steifheiten, desto grösser die Energiefreigabe während des instabilen Bruches. Es wurde eine Methode formuliert, durch die das LSS durch eine kosteneffektive numerisches Modell erstellt wird, während ein Einblick von der offensichtlichen Steifheit in die Struktursteifheit (Quellensteifheit - SS) gegeben ist, ein Parameter der auf der emipirischen Relation zwischen seismischem Moment und ausgestrahlter seismischer Energie von kleinen seismischen Ereignissen vom Interessens-/Volumenbereich basiert. Durch das Kartograpahieren der LSS in Bezug auf die SS wird ein `Steifheitsdiagramm ' konstruiert, welches für seismische Gefahrklassifizierung der unterschiedlichen Strukturen nützlich ist. Eine vergleichende Postanalyse der Dagbreek Verwerfung in Welkom, Südafrika, (Zentrum des Matjhabeng Erdbebens 1990) und in zwei anderen nahe gelegenen Verwerfungen bestätigen die Anwendbarkeit der Methode. Eine Verlängerung der Methode, in der die `Gefahrengröße' als Maß für das LSS verwendet wird, gestattet, daß ein `Steifheitsdiagramm' konstruiert wird, welches nur seismische Daten verwendet.

Jan 1, 2003

Despite the wealth of information available on phase equilibria of oxide systems there remainmany gaps and inconsistencies in our knowledge base. From an industry perspective there is anongoing need to adequately describe the phase chemistry of slag systems in order to optimizeprocess performance and improve productivity. Since this chemical behaviour cannot be predictedfrom first principles it follows there is also an ongoing need for accurate experimental data. The advances made in recent years in the capabilities of sophisticated analytical and measurement equipment have made it possible to develop new experimental techniques for the direct determination of phase equilibria in low order and complex multi-component slag systems. In addition the development of powerful computer modelling tools makes it possible to provide more comprehensive descriptions of the phase chemistry, to present the information in a range of perspectives, and to critically analyse the various types of related thermodynamic and structural information available. This review provides an overview of the types of information that can be used to determine phase equilibria in slags systems, analyses the influence of uncertainty and the relative importance of these types of data, and describes the advantages and limitations of the various experimental techniques that can be employed to obtain this information. Examples of recent studies are provided that demonstrate how an integrated approach to the determination of phase equilibria in complex systems, involving the use of targeted experimental studies and systematic thermodynamic model development, can lead to a better utilization of our current research capabilities and resources and more accurate descriptions of these systems. Keywords: slags, phase equilibria, experimental techniques

Jan 1, 2004

By L. Chen, G. A. Brooks, S. A. Nightingale

The dissolution of alumina and magnesia has been investigated using laser scanning confocal microscopy (alumina) and a rotating finger apparatus (magnesia) to assess the effects of temperature, composition and forced convection on the rate of dissolution in CaO-SiO2-Al2O3based slags. The two techniques have differing strengths and limitations, and provide complementary methods for studying dissolution. Alumina dissolution was studied for temperatures from 1477 to 1577°C. Based upon the data, the rate controlling mechanism was thought to be mass transfer control in the slag. The diffusion coefficients for the alumina particles are estimated to be in the range 10-11to 10-10m2.s. MgO degradation for sample rotation speeds of 50 to 800 rpm at 1500 and 1530°C was studied for both congruent and incongruent dissolution. The results show that the rate of dissolution for this is primarily controlled by a diffusion mass transfer mechanism for congruent dissolution except at the highest rotation speed. For incongruent dissolution, the mechanism is much more complex, with the morphology and distribution of the spinel reaction product having a significant effect. At high speeds and prolonged times, mechanical forces played a major role in the degradation process. Keywords; kinetics, corrosion, refractories, dissolution rate, inclusions, mass transfer, slags, steelmaking

Jan 1, 2004

By S. Ganguly, R. Kononov

Carbothermal reduction of manganese oxides and manganese ores in the solid state was studied in hydrogen, helium and argon at different temperatures, ore compositions and carbon to manganese oxide ratios. Wesselsore (South Africa) and two grades of the Groote Eylandt ore (Australia) with different level of impurities were examined. Ores were characterised by XRD, X-ray fluorescence, optical microscopy and scanning electronmicroscopy. Isothermal and temperature programmed carbothermal reduction experiments were conducted in a fixed bed reactor in a vertical tube furnace, with on-line monitoring of gas composition by the CO-CO2 infrared sensor. The reduced samples were characterised by XRD, SEM and LECO analyses. Extent of reduction was calculated using data on the off-gas composition, and LECO carbon and oxygen contents in the reduced sample. Manganese oxides in the ore were reduced to a-Mn and carbides Mn23C6 and Mn7C3 depending on the carbon to ore ratio. The reduction rate of manganese ores in hydrogen was higher than in helium and argon. Key words: Manganese, Carbothermal Reduction, Hydrogen, Argon, Carbon Monoxide, Helium, Kinetics.

Jan 1, 2007