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By M. Magnelöv, Du Sichen, U. Sjöström

An experimental study has been performed to investigate the behaviour and separation of inclusions at the interface between steel and slag. The study has been limited to liquid inclusions because they can be a potential problem in transient situations such as ladle changes in continuous casting of steel. Model experiments with water and silicon oils have been carried out to study the kinetics of separation of simulated inclusions at an interface. The properties of the inclusions and the slags have been varied by using different oils with different viscosities, densities and surface tensions. The effect of temperature of the liquids has also been examined. Measurements of the terminal velocity, rest time and the behaviour of the liquid inclusions at the interface have been recorded using a video camera. It has been found that the inclusions reach their terminal velocity early in the vessel and the experimental velocities differ somewhat from the values evaluated using ?intermediate law?. The results from the experiments have shown that the size of the inclusions has no appreciable influence on the rest time. Droplets of AK50 oil have been found to have considerably long rest time. A water film surrounding the droplet has been expected to be the main reason for the long rest time. The present study has also shown that the viscosity of the oil has certain effect on the rest time, but only to some extent, since viscosity has double functions. A higher viscosity provides higher resistance to the droplet entering the oil phase leading to longer rest time and at the same time damps the lateral movement of the droplet along the interface, leading to easier stabilization and shorter rest time. On the other hand, a high viscosity of the oil phase results in slow dissolution process. It has been concluded that a meaningful model of inclusion separation at the metal-slag interface must take the interfacial phenomena into consideration. Keywords: Inclusions, terminal velocity, rest time, dissolution.

Jan 1, 2004

By H. Pei

PZH (Pan Zhi Hua) Iron and Steel (Group) Corporation, the biggest steel company in southwest China, has been using titanium-vanadium-magnetite as the main raw materials for blast furnace iron making processing for over 30 years. One of the problems that has a negative affect on the blast furnace operation is slag foaming. Based on the chemical components of the blast furnace slag-bearing higher TiO2, the foaming properties were studied. The TiO2content, which is calculated according to the total titanium content in all the forms of titanium compound in the slag, in this research is 30% weight per cent. Different forms of titanium compounds have different actions on the slag foaming behaviour that depends on the reduction condition in the blast furnace. The relationships among slag foaming performance and the binary alkalinity of the slag, the content of CaF2, MnO in slag, and the amount of gas injected in slag are investigated. The results show CaF2 and MnO have a stronger anti-foaming affect on the slag, even in the lower percentage. The way to measure high TiO2slag foaming performance and how to eliminate foamy slag are also discussed. Keywords: blast furnace slag bearing TiO2, foamy slag, foaming performance

Jan 1, 2004

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

By M. Somerville, S. Sun

The liquidus temperature and viscosity of a range of melter slags produced in South Africa were determined. Drop-quench experiments were carried out on the supplied plant samples to determine the liquidus temperature and phase relations at sub-liquidus temperatures. The temperature measurement range covered 1300°C to 1630°C. Results from these experiments show liquidus temperatures for the melter slags to be in excess of 1500ºC with the chromium containing spinel as the primary crystalline phase. At lower temperatures, an olivine or pyroxene phase co-existed with the spinel phase. The viscosity of the slags was determined over a temperature range of 1350 to 1550°C, under a controlled atmosphere. Results show two orders of magnitude variation in the viscosity (0.2 to 20Pa s) with strong effects of slag chemistry and temperature. Slags with lower SiO2and Cr2O3concentrations were more fluid. Slags with the lowest FeOx and highest SiO2concentrations were the most viscous. These observations are in accord with general behaviour of silicate slags. While the presence of a spinel phase may have an effect on the viscosity of the melter slags, results obtained to date indicate a much stronger effect due to the presence of an olivine or pyroxene phase at lower temperatures. Keywords: phase equilibria, liquidus, viscosity, slags, olivine, spinel, pyroxene

Jan 1, 2004

By L. Holappa

Ferroalloys like FeCr and FeMn are mostly produced in submerged electric arc furnaces. Typical for these processes is that the amount of slag is quite high. The role of slag for the process is thus very essential and specific chemical, physical and electrical properties are required. Slags in FeCr process are Al2O3-MgO-SiO2based with minor contents of CaO and CrOx. Slags in FeMn process are principally similar originating from silicate minerals but can have quite a large composition range depending on the manganese ore and its gangue minerals. Characteristic for FeMn process is that the slag is rich in manganese oxide up to above 30%. A common feature is that the ?ore oxides?, CrOx and MnOxin slag are not only divalent oxides but also containing some higher valent of Cr3+ and Mn3+, respectively. In FeMn production conditions the slag consists mainlyMn2+. This is a clear difference from CrOx containing slags in which both two and three valent coexists in slags in FeCr process conditions. Oxidation state of the slag depends on the ambient oxygen partial pressure and temperature in the examined process. Thermodynamics of slags in ferroalloys production are discussed in terms of phase diagrams, activities and oxidation state of chromium and manganese oxides. Further, slag properties influencing reduction kinetics and furnace operation i.e. viscosity and electrical resistivity are discussed. Keywords: review, slags, ferroalloys, ferrochromium, ferromanganese, thermodynamics, physical properties.

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 J. Hop, A. Støre, T. Foosnæs

The carbon cathode for aluminium electrolysis is also part of the container of the process. In order to understand the behaviour and possible failure of the cathode, detailed material properties under operating conditions are needed. The paper reports experimental studies of bath and sodium in filtration, graphitization with time, loss of strength due to sodium, sodium expansion as function of pressure, as well as creep due to the developed stresses. As an example, sodium and thermal expansion data are used to calculate strain-stress models of realistic cell designs, and possible design weakness can be pointed out. Keywords: carbon, cathodes, sodium expansion, strength, graphitization, creep

Jan 1, 2004

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 Z. Zhang, R. G. Reddy

Experimental and thermodynamic modelling studies on the structure of alkali borate melts and properties are discussed. A thermodynamic structure model for alkali borate melts is developed to describe the distribution of structural groups in the alkali borate melts as a function of composition. A qualitative interpretation for the boron anomaly in viscosity has been proposed, which regards the boron anomaly as a manifestation of the various antithetical effects caused by the introduction of alkali oxide into boric oxide. It has been found that the viscosity of alkali borate melts increases or decreases according to the changes in rigidity and spatial connectivity of the glass network structure, which is the function of temperature and composition. These concepts with some key examples are discussed in relation to their usefulness and practicality in industrial slags. Keywords: alkali borate melts; structural model; activities; structural groups; viscosity;

Jan 1, 2004

By Y. D. Lee, J. H. Park, D. S. Kim, H. S. Song

The viscosities and the infrared spectra of the CaO-SiO2-MgO-CaF2(or Al2O3) slags were measured to enhance our understanding of the interrelationship among the thermophysical property, microscopic structure, and chemical thermodynamics of molten slags. The structural role of CaF2and Al2O3in the calcium silicate melts can be explained by a change of the degree of polymerization (DOP). The effect of CaF2on the viscous flow of molten slags is based on a decrease in the DOP by F-as well as by O2-ions and this was confirmed by the infrared (IR)spectra of the quenched slags. The effect of Al2O3on viscosity increase can be understood from an increase in the DOP by the incorporation of the [AlO4]-tetrahedra into the [SiO4]-tetrahedral units and this was also confirmed by the IR spectra. An amphoteric behaviour of Al2O3in the aluminosilicate melts could be correlated to the effect of ionic species of alumina, that is [AlO4]-tetrahedra and [AlO6]-octahedra, on the stability of silicate polyanions by taking the activity coefficients of slag components into account. Keywords: viscosity; infrared spectra; degree of polymerization; amphoteric behaviour; stability; activity coefficient

Jan 1, 2004

By A. Kondratiev

A structurally-based viscosity model for fully liquid silicate slags has been developed and applied to the Al2O3-CaO-‘FeO’-SiO2system at metallic iron saturation. The model links the slag viscosity to the internal structure of melts through second nearest neighbour bonds concentrations taken from the quasi-chemical thermodynamic model. This viscosity model describes experimental data over the whole temperature and composition ranges within the Al2O3-CaO-‘FeO’-SiO2system at metallic iron saturation and can now be applied to other industrial slag systems.

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 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 Bjørn Nilsen, Werner Stefanussen

The construction of the Guaigui Multipurpose Project includes a 74 metre high concrete face rock fill dam, a 350 metre long diversion tunnel and a 350 metre long spillway tunnel. The topography in the project area is very steep, and the rock masses are characterized as soft rocks. The stability of the 80 to 100 metre high dam abutments and the excavation of the tunnels in soft rock conditions have caused various challenges and problems to be solved. Limited pre-investigations have called to a great extent for estimation of parameters for the stability calculations based on experience. The preliminary calculation of the stability of the planned rock slope above the spillway intake platform has been carried out by conventional partial factor methods and by use of a computed based Slide Program. The two methods of calculation give different results , and that rock support is necessary to obtain an acceptable factor of safety for a slope inclination of 52o. The input parameters for the rock mass characteristics need to be verified for the permanent calculations.

Jan 1, 2006

By X. Pan

Slag-metal equilibrium experiments were conducted at 1500ºC and 1580ºC under 0.03 atm, 0.05atm and 0.83 atm CO partial pressures using silica and Cr-oxide crucibles. The complex slags belonged to SiO2-CaO-Al2O3-MgO-FeOx-CrOxand the metal phase to the Cr-Fe-C-Si-(S)systems. The carbon saturation of the metal phase was avoided using oxide crucibles and thus the results are pertinent to ferrochromium refining slags and processes. From equilibrium data and thermodynamic calculations the CrO /(CrO+Cr2O3) ratio in the slag was determined as 0.75, 0.80and 0.86 under 0.83 atm and 0.05 atm of CO pressure at 1500ºC and 0.03 atm and CO pressure at1580ºC respectively. The results clearly demonstrated that a higher chromium content of the metal results in higher Cr in the slag, and chromium in slag decreases with increasing SiO2. The results were also sensitive to the crucibles used as these oxide crucibles saturated the slag either with respect to SiO2or Cr-oxides. It was also demonstrated that the relative amount of CrO in the slag was higher when SiO2crucibles were used in accord with thermodynamic calculations. Iso-concentration curves for carbon and chromium of the metal phase in equilibrium with the slag were drawn on pseudo ternary SiO2–(AI2O3+CaO+MgO)–(Cr2O3+Fe2O3) diagram. The activity coefficients and activities of carbon and chromium of the metal phase were also calculated from the experimental data and available thermodynamics information and were plotted as iso-activity curves in the same pseudo ternary diagram. Keywords: Chromium, slag, equilibrium

Jan 1, 2004

By S. Asokan, CVGK Murty, R. Upadhyay

The principal mineral sources of titanium are rutile, anatase (both TiO2), ilmenite (FeTiO3) and leucoxene (a weathered ilmenite of variable concentration of TiO2 but similar to pseudorutile Fe2Ti3O9). These titaniferous minerals along with their value added products like Synthetic Rutile and TiO2 slag constitute ?Titanium Feed-stocks? for TiO2 pigment, Ti metal and welding electrodes industries. Unlike in other industries, the demand driver for titanium minerals is not the metal, but the TiO2 pigment ?a specialty chemical. Of the total titanium feedstocks usage in the world, about 93 % is consumed in TiO2pigment, with only about 3 % is utilized in metal production. India?s heavy mineral sands resources are among the largest and also one of the richest grades in the world. The country?s Ilmenite resource base stands at 348 million tonnes of Ilmenite (18% of the total world reserves)along with 18 million tonnes of Rutile, 21 million tonnes of Zircon, 8 million tonnes of Monazite, 107 million tonnes of Garnet and 107 million tonnes of Sillimanite. Though the grades (Total Heavy Minerals (THM) present in the sand) of Indian deposits are relatively rich, the contained ilmenite are termed as sulphate grade with 50-53% TiO2 (Chavra deposit of Kerala and Ratangiri deposit of Maharastra are an exception with 60% of TiO2). While superior grades with adequate reserves lead to a cost advantage in ilmenite production, the lower TiO2 percentage allows the direct use of Indian ilmenite only in the production of TiO2 pigment through sulphate route and for the chloride pigment production; such ilmenite is required to be upgraded either to Synthetic Rutile (SR) or TiO2 slag. However, in order to produce TiO2 slag in India at a globally competitive cost, the issues like high power tariff, inadequate infrastructure, expensive logistics, less enthusiastic market preferences, supply-demand gaps are to be adequately addressed. This paper deals with some of the above issues and possible solutions thereto in production of TiO2 slag from Indian ilmenite.

Jan 1, 2007

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 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 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 L. Andrews

Nickel is recovered as a by-product of the platinum-producing process operated by Anglo Platinum. The metal is mined mainly as sulphide minerals contained in platinum ores. These pass through the concentrating, smelting and converting process route and nickel is finally recovered by electrowinning. Smelting of the concentrated ore in the electric furnace produces a melt with a high slag to matte ratio. The resulting furnace slag is granulated and later milled and floated to recover matte. A project was initiated to investigate the distribution of nickel in the slag in order to improve recovery. Slag samples were examined using a combination of chemical and mineralogical techniques. The granulated slag was found to consist mainly of a silicate glass phase, which reflects the composition of the molten slag in the furnace. Nickel occurs as free matte granules, as matte phases locked inside the glass, and in the glass phase itself. Whereas nickel in the matte is as sulphide, most of the nickel in the glass phase appears to be oxide- bound(i.e. in solid solution). Milled slag as flotation feed showed recovery-limiting features such as free matte with oxidized surfaces and unliberated matte inclusions in the slag. The biggest nickel losses, assuming no tapping problems, are in the glass phase solid solution. Only around 40% of nickel would be recovered from the slag, even under ideal conditions. Spoon and pot slag samples were also examined to see if casting and crushing would improve recovery. Although larger and therefore more easily recovered matte phases formed, nickel partitioned into crystalline silicate phases, limiting the maximum theoretical nickel recovery to 70%.

Jan 1, 2004