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By J. Janssens, B. Coletti, S. Smets, J. Plessers

The oxygen activity of the ladle slag determines the reactivity towards the steel during ladle treatment. Therefore, the in situ measurement of the oxygen activity of slags can be an important tool. The applicability of an electrochemical sensor is examined in this work. The sensor measures the electromotive force (EMF) that is established between a sample of the slag phase that is immersed in the liquid steel bath and a reference system (Cr/Cr2O3). Industrial and laboratory experiments demonstrated the capability of the sensor to detect the influence of the slag components on the measured oxygen potential. Comparison of the measured values with thermodynamically calculated values shows that the measured oxygen activity is systematically too low. This was attributed to a reaction of the steel with the slag sample. To investigate this, further lab tests were performed where the slag oxygen activity was measured after the slag had been equilibrated with the steel. The measured values were dependent on the oxygen activity (aO) of the steel. For industrial applications, it is concluded that the aO of the steel should be known and that this value is necessary for the interpretation of the measured values. Keywords: low carbon steels slags, slag oxygen activity, on-line sensing, thermodynamic evaluation.

Jan 1, 2004

By M. Görnerup, A. Kapilashrami, Seetharaman. S., A. K. Lahiri

Simultaneous reduction and foaming of chromium-rich slag have been studied in a laboratory furnace equipped with X-ray image analysis. Reduction of the metal oxides by graphite generated CO, which caused the melt to foam. The slag composition continuously changed due to reactions and dissolution of lining. Gas generation rate, foam height, and gas bubble size were studied and correlated to slag composition. Viscosity increased significantly during the experiments due to a change in slag composition. Bubble sizes varied little during the progress of reactions but differed considerably for different slags. Bubble sizes were largest for V2O5 containing slag, which is contrary to the general understanding that the presence of strong surface active agents reduces the bubble size. The foaming index did not follow expected trends for bubble size and viscosity, suggesting that foaming index is not a suitable parameter for discussion of foams under dynamic conditions. Keywords: slag, foaming, dynamic conditions

Jan 1, 2004

By S. E. Olsen, M. Tangstad, G. Tranell, K. Berg, S. Gaal

In this study, the reduction behaviours of MnO and SiO2containing slags by solid carbonaceous materials was investigated in both small and larger-scale laboratory experiments. Five types of carbonaceous material were investigated: 2 graphites, industrial coke, anthracite and eucalyptus charcoal. The effects of the reductant type/properties on the reduction kinetics, metal composition and metal yield, have been quantified. Results show that the reduction rate is highly dependant on the type of carbon used. It was found that the reductant type significantly influenced the SiO2reduction while it did not seem to have a large effect on the MnO reduction. This may be due to the different CO2and SiO reactivities of the materials.

Jan 1, 2004

By T. Lindstad, J. Kaczorowski

The Boudouard reactivity of single cokes produced from selected bituminous coals and commercial cokes has been investigated in a thermo gravimetric furnace. The effect of potassium as a catalyst for this reaction was studied, as it is known to accumulate in ferromanganese furnaces. A gaseous impregnation technique using K2CO3 as the potassium source was applied to impregnate the coke samples. The reactivity experiments were designed to simulate conditions occurring in an industrial furnace, as used for production of Mn-alloys. The coke particle size varied from 3.35 to 6.63 mm, while the temperature was maintained between 800- 1100oC with a gas composition from 50 to 75% CO2 in a CO/CO2 mixture. To determine the catalytic effect of potassium, the concentration varied from a fraction of a percent up to 15%wt. The results show that single chars vary significantly in reactivity, depending on the properties of the parent coal, while commercial cokes exhibit similar reaction rates. Temperature and partial pressure of CO2 have the strongest influence on the reactivity, while the influence of gas flow rate and coke particle size were found to be negligible. The catalytic studies revealed that the relative reactivity of non-impregnated samples are preserved after the impregnation, so the least reactive coke is still the least reactive after the impregnation for the whole range of potassium loads. Also, it has been confirmed that the Boudouard reactivity reaches a plateau at potassium concentration of 4%wt.

Jan 1, 2007

By H. Urata, K. Ishii

To determine the effect of F ions in the molten alkali silicate systems on their structures, quenched Na2O-SiO2-NaF systems were investigated by Raman spectroscopy and molecular dynamics simulation. The systematic increase of 1100 cm-1band intensity in the Raman spectra of the silicate melts accompanying the replacement of F for O provides the evidence for concomitant polymerization of melts. From the molecular dynamics simulation, it was confirmed that most of substituted F was mainly coordinated to Na+ ions but not Si4+ions. These results were consistent with the mechanism in which F associated with otherwise network-modifying Na rather than with network-forming Si. Since F was associated to Na+ ions, the replace of O ion by two F ions promote the polymerization of silicate melts. Keywords: fluorine; molten flux; slag structure; molecular dynamics simulation; Raman spectroscopy.

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 D. Zhou, T. Hamano, Tsukihashi. F., W. -G. Seo

The thermodynamic properties for the CaO-CaF2and CaO-BaO systems were calculated by molecular dynamics (MD) simulation using Born-Mayer-Huggins type pair potential. The parameters of interatomic potential were obtained by fitting the thermodynamics properties of CaO, CaF2and BaO with the experimental data. The phase diagrams for the CaO-CaF2 and CaO-BaO systems were calculated by the thermodynamic properties obtained by MD simulation. The eutectic composition and temperature of the CaO-CaF2system calculated by MD simulation were about 28 mole per cent CaO and 1575K, respectively. The calculated eutectic point agrees very well with experimental data, which are about 22 mole per cent CaO and 1633K, respectively. Keywords: molecular dynamics simulation, thermodynamics, phase diagram, calcium oxide, calcium fluoride, barium oxide.

Jan 1, 2004

By V. Tathavadkar

Worldwide TiO2is extracted from natural ilmenite, rutile, and anatase minerals via the sulphateand chloride processes. The sulphate process generates large volumes of less toxic wastes, whereas the chloride process, including the ilmenite-chloride process of DuPont, yields much lower volume of wastes, which are highly toxic and hazardous. The treatment and disposal of such hazardous chloride wastes is both expensive and difficult in terms of long-term monitoring. Besides the waste management and disposal, there is also a shortage of high-grade titanium dioxide minerals in nature, which consequently yields much larger tonnages of sulphate and chloride wastes. In the present investigation we report the results of an alternative titaniferous mineral beneficiation process based on soda ash roasting of minerals. Compared to the conventional processes for beneficiation of TiO2- ores, the alkali roasting of titaniferous offers several advantages including the zero process wastes. In the soda ash roasting process, the mineral is mixed with sodium carbonate and heated above 1023 K in air. The oxidative roasting of ores yields several complex alkali compounds, some of which produce a liquid mixture above 1123 K. In this paper, we have attempted to characterize the composition and physical chemistry of alkali-rich liquid phase. The phase equilibria in the Ti-(M:Fe)-Na-O system are evaluated and compared with the phases formed as a result of roasting reaction. The experimental results revealed that the composition of complex alkali liquid at the reaction interface plays an important role in determining the transport of O2-ions and decomposition of ilmenite. The roles of the crystal structure of mineral phases and their energetics are also emphasized in controlling their decomposition during alkali roasting. The presence of molten alkali in controlling the partitioning of water-soluble alkali salts and insoluble sodium titanate is also explained. Keywords: ilmenite, anatase, alkali roasting, phase equilibria.

Jan 1, 2004

By R. J. Hundermark, S. Sun

The oxidation state dependence of the electrical conductivity of a calcium ferrite slag with 25 wt% CaO was measured at 1300°C using a shallow slag layer and two-electrode technique. The experiments were started in air and the slag was sequentially reduced by means of a controlled gas atmosphere using CO2and CO. The electrical conductivity in air was approximately 300 S/m and increased with reduction to approximately 1900 S/m at a pO2of 10-10atm. The interest in the oxidation state dependence of the conductivity of calcium ferrite slags was to provide a comparison with the conductivity of iron silicate slags and to establish the effect of slag basicity on the electrical conductivity and its oxidation state dependence. The results obtained are discussed in terms of the slag structural information available in the literature. The co-ordination of the ferric ions appears to play a large role in determining the electrical conductivity. Keywords: calcium ferrite, slags, electrical conductivity.

Jan 1, 2004

By Z. Lin, M. Isac, R. I. L. Guthrie

The kinetic and thermodynamic efficiencies of chromium recovery from the slag in an AOD process during the slag de-oxidation period with ferrosilicon is a complex process affected by slag basicity, temperature, the dissolution kinetics of the reducing agents, and intermixing of the slag/metal/alloy addition phases within the vessel. The present work focused on a study and simulation of the fluid dynamics and mixing behaviour of ferrosilicon additions in the AOD process for the production of stainless steel. In order to visualize the mixing behaviour, a two dimensional slice model of an AOD vessel was first built and filled with ZnCl2solution and then covered with silicone oil in order to represent the bulk liquid steel and slag phases, respectively. The injection of argon/oxygen process gases was simulated using air or helium. Particle trajectories and intermixing of the phases was monitored with a high-speed camera. To simulate the 75FeSi additions, glass spheres were used. A three-dimensional version of the AOD model was then constructed in order to confirm the adequacy of the slice model. Similar particle mixing behaviour was observed. Both models demonstrated that the ascending gas/liquid plume created two asymmetric mixing zones: a smaller rapidly re-circulating mixing zone adjacent to the side-wall locating the tuyere(s), and a larger mixing zone in the main part of the vessel. The process efficiency during the reduction period is governed by the thermal behaviour of ferroalloy as well as the mixing efficiency in the main large mixing zone. To enhance the recovery efficiency for chromium, small Fe-Si particles are suggested, given their wide distribution within the slag phase, and their large interfacial areas and rapid melting times for Cr2O3reduction from the slag. Keywords; modelling, ferrosilicon, chromium oxidation, AOD steelmaking.

Jan 1, 2004

By S. R. Sankaranarayanan, T. Sowmya

Slags and fluxes used in metallurgical processes are typically made up of oxides (especially silicates), with additions of fluoride and carbonaceous matter. Despite the efforts made towards understanding the role of slags in various processes, little information is available on the structure of these slags. Tools such as X-ray diffraction, spectroscopy, and electron microscopy could be used for this purpose. This paper is based on an ongoing spectroscopic and structural investigation of slags and related materials. Spectroscopic studies of various commercial slags (predominantly ferrous), ores, glass and related materials, covering a wide range of compositions, have been carried out to understand the structure. The infrared spectra were recorded, predominantly, using FTIR spectrometer (Bruker IFS 66U) spanning 4000 to 100 cm-1using the KBr pellet method. The resolution was typically 4 cm-1. The spectral outputs have been compiled in terms of bands present (corresponding to different bonds) and then compared with the typical bands expected for such bonds. Efforts are in progress to identify the trends with respect to the chemical composition?for example, the effects of SiO2, Al2O3, and non-bridging oxygens. Data obtained so far indicate some trends such as (i) a shift in the Si-O band (969 to 1099 cm-1) towards a higher wave number with increasing silica content (almost 2 to 92 weight percentage) and (ii) further strong shifts as a function of the alumina content. These are being further investigated structurally and in terms of chemical composition/parameters. Keywords: slags, silicates, structure, spectroscopic analysis, shifting of bands

Jan 1, 2004

By Y. Wang, S. Sridhar, B. Coletti, G. N. Shannon, S. Vantilt

The final removal of inclusions in the ladle, tundish, and mold in a continuous casting process involves the kinetic steps of liquid film drainage, interface rupture, and absorption of the inclusion into the overlaying molten slag. During this process, oxide inclusions can undergo chemical reactions with the slag. This paper presents recent results on imaging the slag/steel interface and elucidates the evolution of Al2O3and Al2O3-CaO inclusions during their separation from the steel and on their incorporation into the slag. Experimental results, obtained through a Confocal Scanning Laser Microscope, are compared with thermodynamic predictions.

Jan 1, 2004

By J. Nell

An overview is given of the matte melting process used for the beneficiation of South African Platinum Group Metal (PGM) ores. Most producers use six-electrode furnaces to melt the concentrate and Pierce Smith converters to oxidize excess iron sulphide from the furnace matte. Concentrates from two reef-types (the so-called Merensky and UG-2 reefs) dominate the feedstock supply. Concentrate from the Merensky reef is low in chromium and do not pose significant melting problems. Concentrates from the UG-2 reef contain much higher levels of chromium, which results in the formation of chromium-rich spinels during melting. This is attributed to the low solubility of chromium in furnace slag under typical operating conditions (an oxygen partial pressure of 10-8-10-9bar at temperatures of 1550°C to 1600°C). During the converting process care is needed to avoid excessively oxidizing conditions, which result in cobalt, nickel and copper losses to the slag. High nickel losses result in the formation ofFe2NiO4(trevorite), which often forms solid solutions with FeCr2O4and Fe3O4. In future, the main challenge in the processing of South African PGM ores will be to cope with ever increasing levels of chromium in the concentrate. A short-term solution to the problem would be to melt the concentrate under slightly reducing conditions to promote the formation of CrO, which is more soluble in the slag than Cr2O3. A longer-term solution to the problem would be to abandon the current matte-smelting process in favour of an alloy-based process, which would offer total flexibility with respect to the amount of chromium that can be tolerated in the feed. Key words: Merensky, UG-2, furnace, slag, matte, converting, spinel, chromium.

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 B. Friedrich

In a German governmental funded three-year research project, a closed loop recycling process for Nickel-Metalhydride-Batteries (NiMH) is under development. Today the discarded batteries are used in the steel industry as a cheap nickel source. Cobalt and rare earth (RE) are slagged and lost for reuse. The entire value of the metals in discarded Ni-MH is estimated to be 4?-4.5 ?/kg. Spent NiMH-batteries containing 36?42 per cent Ni, 3?4 per cent Co and 8?10 per cent rare rarth (Ce,La, Pr, Nd). The dismantled and processed NiMH-batteries are melted in a DC electric arc furnace producing a nickel-cobalt alloy and a slag phase highly enriched with RE-oxides. The key to success in this process is to find a suitable slag system, which ensures best separation of NiCo-alloy from the rare earth oxides and high concentration of RE in the slag. Different oxidic and halogenic slag systems are investigated in the melting process. So far a slag system based on 65per cent CaF2 and 35 per cent CaO delivers the best separation of the two phases and metal yields. A slag with a composition of 20?25 per cent La, 13-16 per cent Ce, 1.5?2.5 Pr, 4.5?6.5 per cent Nd is obtained and further treated to misch metal hydro-/electrometallurgically. The first results of the influence of rare earth oxides on the density of CaO-CaF2slag system are shown at 1600°C. Keywords: battery recycling, CaF2, CaO, rare earth oxides, slag characterization, density measurement

Jan 1, 2004

By M. Suzuki, T. Shiomi, M. Nakada, K. Tsutsumi

Mold powder plays an important role in the continuous casting process for high quality steel production. It is well known that mold powder entrapment causes surface defects in steel sheet and the high viscosity of mold powder prevents the entrapment of mold powder in molten steel in ultra low carbon steel. This paper deals with the entrapment of mold powder caused by suction by Karman?s vortex in a laboratory experiment. At first the effect of the viscosity of oil and interfacial tension between water and oil was investigated in a water model experiment. Then hot model experiments were carried out by mold powder and molten steel. The amount of mold powder entrapment was affected by the viscosity and the interfacial tension between molten steel and mold powder. As a result, the following equation of the mold powder entrapment was obtained. m=1.06*107?-0.255?m-s-2.18 The amount of mold powder entrapment decreased when the viscosity and interfacial tension increased. But the effect of viscosity was larger than that of interfacial tension in the case of the industrial mold powder when the viscosity was under 0.5 Pa.s, interfacial tension was from 1200to 1300 mN/m.

Jan 1, 2004

By K. Ding

The thermodynamic activity of MnO was measured in MnO-CaO-MgO-SiO2slags that are typically encountered in the production of manganese containing stainless steels. Gas equilibration-quenching technique was employed in measuring the activities. Activity of Mn in Pt-Mn alloys were redetermined at 1600°C which reconfirmed earlier results of strong negative deviations. MnO activities were then measured by equilibrating slags of various compositions based on a statistical experimental design procedure with Pt-Mn alloys under controlled partial pressure of oxygen in MnO saturated platinum crucibles at 1600°C. Activities of MnO were found to increase with increasing concentration of MnO, basicity and CaO to MgO ratio. Two multi-coefficient repression models were developed to predict the activities and activity coefficients of MnO in slags at 1600°C. Keywords: activity, MnO, slag.

Jan 1, 2004

1. Book review Technology of metal powders- recent developments, edited by L. H. Yaverbaum. New Jersey, Noyes Data Corporation, 1980. 400 pp. (Reviewer: B. K. Loveday) 2. New books The use of microprocessors, by M. Aumiaux. New York, Wiley, 1980. 176 pp. $25,50. Aluminium smelter technology, a pure and applied approach, by K. Grojtheim and B. J. Welch. Diisseldorf, Aluminium-Verlag GmbH (P.O. Box 1207, D-4000, Federal Republic of Germany). 146 pp. DM48. Coal-bridge to the future. New York, Harper & Row, 1980. $35. System modeling and response.. theoretical and experimental approaches, by O. Doebelin. New York, Wiley, 1980. 576 pp. $26. Environmental and climatic impact of coal utilization, edited by J. J. Singh and A. Deepak. New York, Academic Press, 1980. 646 pp. $39,50. Proceedings of the Third European Conference on Mixing, York, England, April 1979, edited by H. S. Stephens and C. A. Stapleton. BHRA Fluid Engineering (Cranfield, Bedford Mk43 OAJ, U.K.), 1980. 2 volumes. 500 pp. $50. Lignite technology, edited by P. Nowacki. New Jersey, Noyes Data Corporation, 1980. 228 pp. $42. The application of rock mechanics to cut-and jill mining. London, Institution of Mining and Metallurgy, 1980. Papers presented at the Fifth International Symposium on Jet Cutting Technology, Hanover, Federal Republic of Germany, June 1980, edited by H. S. Stephens and B. Jawis. BHRA Fluid Engineering (Cranfield, Bedford Mk 43 OAJ, U.K.), 1980. 438 pp. £38. World coal resources.. methods of assessment and results, by G. Fettweis. Amsterdam, Elsevier, 1979. 425 pp. $80,50. Geophysical and geochemical techniques for exploration of hydrocarbons and minerals, edited by M. Sittig. New Jersey, Noyes Data Corporation, 1980. 300 pp. $40. Financial Times mining international year book 1980. Longman Group Ltd (Periodicals and Directories Division, Longman House, Burnt Mill, Harlow, Essex CM20 2JE, England). £24 surface, £34 airmail. National Symposium on the Availability of Strategic Minerals, edited by M. J. Jones. London, Institution of Mining and Metallurgy, 1980. 109 pp. 3. NIM reports Report No. 1941 The recovery of chromite and platinum from the UG-2 Upper Chromitite Layer .of the Bushveld Complex at the Pandora Mine (first published 10th Mar., 1978). Report No. .2012 A mineralogical investigation of borehole cores from the Trompsburg Complex (first published 6th Apr., 1979). Report No. 2038 The leaching of sphalerite in acidic ferric sulphate media in the absence of elemental oxygen. Report No. 2052 An investigation of the impurities in native gold by neutron-activation analysis. Report No. 2056 The mineralogy and geochemistry of the copper, lead, and zinc sulphides of the Otavi Mountainland. Report No. 2058 A n elementary introduction to image analysis - a new field of interest at the National Institute for Metallurgy. Report No. 2059 Distributed computer control of industrial processes. Report No. 2060 The analysis, by atomic-absorption spectrophotometry, of activated charcoal.

Jan 1, 1980

A physical modelling study has been carried out to simulate the slag-metal dispersion induced by a high-strength bottom gas injection. Water and kerosene were utilized to simulate metal and slag respectively. A water model of CLU (Creusot-Loire Uddeholm) vessel was used with three different nozzle orientations, namely, off-centre, triangular off-centre and centre. The gas flow rates changed from 0.00599m3/sec to 0.01081m3/sec. Height of heavy and light phases was kept fixed at 0.23 m and 0.02 m respectively. The dispersed phase holdup was determined at various axial and radial distances, gas flow rates, and tuyere configurations. The observations revealed that at a fixed gas injection rate, as the vertical distance increased in the centerline, straight off-centre orientation resulted in greater dispersed phase hold up values than those of the centre configuration and the triangular off-centre orientation. The dispersed phase holdup was found to increase with gas injection rate and decreased with axial distance. The variation of the dispersed phase hold up with the dimensionless axial distance and the gas injection rate was correlated by using the Modified Froude Number. The experimental values of the dispersed phase holdup were found to be in good agreement with the correlated values obtained from the modelling equations. The findings of the present study may be utilized in the ferroalloy refining vessels in terms of designing tuyere locations for optimum processing conditions.

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