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By A. D. Pelton, Y. -B. Kang, S. A. Decterov

Computerized thermodynamic databases for solid and liquid metal, slag and solid oxide phases in the Al2O3-CaO-CoO-CrO-Cr2O3-FeO-Fe2O3-MgO-MnO-NiO-SiO2-S system have been developed by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain parameters of models specifically developed for molten slags, liquid steel and solid oxide solutions such as spinels, pyroxenes, olivine, monoxide (wustite, periclase, lime), corundum, etc. By means of the optimization process, model parameters are found which reproduce all thermodynamic and phase equilibrium data within experimental error limits. Furthermore, the models permit extrapolation into regions of temperature and composition where data are not available. The databases are automatically accessed by user-friendly software that calculates complex equilibria involving simultaneously slag, metal, refractories and gases, for systems with many components, over wide ranges of temperature, oxygen potential and pressure. A short review of the available databases is presented. The critical evaluation/optimization procedure is outlined using the Al2O3-CaO-FeO-Fe2O3-SiO2and Al2O3-CaO-MnO-SiO2systemsas examples. Several applications of the databases to deoxidation of iron and to inclusion control in steel are discussed. Keywords: thermodynamics, phase equilibrium, phase diagrams, databases, ferrous metallurgy, steelmaking, inclusion control, slags, oxide systems.

Jan 1, 2004

By M. A. W. Bryson

Platinum group metals are extracted almost exclusively in South Africa from three very different zones in the Bushveld Igneous Complex, called the Plat, Merensky, and the UG-2 reefs. The Plat reef is currently being exploited only by Anglo American Platinum, whereas the Merensky reef is exploited by them, Impala Platinum, Northam, and Lonplats. The UG-2 reef, on the other hand, is also processed by these producers, but Kroondal and Barplats have operations that exclusively treat ore from this reef. At present the extraction of pgms from ores in South Africa follows the traditional route of upgrading to a concentrate in a minerals processing circuit, further upgrading to a matte in a smelter, and final upgrading and separation of the individual metals in a refinery. Thus all operations that extract pgms require a minerals processing circuit, the design and performance of which is a topic of much interest, as it is a poorly understood and not a very efficient process in relative terms, compared to the other processes. Recoveries across the minerals processing circuit of between 75 and 90% are the norm.

Jan 1, 2004

By S. Luyckx

This paper reports hardness and abrasive wear resistance test results from a wide range of WC-Co alloys, varying in cobalt content as well as WC grain size. The results show that the abrasive wear resistance increases with increasing hardness and that the rate of increase is higher for larger WC grain sizes. The increase in abrasive wear resistance was found to be parabolic up to a critical hardness value and exponential above that value. The transition from parabolic to exponential behaviour was found to occur at the same contiguity value for all grain sizes, which suggests that at that contiguity value the WC skeleton becomes continuous in all WC-Co alloys.

Jan 1, 2004

By J. Härkki, R. Hiltunen

The Akanvaara intrusion (surface area 50-55 km2) in Savukoski, Northern Finland, hosts 23 distinct monocumulate layers of small euhedral chromite crystals enclosed in a silicate matrix. These chromitite layers have been divided into four groups; UC (upper chromitite), ULC (uppermost lower chromitite) LC (lower chromitite) and LLC (lowermost lower chromitite). The driving force for investigating the Akanvaara chromites and their reduction behaviour originated from their very low MgO content and relatively low Al2O3 content, giving them a unique quality which based on thermodynamics should facilitate the reduction. Another interesting feature is the high amount of V2O3 present especially in the upper chromitite. The chromites included in this study are from the UC and ULC layers (24.9 and 22.7 per cent Cr2O3 respectively). To obtain a better understanding of the reduction behaviour of Akanvaara samples in comparison to MgO-bearing chromitites, Kemi chromite from the ferrochrome works in Tornio, Finland, was included in the study as a reference sample. The reduction experiments were isothermal in a temperature range of 1000-1400°C in CO atmosphere. Experiments were also conducted with coke addition in pellets and briquettes in CO/Ar/H2 atmospheres. The results of the reduction experiments complemented with microanalytical research indicate that the Akanvaara chromites do reduce to a higher degree than the Kemi chromite. Although the aim was to characterize the mechanisms of reduction focusing on gas-solid reactions, the nature and amount of the gangue minerals was such that a considerable amount of slag phase was formed, which affected the reduction mechanisms extensively. The structural features together with low MgO and high FeO content in both Akanvaara chromites are important factors resulting in better reducibility than in the Kemi chromite.

Jan 1, 2004

By J. -C. Tricket, W. A. Düweke, S. Kock

The high-resolution three-dimensional (3-D) seismic reflection data acquired for Impala Platinum between 1998 and 2002 in the western Bushveld Igneous Complex form an integral part of Impala?s mine planning and development programme. These data are of sufficiently high quality to provide unprecedented 3-D models of the geological structure of the Merensky Reef and UG2Chromitite Reef, from which the mine deduces the size, geometry and distribution of mineable blocks. Conversely, the seismic data details zones of un-mineable ground caused by structural disturbances in the form of potholes, fault zones and pegmatoid intrusions. Furthermore, variations in dip and strike are well imaged, allowing the mine planners to optimize the mine design and layout. Current interpretation work is focused on enhancing the accuracy of these geological model seven further through the analysis of ?seismic trace attributes.? Preliminary testing on the Impala Platinum 3-D seismic volume has shown that attribute analysis has the potential to illuminate a number of geological reef disturbances that are otherwise ?invisible? in the original seismic time volume. Potential areas of improvement include inter alia: ?Improved definition of major fault zones ?Improved definition of zones of reef depression (?slumping?) ?Identification of reef terracing and/or reverse dip.. Keywords: 3D reflection seismics; Impala Platinum Ltd; seismic attribute analysis; Seismic Micro Technology (SMT); rock solid attributes; dip-azimuth; instantaneous phase and similarity.

Jan 1, 2004

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

By Z. Zhang

The author recently has reviewed the publications on the slag-related research in China since the Sixth International Conference on Molten Slags, Fluxes and Salts in June, 2000. In fundamental aspects, the physical property predictions and measurements, slag-metal reactions, slag-refractory reactions have received close attention, and are briefly described here in this report. More than half of slag-related publications deal with plant investigations due to the requirement of technological improvements and environmental protection. In the present paper, the research on slags in various treatments related to clean steel production and the utilization of the waste slags is briefly reviewed.

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 W. Banda

Paper written on project work carried out in partial fulfilment of Phd. (Process Engineering) degree* The recovery of cobalt and copper from waste slag was studied in a plasma DC-arc furnace in reducing conditions. Three fluxes, CaO,CaF2, and TiO2, were investigated for their influence on selective recovery of cobalt into an iron-rich alloy. A further investigation on the influence of furnace power on the reduction of slag to recover cobalt to the alloy showed that a change in power setting had an unexpected effect on the recovery of metals to the alloy, in that selectivity of base metal recovery over iron recovery decreased at an increased power level. Keywords: DC-furnace, reduction, nonferrous, slags

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 P. J. Bhonde, R. D. Angal

Conventionally low carbon ferromanganese is manufactured globally by refining high carbon ferromanganese in liquid state. This process is an expensive and lengthy technique. Hence, the present work was undertaken with the objective of understanding the feasibility and kinetics of the solid state refining of ferromanganese. The process involved transformation of carbon rich carbides viz. Mn3C2, Mn7C3 into metal rich carbide i.e. Mn15C4, Mn23C6 by subjecting the alloy powder to a flowing stream of carbon dioxide. Effect of the process governing parameters such as time, temperature, particle size, pressure on the extent of decarburization was studied. Without any loss of manganese in the form of fumes or slag, it was observed that, there was substantial reduction, viz. 65 per cent in the total carbon content, by this technique. Subsequently, the process was investigated to find out the mechanism of carbon removal. Depending upon the temperature and the particle size, it was found that the rate controlling mechanism changes from chemical reaction control to product layer (ash) diffusion control. The activation energy for each of the aforesaid mechanism was computed. The values thus obtained substantiated the aforesaid mechanisms.

Jan 1, 2004

By O. Gunaydin

Performance measurements of large-diameter circular saws were conducted on eight different carbonate rocks in marble factories located in some areas of Turkey. Rock samples were collected from these factories for laboratory tests. Uniaxial compressive strength, tensile strength and impact strength were determined in the laboratory. The brittleness of B3 (the ratio of compressive strength minus tensile strength to compressive strength plus tensile strength), the brittleness of B5 (the product of percentage fines in the impact strength test and compressive strength) and the brittleness of B8 (half of the product of compressive strength and tensile strength) were calculated from the test results. Hourly slab productions were correlated with brittleness indexes. It was concluded that sawability of carbonate rocks can best be predicted from the brittleness of B8.

Jan 1, 2004

By H. Jalkanen, L. Holappa

The main role of slag in oxygen converter processes is to absorb the non-volatile oxidation products of hot metal impurities, Si, P, Mn, Ti, V, etc. The importance of converter slag as deP and de Smedia has ceased with implementation of special pre- and post-converter treatments. The transfer from top blowing (LD) to combined blowing converters has decreased the amount of slagged iron that, together with the tendency towards lower silicon and manganese contents, has decreased slag to steel ratio. Still the control of slag forming and behaviour during the blow is of great importance. In this paper the thermodynamics of the slag forming reactions, the role of slag in the modern oxygen converter process for impurity elimination, splashing, lining wear, dust formation and post combustion are discussed on the basis of common knowledge and experience of Finnish steel plants.

Jan 1, 2004

By Y. Nakata, K. Nagata

Plasma is partially ionized gas composed of ions, electrons and activated elements at high temperature. Some flying ash from incinerated municipal waste is melted to become glass by a transfer-type arc plasma furnace. As the glass is ionic silicate, when an electric current passes through anode to cathode, ions in molten slag electrochemically react with electron in plasma at the surface of molten slag. In case of molten Na2O-SiO2, sodium ions in the molten slag carry electric current and SiO2are reduced to evaporate as SiO gas by electron in plasma. The cases of Ag+in NaNO3-KNO3molten salt and Fe2+in FeO-SiO2slag were examined. The amount of cathodic reaction is larger than that of anodic reaction and not apparently according to the Faraday?s law on the electrochemical reactions.

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 A. M. Hearn, J. G. Roos

Energy consumption, being a large proportion of the input of the ferroalloy production process, can be measured in terms of the efficiency with which the energy is utilized and the effectiveness with which it is used. The efficiency of the usage of energy revolves around the specific consumption of the energy for the production of the alloy, which encompasses the thermodynamic aspects of the process and is more of a metallurgical function that will not be addressed further in this paper. The effectiveness with which the energy is utilized is determined by the optimisation of the electricity supply from the utility (in this case Eskom). The South African electricity supply industry is on the brink of considerable restructuring, implying changes in ownership, structure and regulation. In other countries, however, restructuring has often seen higher prices. Owing to the diversity of growth prospects in South African markets, Eskom is turning to new market management and generation strategies. In future, Eskom will develop pricing strategies to increase demand from attractive customer segments such as paper & pulp, iron & steel, aluminium, and other metallurgical industries. There will be a broader spectrum of product offerings, including dynamic pricing options and demand-side management incentives. In a future electricity market that will become more dynamic and demanding, it will become increasingly important for electricity consumers to optimise their electricity supply. There are many facets in optimising the electricity supply, which include optimal utilisation of the tariff, integrating energy cost management into the production planning process, implementation of demand-side management actions, modelling, scenario planning (.what-ifs?.), optimisation, maintenance scheduling coordinated with the tariff periods, etc. This paper gives consideration to the status of the development of technology at the manganese alloy works of Samancor at Meyerton, South Africa in order to increase the effectiveness with which energy is utilized.

Jan 1, 2004

By B. Kruger

After the milling and flotation of the platinum bearing ore, the flotation concentrate is electrically smelted in 6-in-line electric arc furnaces and the resulting furnace matte treated in Peirce Smith converters to remove the iron. The iron-free (less than 1% Fe) converter matte is granulated and sent to the base metals and precious metals refineries for further processing. During the smelting and converting processes two distinct gas-strength gas streams are produced: ?The Peirce Smith converter off-gas contains 4%?9% SO2which is treated in a conventional sulphuric acid plant to produce 94% H2SO4. ?The electric furnace off-gas contains 0.9% SO2which was (until September 2002) vented through a 91- metre high stack to atmosphere. In October 2002 Impala Platinum commissioned a SULFACID® plant at its smelter in Rustenburg, which recovers the SO2from the electric furnace off-gasses into a weak sulphuric acid solution. The SULFACID® technology utilizes wet activated carbon to oxidize the SO2toSO3. The SO3reacts with the water on the catalyst and is washed off the catalyst bed as a sulphuric acid solution with up to 13 wt. H2SO4. The plant operates at 60ºC and at atmospheric pressure. The SULFACID® technology is widely used in the pigment industry. This is, however, the first application of the technology on electric furnace off-gas. Keywords: SO2, sulphuric acid, electric furnace, off-gas, SULFACID®

Jan 1, 2004

By S. Parada, P. T. Jones, M. Guo, S. Smets

The corrosion behaviour of a high-quality rebonded magnesia-chromite refractory in contact with a vacuum oxygen decarburization (VOD) slag with high Al2O3content (15?20 mass per cent) is investigated under VOD process conditions by rotating finger tests in a vacuum induction furnace. The refractory degradation mechanisms are studied by the characterization of corroded microstructures using scanning electron microscopy, equipped with energy dispersive spectroscopy. The influence on the refractory wear of the process temperature and the Al2O3content in the slag is discussed. Keywords: corrosion, magnesia-chromite refractory, VOD slags, vacuum induction furnace

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. Shiraishi, Y. Sakurai

A new method, the gliding cylinder method, was proposed as a wide range viscometer for the measurements of molten salts, slags, and glasses. The method consists of two coaxial cylinders, cylindrical bob and a vessel containing a liquid sample. There is a narrow gap between bob and vessel. When the vessel moves against the bob, the generated force on the bob consists of three types of resistance: (1) Stokes’s resistance on the bob, (2) a capillary flow resistance though an annular gap between vessel and bob, and (3) lubricating resistance in a gap. The last two can be calculated on a theoretical basis but the first cannot be estimated by a simple calculation since a wall effect did not calculate easily. However, it can be assumed that the generated force depends on both the viscosity of a liquid and velocity of the vessel. Thus, the relation between viscosity and a force at desired velocity of the vessel was measured using several standard reference materials including glycerol aqueous solutions and standard reference oils. The results depended on the magnitude of the gap between the bob and the vessel. For the wider gap, it was shown that the viscosity is a linear function of a gradient of force with respect to a vessel velocity. In contrast, if the gap is small, the viscosity depends on the gradient (of force with respect to velocity). This implies that the non-linear phenomena would occur in Stokes resistance. Though detailed analysis is in a further investigation, a calibration method can be applied to determine the viscosity by this method, because good correlation was obtained among these quantities. Viscosity of molten salts, such as NaNO3and ZnCl2was measured by this method as high temperature demonstration. Keywords: viscometer, viscosity, sphere pull-up method, fused salts, molten slags, glass melts

Jan 1, 2004