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By H. Hearnden

Whereas in the past, ladles were simply a means of transferring molten products from furnace tapholes to points of discharge be they casting pans or waste dumps, the ladle is now becoming a more integral and versatile piece of equipment in the pyrometallurgical plant. The drive behind this development is the need for continuous improvement in performance where better, faster and cheaper means remaining competitive in the global market. This paper will explore the technologies available for the rendering of a costly and otherwise cumbersome piece of pyrometallurgical equipment more efficient and versatile in adding value to the final product. Essentially it all revolves around heat and more importantly the loss of it when tapping. The common practice is to move the molten product to its point of discharge quickly with the minimum of interruption to prevent skulling and hence the cost associated with clearing it. The advances in Oxy-fuel burners, AC or DC ladle furnaces, converters, gas purging and high velocity, bath injection systems has increased the versatility of processes and enhanced the potential for adding value to intermediate products through down stream practices such as granulation and atomisation.

Jan 1, 2004

By P. R. Scheller

Reactions between metal and slag are of decisive importance for metallurgical processing. In the continuous casting process, where metal solidifies at the metal-slag interface, reaction products can cause surface defects, with quality damages of the cast products as a consequence. These investigations are focused on the contact area between casting flux and metal. The samples were taken from the mould during the casting process. The results show that layers up to approximately 300 nm from the slag/metal interface represent a specific reaction space. Sodium in this layer on the slag side plays a specific role, which is explained on the basis of experimental results. The transport of oxygen near the interface and the charge transfer is explained on the basis of the ionic character of the slag. The mass transfer rate of oxygen crossing the interface is calculated from measured data, and conclusions concerning the stability of the interfacial tension are made. Keywords: mass exchange, metal slag reaction, interface, ion transport, oxygen transfer, oxidation, casting slag, flux, sodium

Jan 1, 2004

By A. McLean, M. Iwase, K. Wakimoto, K. Katogi

For many decades control strategies have been based upon samples taken from liquid steel, molten slag and gas phase as well as from solid products. Because of recent developments in the areas of dynamic control models, artificial intelligence and expert systems, there is an increasing incentive to develop diagnostic sensors, which permit in-situ rapid determinations of concentrations of various elements in molten steel. In this paper, an overview is given on recent developments in the areas of sensors for use in ferroalloy and steel production. Particular emphasis will be given on (i) innovative application of sensors for on-line determinations of dissolved elements, Si, P, N, H and Cr in molten iron and ferroalloys, (ii) evaluation of inclusions in liquid metal and (iii) rapid determinations of slag compositions.

Jan 1, 2004

The effect of composition on electrical conductivity (resistivity), viscosity and liquidus temperature of the slags encountered in electric smelting of PGM-containing suphide concentrates is reviewed along with the relationsip between slag composition, slag-matte separation and metal losses to slag. Optimization of slag composition at furnace temperature is attempted on the basis of opposite and parabolic trends of the viscosity-conductivity relationships of the slags. The importance of surface tension of slags is emphasized using available and estimated information, which are grouped into a useful correlation. These values are coupled with or incorporated into slag viscosity plots to illustrate the correlation between the two factors which influence slag-matte separation as well as refractory attack. The electrode in the slag-resistance furnace is the central factor in the design and operation of the furnace by its role of conveying the smelting power. The obvious parameters are the size and positioning in the slag bath, which are defined by slag resistivity, furnace resistance, cell constant and power input. The flow of heat generated by the electrode current determines the energy distribution and furnace dimensions creating viscosity profiles, which in turn affect flow conditions. Thus the flow of slag and matte isdiscussed in conjunction with the furnace geometry, stirring action of the electrodes, buoyancy and electromagnetic effects. The action of the electric furnace as a settler is discussed. The rectangular furnace is considered as a channel reactor in this analysis and the action of the electrodes is described to indicate a balanced settling rate in the area of electrode action. Discussion of the design and production capacity of the electric furnace with reference to operating current, power input, furnace dimensions and electrode size are based on considerations derived mainly from slag properties such as its resistivity, viscosity and liquidus temperature.

Jan 1, 2004

By E. Milke, A. Arnold, B. Friedrich, A. Sydykov

CaF2is often used as a fluoride addition to the chloride salt flux in the melting of aluminium scrap. The solubility of CaF2in the chloride salt system is limited. Dissolved CaF2is considered to improve the properties of salt fluxes. Experimental investigations indicated that the solubility ofCaF2in 70 wt % NaCl/30 wt % KCl, German salt flux used in aluminium scrap melting, might be lower than expected according to literature data. The pseudo binary section CaF2-(70 wt % NaCl-30 wt % KCl) was investigated by differential thermal analysis (DTA). The determined solubility of CaF2appeared to be considerably lower than presented in the literature. The pseudo binary section calculated using thermodynamic data partially confirmed the results. DTA allowed us alsoto determine the crystallization temperature interval of the two phase eutectic consisting of the solid solution NaCl-KCl and CaF2. Keywords: aluminium recycling, phase system, salt flux, CaF2, NaCl, KCl, solubility

Jan 1, 2004

By N. R. Shoko, J. Chirasha

Zimbabwe Alloys has been producing Low Carbon Ferrochrome since 1953. A number of operational and technical advances have been made since then. Some of these advances improved production significantly. Process control, however, remained a challenge not only in the production process itself but also in the handling of finished product. In addition the handling of the slag created an environmental problem. Process control issues were addressed by Zimbabwe Alloys Limited and Japan Metal & Chemicals (JMC) entering into a Technical Transfer Agreement. The aim of the technical transfer was to improve production, alloy quality and, thereby, the financial performance of Zimbabwe Alloys. In addition, the Low Carbon Ferrochrome production process was made environmentally friendlier by modifying the final slag handling methodology. The aspects that are covered and discussed in this paper are, ladle refractory lining changes, improved control of the process, changes in the alloy casting methodology and granulation of the final slag. The improved control of the process was enhanced by the conversion from ladle duplexing to argon purging, introduction of on-line sampling and introduction of second stage process. The combined effect of the above was a significant improvement on on-grade material production, production efficiencies, unit cost of production and a cleaner working environment.

Jan 1, 2004

By R. Dippenaar

The emergence of new steel grades is largely driven by the need to produce high quality steel at a competitive price. The principal aims are to attain ultra-high purity, (especially low interstitial elements) and ultra-cleanliness (by the control of the inclusion content and size). Whereas the steel used to build the Titanic contained 650 ppm sulphur, resulting in MnS stringer-inclusions 25 mm in length, modern quality requirements for arctic pipelines would only allow 10 ppm of sulphur and inclusions in ball-bearing steels must be smaller than 5µm. Most developments are aimed at hot-metal treatment before refining and ladle treatment after decarburisation. Because ferroalloys are added during or after the refining step, it is the secondary (ladle) refining production technologies that are of specific interest to the ferroalloy producer. Through ladle treatment, hydrogen and nitrogen contents are reduced, ultra-low levels of solute impurities are attained and the shapes as well as the composition of inclusions are modified. Steelmakers are concerned about the cost effectiveness of the use of ferroalloys such as consistent product analysis and delivery, improved financing arrangements and technical support. Minimal variation in product sizing is vital because it impacts on handling problems and because particle size determines the rate of particle dissolution. The required ferroalloy product quality depends on the specific use but in general sulphur, phosphorous and nitrogen contents are of concern. Apart from the presence of trace and impurity elements, ferroalloys also contain inclusions. For example, ferromanganese may contain MnO-MnS-SiO2 inclusions while high-carbon ferro-chrome may contain different kinds of Cr-Mn-spinels. The presence of these impurities and inclusions has a significant impact on steel production techniques and cost and hence, on the selection and use of ferroalloys. The interrelationship between ferroalloy quality and steel production technology is plant and product specific and hence, effective communication between ferroalloy suppliers and steel producers is essential.

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

By Du Sichen, K. Mukai, S. Seetharaman

Viscosities of slags constitute an important physical property needed for an understanding of the mass transfer phenomena in metallurgical processes. Viscosity is also the key that leads to a better understanding of the structure of slags. It is well known that the viscosities of silicate slags decrease with the addition of basic oxides due to the breaking of the silicate network. The measurements of slag viscosities often pose experimental challenges, especially to the choice of materials. The keynote lecture takes up the experimental problems and the various techniques adopted. Dynamic viscosity measurement, as a powerful tool towards an understanding of the kinetics of some high temperature reactions, is brought out. A number of semi-empirical models have been developed to estimate the slag viscosities in the case of multi component slags. A critical survey of these models is presented in the lecture. Earlier models by Riboud et al., Urbain et al. and Mills et al. have been developed further into a new generation of models. Some of the current important models are (1) Model by Iida et al. (2)CSIRO model (3) Pyro research Model (4) Model by Tanaka et al. (5) Model approach by Reddy et al. and (6) KTH-model. The predictions and capabilities of the various models are compared. Estimations of viscosities from thermodynamic data and prediction of liquidus temperatures from viscosities are presented. The concept of surface viscosities with reference to slags and viscosities of two-phase mixtures are also taken up in the presentation.

Jan 1, 2004

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 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 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 P. Sharma

Longwall panels facing wind blasts have been investigated at both Newstan and Moonee Collieries in the Newcastle Coalfield under the Wind Blast Project of the School of Mining Engineering, The University of New South Wales. The fluid mechanics involved in the compression and expulsion of air during wind blasts have been defined and the overpressure and air velocity time histories utilized to determine the wind blast parameters and define the relationship between them. The characteristics of wind blasts pressure pulses in mine roadways show some similarity with transient phenomenon like air blasts from explosives and shock waves from the failure of pressurized vessels. The peak wind velocities in roadways, however, exhibit marked deviations from theoretical predictions based on compressible fluid flow and Rankine-Hugoniot relationships applied to goaf air displacement and panel geometry. Peak overpressures and wind velocities have shown a positive correlation with the areas of goaf falls, with the values peaking off for larger areas. The field investigations have helped the mine management in risk assessment and in evaluating the success of induced caving by hydrofracturing to mitigate the hazard.

Jan 1, 2004

By S. E. Olsen, M. Tangstad

The main source of Mn in raw materials for SiMn production is Mn-ore and Mn-rich slag from the high carbon FeMn production. The amount of slag per tonne of SiMn metal is mainly determined by the ore/slag ratio. Increasing share of FeMn slag at expense of Mn-ore will lead to larger slag/metal ratio in the SiMn process. High volume of slag leads to an increased consumption of energy and probably to higher losses of metal inclusions in the final slag. Excavation of a SiMn furnace has shown that only modest pre-reduction of Mn-ore with CO gas seems to be obtained. Nearly all reduction of MnO was finished at the top of the cokebed. Dissolution and reduction of quartz obviously takes place in the cokebed zone after the main reduction of manganese oxide is finished. Probably the ?pick up? of Si in the metal is quite fast and takes place as the metal trickles down through the cokebed towards the metal bath. The distribution of Si between SiMn alloys and multicomponent MnO-SiO2-CaO-Al2O3-MgO slags is mainly determined by the process temperature, the silica content of the slag and its R-ratio = (CaO+MgO)/Al2O3. As an example, the equilibrium content of Si in the alloy will increase by about 6 % if the R-ratio is reduced from 2 to 1, provided constant temperature and silica content. The effect of temperature is also considerable. The equilibrium content of silicon will increase by approximately 6 % per 50°C in the temperature range 1550°C to 1700°C. The equilibrium content of MnO in SiMn slags depends first of all on the temperature and secondly on the silica content of the slag. At 1600°C the MnO content decreases from about 9 % at silica saturation to a minimum of about 3-4% when the silica content is reduced to about 40-45%.

Jan 1, 2004

High pressure grinding technology has gained further interest in various industries. So far in the mining industry, machines are in operation in diamond mines and iron ore applications. In gold and copper ore processing, test work has been conducted showing considerable operational and process benefits. Similar benefits can be expected from HPGR applications in the platinum industry due to the preferred ore breakage along grain boundaries, thus liberating the PGE particles. This paper will provide an update on the state of high pressure grinding roll technology. Developments in the design of high pressure grinding rolls, for minimized maintenance requirements and availability just as high as conventional mills, will be presented. Plant flow sheets and concepts will be discussed, which allow for a reduction of capital and operating cost in comparison to existing two-stage milling circuits.

Jan 1, 2004

Viscosity measurement was carried out over a narrow range of silica content around the fayalite composition. A wide range of temperature and oxygen potential was covered where the slag was completely liquid. In order to keep the slag composition and the Fe3+/Fe2+ratio constant, theCO2/CO ratio was kept constant as the temperature was varied. Increasing the Fe3+content has little effect on viscosity for slags with a silica mole fraction of 0.31. At higher silica contents, increasing the Fe3+content brings about a small decrease in the viscosity.

Jan 1, 2004

By S. Ndlovu

To investigate the influence of orientation of crystal lattice on the bacterial leaching of pyrite crystals, single crystals of 100, 111 and110 plane orientations were used for the study. Experiments were carried out in the presence of a Thiobacillus ferrooxidans culture. The different corrosion patterns observed on the surfaces of the bioleached samples suggests a variation in cell-surface interaction from one crystal plane to the other. The surface corrosion patterns generally reflected the influence of the symmetrical arrangement of the atomic planes in the lattice on which they formed. The results indicate that the surface properties of mineral sulphides may control the evolution of corrosion patterns and consequently the initial oxidation process in acid bacterial leaching.

Jan 1, 2004

By X. Pan

Slag-metal equilibrium experiments were conducted at 1500ºC and1580ºC under 0.03 atm, 0.05 atm and 0.83 atm CO partial pressures using silica and Cr-oxide crucibles. The complex slags belonged toSiO2-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, 0.80 and 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 thermo-dynamic calculations. Iso-concentration curves for carbon and chromium of the metal phase in equilibrium with the slag were drawn on a 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 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 P. C. -H. Rhee, H. -G. Lee, J. -H. Choi, D. S. Kim, S. -B. Lee

In order to predict the composition of inclusions and to ascertain a method to prevent inclusions from forming in liquid Fe-16 mass Cr alloy, a thermodynamic database was developed through a quantitative determination of thermodynamic relationships of Cr-Al-Si-Mn systems in the liquid Fe alloys. Applications of the databases to the prediction of Mn/Si complex deoxidation with Alin Fe-16 mass Cr alloy were demonstrated in succession. The electromagnetic levitation technique using a cold crucible was employed to separate inclusions from liquid metallic alloys completely and to prevent any contamination from surroundings. Various interaction parameters in the liquid Fe-16 mass per cent Cr alloy system were determined; these are: [eAl(Fe)Cr= 0.19/T, rAl(Fe)O,Cr= -0.01, rAl(Fe)O,Cr= -0.00013, eS1Cr(Fe)= -0.38/T,rSi(Fe)O,Cr= 0.007, rO(Fe)Si,Cr= 0.0044, rA1(Fe)Si,Cr= -0.0075, rSi(Fe)A1,Cr= -0.0078, rSi(Fe)Mn,Cr= 0.005, and rMn(Fe)Si,Cr=0.01.] An improved database, utilizing interaction parameters for molten metal determined in this study, and the Fact Sage slag database of the MnO-SiO2-Al2O3-CrOx-MgO system were used for thermodynamic calculations. These were carried out under various thermodynamic conditions, and results were compared with experimental data of Si/Al, Mn/Si, and Mn/Si/Al deoxidation equilibria. With the abovementioned results, together with experimentally obtained data, thermodynamic conditions were determined, in particular Mn and Si contents, under which liquid inclusions form in liquid Fe-16 mass per cent Cr alloy. The critical Al content in liquid Fe-16 per cent Cr alloy, above which solid inclusion of corundum phase ((Al,Cr)2O3) formed, was as low as 10 ppm. This indicates that extreme care must be taken in controlling the Al content in the metal to avoid formation of solid corundum phase ((Al,Cr)2O3) inclusion. The compositional change prediction of inclusions, which originate from slag entrapment and by Ca addition, was demonstrated by use of the alloy database optimized through this study, and the Fact Sage oxide database. For Si-deoxidized Fe-16 per cent Cr alloy, high Si and low basicity of slag are effective to obtain liquid inclusions. For Al-deoxidized Fe-16 per cent Cr alloy, it is important to keep the Si content lower than 0.1 per cent and it is required to add Ca. Keywords: inclusion, thermodynamic simulation, deoxidation, Fe-16 per cent Cr alloy,stainless steel, interaction parameter, cold crucible

Jan 1, 2004