Within several cooperative projects, KTH (Royal Institute of Technology), Ovako Steel AB, and MEFOS have investigated the desulphurisation of bearing steel during vacuum degassing. The work includes thermodynamic calculations of the slag-metal equilibrium, CFD modelling of slag-metal reactions, and plant trials. Results from the various studies are presented and discussed in this paper. Models for predicting slag properties (sulphide capacity, viscosity, and oxide activities) in liquid slags as functions of slag composition and temperature have been used for the calculation of data which have been employed in static and dynamic modelling of sulphur refining. The results from static modelling show that the method allows fast and easy evaluation of the theoretical desulphurisation conditions during degassing at Ovako Steel AB, as well as theoretical determination of the parameters that have the greatest influence on the equilibrium sulphur distribution. The conclusion from dynamic modelling is that the vacuum degassing operation can be described dynamically with the present knowledge of sulphide capacity, sulphur distribution, viscosity, and oxide activities of ladle slags if this knowledge is combined with fluid flow modelling to derive the overall kinetics. The presented model approaches have been found useful in understanding the sulphur refining process at Ovako Steel AB. The dynamic modelling concept is also believed to have potential for dynamic descriptions of other slag-metal reactions in steelmaking. © 2002 IoM Communications Ltd.
Measurements of the thermal conductivity of casting powders are needed to determine the magnitude of the vertical heat flux in the powder bed of a continuous casting mould. The thermal conductivities and thermal diffusivities of four mould powders have been determined using the transient plane source (TPS) and the transient hot wire (THW) methods. The values reported in this investigation are in good agreement with the results of earlier studies which used the THW method. However, the results were significantly different from λeff values obtained in thermal insulation tests. This was attributed to the large contribution to λeff from gaseous conduction which arises from the large temperature gradient across the sample. It was found that the thermal conductivity (λpowd) of the powders had a mean value of 0.125±0.025 W m-1 K-1 for the four powders studied; this value is in good agreement with two other studies; it increased as the temperature increased with a mean temperature coefficient of (dλ/dT59×10-5 W m-1 K-2 for the range 295-1100 K and increased as the bulk density increased (λ295=0.010+1.69×10-4ρbulk W m-1 K-1).
Measurements of the thermal conductivity (λ) and thermal diffusivity (α) have been carried out on samples of Na2O·SiO2 and four mould slags for temperatures between 295 and 1300 K. These measurements were carried out using the transient plane source (TPS) method (295-373 K) and the transient hot wire (THW) technique (295-1300 K) and the laser pulse (LP) or laser flash method in the case of Na2O·SiO2 Values of l295 were very similar (1.07±0.03 W m-1 K-1) and all samples exhibited a maximum at the critical temperature (Tcrit 51040±10 K) beyond which there was a sharp drop in λTHW with increasing temperature. Measurements were also carried out on semi-crystalline samples with increasing λ and fraction of crystalline phase. These samples also exhibited a sharp drop in the thermal conductivity for temperatures above Tcrit and λTcrit was found to be 1.6±0.05 W m-1 K-1. Thermal conductivity (λLP) values calculated from reported thermal diffusivity (αLP) values were in very good agreement with the measured λTHW values for temperatures between 295 K and Tcrit but λLP values did not decrease with increasing temperature above Tcrit (cf. λTHW). Consequently, it was found that λLP≈7λTHW for mould slags.
The main focus of the present work was to develop a sampler to obtain the physical description of the slag-metal interface in the presence of bulk flow. Industrial trial experiments were carried out in the ladles at Uddeholm Tooling, Hagfors, Sweden using the designed sampler. Samples of the slag-metal interface were successfully taken in both gas stirring and induction stirring modes. The similarities of the appearance as well as the micrographs of the samples suggested that the slag-metal interfaces in the two stirring modes were very similar except in the open eye area. In the case of both stirring modes, metal droplets were found in the slag bulk. On the other hand, no appreciable amount of slag was detected in the metal bulk. Further systematic investigation using a large number of samples is required to obtain a quantitative description of the interface. © 2006 Institute of Materials, Minerals and Mining.
plant trial has been performed, with recycling of ladle slag to the LD converter at SSAB EMEA, Luleå, Sweden. The effect of ladle slag addition on the slag and steel composition, together with the slag weight, was investigated with sampling both during the blow and at blow end. The addition of ladle slag resulted in an increase in slag weight between 1 and 2 t throughout the blow and an increase of 3 wt-% in the slag Al 2O 3 content. This indicated that the ladle slag melted during the initial stages of the blow and enhanced the early slag formation. Lime additions were reduced with 3·5 kg t -1 liquid steel without drawbacks on the phosphorus or sulphur refining. Heats with added ladle slag had an increase in blowing time with ~4% and an increased tendency for slopping. However, this can be handled by different lance and addition programmes. © 2012 Institute of Materials, Minerals and Mining.
The influence of recycled ladle slag on the basic oxygen furnace (BOF) process under production conditions was investigated in plant trials. More specifically, 25 heats with ladle slag additions and 23 heats without ladle slag additions were studied. Both steel and slag samples were collected, from which the chemical compositions were determined. In addition, several process parameters were monitored. Overall, it was found that recirculation of ladle slag during normal production conditions works fine. On the positive side, it was seen that the steel quality concerning the phosphorus and sulphur contents of liquid steel has, in accordance with previous studies, not been affected by the ladle slag additions. Furthermore, no major differences in the slag composition occur when the recycling of ladle slag to BOF is performed. Finally, in comparison to previous studies, the increased tendency for slopping when adding ladle slag could be eliminated with a change in the lance schedule. However, on the negative side, it was seen that the addition of ladle slag leads to an increased blowing time due to lower iron ore additions. Moreover, the slag weight at tapping increased due to an increased weight of added slag formers. © 2012 Institute of Materials, Minerals and Mining.
In order to gain an insight into the mixing behaviour of slag and metal under different stirring conditions, samples of slag/metal interface were collected from an industrial 65 ton ladle furnace using a new sampling technique. Different stirring conditions and sampling positions in the ladle were chosen. Complementary cold model experiments were also performed. The experimental results strongly suggested that the shear force between the two liquids played an important role in slag-metal mixing. Evidence for the existence of slag droplets each surrounded by a very thin metal film was found in the samples taken under both gas stirred and induction stirred conditions. This observation strongly suggested that slag-metal system behaved similarly as oil-water system, wherein, the shear force owing to the bulk flow led to a packed 'sphere bed' of oil droplets each coated by a thin water film above the water bath. On the basis of the experimental results, preliminary mathematical models were developed to describe the rate of mass exchange at the slag/metal interface. © 2006 Institute of Materials, Minerals and Mining.
In this paper, the reduction of chromite ore by coke was investigated by means of thermogravimetric analysis under non-isothermal conditions (from room temperature to 1823 K). The fractional reduced samples were examined by SEM/EDS and X-ray diffraction analyses. The experimental results showed that the reduction of iron in the chromite ore started before that of chromium in the ore, and the reduction of chromium and iron in the ore overlapped to some degree. Chromium iron carbide (Cr,Fe)7C3, was found to be the intermediate phase during the reduction, and a chromium gradient was found in the spinel phase of the fractional reduced sample at 1673 K. A four-stage reduction process was proposed: one stage involving the reduction of iron in the chromite ore and three stages involving the reduction of chromium in the ore. The activity aspects of component FeCr2O4 and component MgCr2O4 in the chromite ore were considered. The difficulty in the reduction of the chromite ore is attributed to the fact that, as the reduction proceeds, the activity of the component MgCr2O4 in the fractional reduced ore will decrease to a very low level, which makes further reduction very difficult.
Basic oxygen furnace (BOF) slag contains a significant amount of iron-containing species, which is considered to be iron resources and therefore need to be recovered. In this work, the oxidation behaviour of BOF slag under air (at selected oxidation temperatures and holding time) was investigated to explore the potential of transforming non-magnetic wustite in the BOF slag into magnetic spinel, which may subsequently be recovered by magnetic separation. The experimental results show that the iron-containing spices in the BOF slag can be oxidised into magnetic spinel phases in the investigated temperature range of 1000–1150°C and thereafter be recovered by magnetic separation. The formation of these phases is closely related to the oxidation temperatures and holding time: a higher oxidation temperature and longer holding time lead to a larger amount of formed magnetic species; however, the amount of formed magnetic species decreases at elevated temperature (>1050°C) and with extended holding time (>40 min).
Iron losses during hot metal desulphurisation using magnesium and calcium carbide have been studied by large scale investigations of slag from the slag pit as well as slag sampling during desulphurisation at SSAB EMEA in Luleå. The desulphurisation slag after co-injection is normally solid and contains a large amount of iron. An alkali containing mineral, nepheline syenite, was mixed with calcium carbide to enhance the separation of iron from the slag. Even though the addition of nepheline syenite resulted in a more fine grained slag, no reduction of the iron content in the slag was observed before slag skimming. Nepheline syenite has a positive effect on slag skimming; however, the total magnetic iron losses have not decreased significantly. The increased turbulence during injection of magnesium could explain the lack of improved iron yield. The addition of nepheline syenite does not have a negative influence on the reagent efficiency.
Iron losses during calcium carbide based hot metal desulphurisation have been studied via large scale investigations of slag from the slag pit as well as slag sampling during desulphurisation at SSAB EMEA in Luleå. The desulphurisation slag, after injection of calcium carbide, is normally solid and contains large amounts of iron. An alkali containing mineral, nepheline syenite, was mixed together with the calcium carbide to form a more fluid slag as the iron losses originate from enclosed metal droplets in the slag as well as drawn off hot metal during slag skimming. The slag amount after slag skimming decreased from 28.1 to 25.1 kg t-21 hot metal with addition of 5 wt-% nepheline syenite to the calcium carbide, and the magnetic fraction of the slag from the slag pit decreased from 2.5 to 1.9%. Finally, no negative effect on the reagent efficiency was observed during the trials with addition of nepheline syenite.
Microwave technology has for decades been a tool for astronomers in their work to map and understand the complexities of the universe in terms of composition and extent but it is also used at laboratory scale by spectroscopists to examine the properties of atomic and molecular compounds. This paper discusses the use of microwave technology for the investigation of liquid slag structures. Preliminary results indicate that alteration of slag composition could be correlated-to the measured microwave refractive index. Investigations have been performed on Al2O3-CaO-SiO 2. © 2005 Institute of Materials, Minerals and Mining.
The focus was to study the elimination of non-metallic inclusions during the final part of the ladle refining of tool steel (AISI H13). More specifically, the final stirring treatment in a ladle before casting was modified to study how the number of inclusions could be decreased. The following three stirring treatments were tested: a conventional induction stirring with a 650 A current for 20 min, a short induction stirring with a 650 A current during 10 min, and a combined gas and induction stirring during 20 min (no open eye and a 600 A current). Steel samples were collected from the ladle before and after the final stirring period of the ladle treatment. Thereafter, the numbers of inclusions in steel samples were determined using a light optical microscope based on a classification according to the Swedish standard SS111116 (JK Scale II). Overall, the results showed that a combined gas and induction stirrings was the most efficient way of decreasing the number of DM, DH and DP inclusions. The decrease in the inclusion number in four heats was the following for the different size classes for a combined stirring procedure: 15-40% for DM type inclusions, 30-61% for DH type inclusions and 50-100% for DP inclusions. In addition, it should be mentioned that a stirring practice with induction stirring during 10 min resulted in a 67-100% decrease in the DH type inclusions. However, the results for a combined stirring case for DH type inclusions were more stable than those for a shorter induction stirring time.
The oxygen bearing gases of the atmosphere in a reheating furnace oxidise the feedstock producing scale on the surface of the metal and, for high carbon steels, cause decarburisation of the surface layers. Modelling of these effects has to take into account the competitive nature of the two processes, scale formation and decarburisation, and complications that arise from changes in the controlling mechanism. Initially, the rate of scale formation may be controlled by effects in the gas phase, or nucleation of scale on the metal surface. Subsequently, scale growth is influenced by the gas composition and may be disturbed by the accumulation of oxidation products at the scale-metal interface. Voids and cracks within the scale may either inhibit solid state diffusion within the scale or provide channels for oxidising gas to access the scale-metal interface, For decarburisation, complications arise if a ferrite rim creates a step in the carbon profile or if retention of carbon monoxide within the scale provides a thermodynamic barrier to the reaction. This paper considers these complications and how they may be handled in mathematical models.
Selected IMPHOS heats,1,2 have been used to make observations on decarburising and dephosphorising performance, scrap melting and slag foaming characteristics during BOS refining. If it is assumed that decarburisation takes place solely in the slag/metal emulsion then maximum metal residence time in the emulsion is just under 9 seconds and at peak decarburisation time, the maximum amount of metal in the emulsion is ∼50% of the total metal content in the converter. To evaluate the effects of changes in slag component chemistry on phosphorus refining it is necessary to account for changes in slag weight, which can change substantially throughout a heat and be significantly different heat-to-heat. Dephosphorising performance depends on the thermodynamic stability of slag phases that are able to take up phosphorus and the distribution of phosphorus between these thermodynamically stable phases. The application of proprietary thermodynamic models such as MTDATA and FACTSage has helped to clarify such events. Skull build-up on the scrap pile is at a maximum when the bulk bath temperature is ∼1460°C. At this time, the solid scrap and skull component of the bulk bath makes-up just over 60% of all the metal charged to the converter. All scrap and skull is melted out at a bulk bath temperature of ∼1610°C. The stability of the foamy slag/metal emulsion changes over the period of the blow. Slag height increases with an increase in FeO(tot)wt-% and decreases with a decrease in decarburisation rate and the collapse of the foamy slag. © 2013 Institute of Materials, Minerals and Mining.
A unique in blow sampling system has been applied to a blowing converter to retrieve simultaneously representative bulk metal bath and slag/metal emulsion samples from seven specified positions and every 2 min from start of blow. Full sample datasets from 20 heats have been grouped according to differences in the bulk bath phosphorus removal profiles and analysed with respect to relative refining ability of the slag/metal emulsion and the bulk metal bath. The complexity of the thermokinetic relationships behind the removal of carbon and the transfer of silicon, phosphorus, manganese and sulphur between the metal and slag is highlighted and the metal circulation rate in the emulsion is derived. © 2011 Institute of Materials, Minerals and Mining.
When you look into the continuous casting mould you can see very little. Consequently, steelmakers have had to rely on plant trials, simulation experiments and physical property measurements on fluxes and steels to gain an understanding of the mechanisms responsible for process problems and product defects. However, in recent years, mathematical modelling has advanced to the stage where they can provide us with great insight into these mechanisms. As a nonmathematical modeller, I was initially sceptical of some of the predictions of the mathematical models. However, I have been completely won over by the ability of these models to simulate accurately the mechanisms responsible for various defects, such as slag entrapment, oscillation mark formation, etc. Mathematical modelling literally allows us to 'see' what is happening in the mould. It is a remarkable tool. © 2014 Institute of Materials.
The focus of the present work was to examine whether vanadium rich phase(s) could be obtained in converter slags having high V2O5 contents. Slags from SSAB Oxelösund, Sweden and Ma Steel, China were studied, Despite of the composition difference, slags from both industries were found to contain essentially the same phases after heat treatment. No vanadium rich phase could be obtained by only heat treatment of the slag. The addition of 12mass%SiO2 changed substantially the phase relationships In the slags. Two vanadium rich phases were detected in the slag samples with SiO 2 addition. One of the phases was expected to be a solid solution of 3CaO.V2O5 and 3CaO.P2O5 with <3 mass%SiO2 dissolved. The other vanadium rich phase had high SiO 2 content. About 67-68 mass% vanadium was captured by the vanadium rich phase(s) after the treatment. The present finding would open up new opportunities for recovery of vanadium from converter slags. © 2007 Institute of Materials, Minerals and Mining.
The solubility of vanadium oxide in the SiO2–CaO–VOX system was investigated as a function of basicity (CaO/SiO2) at a fixed temperature of 1600°C and oxygen partial pressure of 10−10 atm. Formed phases and microstructures of saturated samples were identified with SEM–EDS analysis and XRD. Maximum solubility of vanadium oxide was between 15 and 20% independent of basicity. Pure karelianite (V2O3) was formed in all samples at saturation of vanadium oxide. The morphology of karelianite changed with the change in basicity in the slag, where needles or threads were formed for slags with basicity B2 = 0.54 and B2 = 0.67 and stars or dendritic patterns were formed with basicity B2 = 1.0 and B2 = 1.22. Wollastonite (CaSiO3) was also formed in the slags with star or dendritic patterns.