Search Documents

By M Ranjan, C R. Borra, P Palai, P P. Sahoo

Change in mould slag composition during casting of medium alloy steel is caused by the redox reaction between molten steel and mould flux. Mould flux generally contains a certain amount of SiO2, but elements such as Al, Mn and Ti in high/medium alloy steels reduce SiO2 in the mould flux, causing remarkable changes in the composition of the mould slag. As a result, the properties of the mould slag change greatly as continuous casting proceeds. This causes casting instability, process abnormality and casting defects. Effect of Ti as an alloying element in steel on mould slag is studied extensively through high temperature laboratory measurements and plant measurements. TiO2 gets picked up by the mould slag up to 3 per cent during casting a steel grade containing 0.1 per cent Ti. This changes the mould slag composition and results in decreasing the slag viscosity by up to 10 per cent and decreases slag break temperature by 30–40°C.

Aug 21, 2024

By R G. Reddy, A Yahya

The sulfur distribution ratio (Ls) is an expression of the amount of sulfur in slag to the amount of sulfur in molten metal. The sulfide capacities calculated from Reddy-Blander (RB) model were used to calculate the sulfur distribution ratio (Ls). A new Reddy model for sulfur distribution ratio (Ls) was developed for modelling Ls for ironmaking, steelmaking, and secondary steelmaking conditions. Besides calcium oxide, the major component in the ladle furnace (LF) slags is alumina. The Ls was calculated for typical LF slags as a function of temperature and composition. The model calculated Ls values are in good agreement with the experimental and industrial slags data. The extremely low oxygen potential in these furnaces after fully-killed steel is favourable for desulfurisation. For any given slag’s composition and temperature, its sulfide capacity can be calculated a priori. The equilibrium sulfur distribution ratio between this slag and liquid metal in a particular vessel can also be calculated a priori. The Ls for ladle furnace (LF) slags is about twice those for blast furnaces (BF) slags and ten times those of basic oxygen furnace (BOF) slags. The desulfurisation of pig iron in BF and desulfurisation of steel in LF during secondary steelmaking are recommended. Steel desulfurisation in steelmaking furnaces is not effective. Since the model used to calculate the sulfur distribution ratio (Ls) is a priori, it is a useful tool for the iron and steel makers in improving the product quality and optimisation of the industrial furnace operations.

Aug 21, 2024

By A Nigam, K Biswas, R Sarkar

Because of the problems with 1st and 2nd generations of Advanced High-Strength Steels (AHSS), a 3rd generation of AHSS steels has become prominent and these steels have properties in between the 1st and 2nd generations of AHSS. However, although the 3rd generation of AHSS is a promising candidate as a replacement for its predecessors, there remain some challenges in processing these steels which are essentially medium Mn (Mn content ~ 5–7 wt per cent) and high Al (Al content ~ 1– 3 wt per cent) steels. The use of conventional casting powders based on the CaO-SiO2 system is unsuitable for high and medium Mn/Al steels. This work investigates the development of CaO-Al2O3- based mold fluxes for casting third-generation AHSS steel. Mold fluxes, with otherwise similar compositions but different C/A ratios, are tested and their crystallisation behaviour is examined using differential scanning calorimetry (DSC). A calcium aluminate phase having a composition Ca12Al14O33 was found to be the main crystalline phase in the mold fluxes. A decrease in crystallisation temperature was observed as the CaO/Al2O3 ratio increased from 1.00 to 1.33. The effective crystallisation rate constant exhibited an increase with decreasing crystallisation temperature, indicating a potential influence of nucleation rate on the overall crystallisation rate and suggesting an anti-Arrhenius behaviour in the crystallisation process of these mold fluxes.

Aug 21, 2024

By Z Li, Z Yan, T Htet, S Zhang

During the pyrometallurgical processes, a substantial quantity of high-temperature ironmaking and steelmaking slags, generated at temperatures ranging from 1400 to 1600°C, is wasted, as the heat contained in these slags is released into the environment during the tapping process without effective utilisation. On the other hand, a significant amount of energy is required to reheat the cold materials for the manufacturing of glass and mineral-wool, often necessitating the addition of high-silica materials to facilitate the production process. In this study, an innovative approach is presented to harness the heat present in molten metallurgical slags to directly produce new raw materials for glass and mineral-wool manufacturing while simultaneously reducing energy consumption and mitigating CO2 emissions. The theoretical amount of waste glass that can be effectively added in the process has been estimated via thermodynamic calculation. Experimental assessments were conducted to examine the impact of high-silica waste materials on the dissolution, melting and fluidity. Potential recipes for glass and mineral-wool manufacturing were suggested and an assessment of the energy savings, and reduction in CO2 emissions with manufacturing of glass and mineral-wool using this innovative approach were included. It was determined that the processes could lead to a reduction of over 26 kg of CO2 emissions per 100 kg of new material used, primarily due to the utilisation of heat from slag and the accelerated smelting process.

Aug 21, 2024

By B A. Webler, P Su, P C. Pistorius

Advanced high-strength steels (AHSS) typically have much higher aluminium concentrations (by an order of magnitude or more) than conventional low-carbon aluminium-killed steels. The resulting lower oxygen activity at the steel-slag interface changes the kinetics and thermodynamics of steelslag reactions. Previous work showed that the rapid transformation of alumina inclusions to spinel inclusions, and spinel to periclase, occurs because of the relatively high concentration of dissolved magnesium. In this paper, experimental results on nitrogen removal by ladle slag are compared with predictions based on the available thermodynamic databases. As in previous work, the kinetics was modelled by assuming mass transfer control, with steel or slag mass transfer limiting. The results show that significant removal of nitrogen by steel-slag reaction is possible.

Aug 21, 2024

By A Vickerfält, J Huss, J Martinsson

The European Union has listed vanadium (V) as one of the critical raw materials for the transition to a future green society, as stated in the Critical Raw Material Act, written by Grohol and Veeh (2023). In the steelmaking industry based on V-containing iron ore, V is a possible by-product from the slag. A requirement for slags to be suitable for V extraction is a V content preferably above 8 wt per cent as V2O3 and a phosphorus (P) content below 0.1 wt per cent as P2O5. Hence, it is important to keep V in the slag phase while the P is moved to the metal phase during the steelmaking process.

Aug 21, 2024

By A Kamaraj, M Mohanasundaram, R Kumar, P Tikare

This study presents a comprehensive thermodynamic optimisation and sustainability analysis of the secondary copper smelting process for Waste Printed Circuit Board (WPCB) recycling. The study investigates various scenarios with different proportions of WPCB in the input stream, ranging from 0 per cent to 100 per cent. Through thermodynamic modelling using FactSage™ version 8.1, the optimisation process is conducted in three stages. The results of the thermodynamic modelling indicate that the best-case scenario for WPCB recycling is achieved with a 40 per cent proportion of WPCB in the input stream. This case exhibits a maximum copper recovery of 99.93 per cent while minimising the formation of other waste. In addition to the thermodynamic analyses, environmental factors such as the carbon emission index and resource utilisation efficiency are studied. The 40 per cent WPCB recycling case exhibits a resource utilisation efficiency of 93.055 per cent and a carbon emission rate of 0.133. The present investigation highlights the significant benefits of a 40 per cent WPCB recycling scenario through a secondary copper smelting process in terms of base metal recovery and energy efficiency, thus emphasising its potential for sustainable PCB waste management and resource utilisation.

Aug 21, 2024

By M Kim, J Park, I-K Suh, E Kim, J Lee

One of the key technologies in developing hydrogen-enriched ironmaking operations is the control of the carburisation, melting, and dripping behaviour of the iron ore burden materials. When a hot compacted iron (HCI) is charged in the blast furnace or the FINEX Melter-Gasifier, iron oxide reduction, the reduced iron’s carburisation, and the melting of iron and slag occur successively. This study investigated the reduction, carburisation, melting and dripping behaviour of HCI under a COH2 gas mixture using the high-temperature X-ray radiographic technique. Under 100 per cent CO gas atmosphere, the dripping temperature was 1410°C. When 5 per cent H2 was introduced, the dripping temperature slightly decreased to 1400°C. Furthermore, the dripping temperature gradually increased as the H2 gas composition increased. As 30 per cent H2 was introduced, the dripping temperature reached 1414°C. The carbon concentration in the drained metal samples gradually increased with increasing H2 composition. It is considered that H2 decreased FeO content in the slag, yielding the increased melting temperature and viscosity of the slag. On the other hand, H2 accelerated the carburisation of the reduced iron by CO gas, enabling the homogenisation of the oxide materials to form a liquid phase. Therefore, it is considered that introducing H2 in the reactor is helpful to increase productivity and energy efficiency by accelerating the liquid phase’s formation.

Aug 21, 2024

By R G. Reddy, Z Zhang

Viscosities of CaO-aluminosilicate ternary melts were estimated using a structure-based model. The model considers depolymerisation effects and related breakdown of the silicate network structure on the addition of metal oxides to the melts. The predicted values are in good agreement with the experimental values over the whole temperature and composition range.

Aug 21, 2024

By G M. Zhomin, A S. Arkhipin, A Kondratiev

Viscosity of multicomponent slags is one of the crucial physicochemical properties for many industrial processes and technologies. While the viscosity-temperature relationship of completely molten slags can well be described by an Arrhenian-type law, the compositional dependence of viscosity is still not fully understood, especially in compositional regions with the lack of experimental data (eg at the glass-former concentration of 90 molar per cent or higher). In the present work major compositional relationships of the activation energy of viscous flow have been revised for numerous binary and ternary slag systems on the basis of experimental data collected and stored in the viscosity database OxiVis. For example, it has been found that the activation energy relevant to the polymerisation effect in binary systems of the MO-GFO type, where MO is the modifier oxide (ie monovalent K2O, Na2O, Li2O and bivalent CaO, MgO, BaO, MnO, PbO etc) and GFO is the glass-forming oxide (SiO2 or B2O3) is not always proportional to the third power of XGFO (contrary to the Urbain formalism) and can vary significantly dependent on the slag system. Also, the activation energy of the charge compensation effect has been revised for ternary systems of the AO-MO-GFO and AO-MO type, where AO is the amphoteric oxide (Al2O3, Fe2O3 or other). A simple polynomial model has been proposed on the basis of the carried-out analysis for estimation of viscosities of multicomponent slag systems. The model has been optimised against the experimental viscosities in the selected binary, ternary, and higher-order oxide systems and has been shown reasonable agreement with the experimental data.

Aug 21, 2024

By A Van den Bulck, K Verbeken, O Vergote, I Bellemans

Viscosity is one of the most important physicochemical properties during pyrometallurgical operations. In the sub-liquidus regime, an important factor is the presence of suspended solid particles, yet its influence is not well-described in earlier literature, despite the significance of this factor. This project aims to determine the influence of spinel particles (Zn(Al,Fe)2O4) on the rheology of a multiphase synthetic PbO-SiO2-ZnO-Fe2O3-CaO-Al2O3 slag system. Three data sets with a wellcontrolled methodology and three different spinel sizes (small (13 μm), medium (34 μm) and large particles (76 μm)) were published previously, using a custom-built high-temperature rheometer. This study presents an additional data set of slag viscosity measurements, performed using a different apparatus, the Anton Paar FRS 1800, to verify the consistency of the earlier determined viscosity behaviour. Within this data set, no consistent trend could be found between the predicted wt per cent spinel and the relative viscosity. Therefore, additional quenching experiments were conducted to identify the morphology and experimentally determined volume fraction of the spinel particles in the slag. These measurements revealed a difference in spinel size across the samples and corresponding viscosity behaviour, emphasizing the importance of spinel particle size on slag viscosity. Once the spinel size was taken into account, consistent viscosity results (relative apparent viscosity and flow index) were observed across the two devices. This study confirms that, once all parameters affecting slag viscosity are considered, the viscosity behaviour of a heterogeneous slag can be uniquely determined. The resulting optimised slag viscosity models can be used to predict viscosity before processing, addressing relevant phenomena such as slag tapping, slag foaming and copper droplet settlement.

Aug 21, 2024

By R G. Reddy

The complexity in treating environmentally harmful impurities such as As, Sb, Bi from the base metal matte or metal in the smelting stage are responsible for the high cost of the refining process. The impurity capacities (such as arsenic, antimony and bismuth) of slags were calculated a priori using Reddy-Blander (RB) model. The capacity predictions were for a wide range of matte and slag compositions in copper smelting conditions. The calculated impurities capacities and impurity distribution ratios results are in good agreement with the available experimental and industrial slags data. The a priori knowledge of impurities is useful for reduction of energy consumption and enhanced environmental control in the current and future non-ferrous metal processes.

Aug 21, 2024

By S Wan, F Zhang, J You, K Tang, X Tang, C Bessada, A Canizarès, Q Zhang, L Lu

Microstructure of CaO-SiO2-based glassy samples with various Al2O3 contents were examined quantitatively by Raman spectroscopy and 27Al MAS NMR (magic-angle spinning nuclear magnetic resonance). Sequence of multiple cluster models of aluminosilicate system modified with Ca2+ and Na+ cations have been designed, and Raman spectra simulation were carried out after geometric optimisation by quantum chemistry (QC) ab initio calculation. The functional relationship between Raman scattering cross-section (RSCS) and stress index of silicon-oxygen tetrahedron (SIT) for aluminosilicates was established, which was applied to the calibration of experimental Raman spectra. Some five-fold coordinated aluminium (AlV, around 5 per cent) and less than 2 per cent sixfold coordinated aluminium (AlVI) were detected by 27Al MAS NMR, while most of aluminium remained in tetrahedral sites (AlIV). The hyperfine quantitative results of Raman spectroscopy and NMR showed a gradually production of AlIV with addition of Al2O3, along with the significant adjustment of Qi species distribution, in which Q1, Q2 reduced and fully polymerised Q4 increased while Q3 showed a non-monotonic variation and obtained the maximum at Al2O3 = 18 mol per cent. Furthermore, the effects of aluminium to bridging oxygen bond types (T-Ob, T = Si, Al) and the degree of polymerisation were also discussed in detail. The evolution of microstructure and its correlation with the viscosity of CaO-SiO2 based melts, incorporating various Al2O3 additives, have been investigated by employing in situ high temperature Raman spectroscopy at 1823 K and viscosity model. These structural features related to composition are essential theoretic foundation to understand their properties. The average Qi evolution culminates in an overall enhancement of the degree of polymerisation. Viscosity was determined utilising a rigorously selected viscosity model, elucidating a consistent upward trajectory as Al2O3 content is incrementally added. Furthermore, a quantitative analysis of the relationship between viscosity and structure was conducted based on the average number of non-bridging oxygen per network-forming tetrahedron (NBO/T). It provides valuable insights for examining and predicting viscosity behaviour of aluminosilicate systems.

Aug 21, 2024

By K S. Park, J K. Kim, J H. Park, Y Su

The present study investigates the possibility of the direct removal of oxygen from the Ti-30Ni (wt per cent) alloy melt through the thermodynamic equilibrium reactions at 1623 K in the vertical tube furnace. The deoxidation efficiency of Ti-Ni alloy melt by adding different contents of metallic calcium (Ca) as a deoxidant was evaluated with the binary CaF2-MgCl2 flux. The thermodynamic equilibrium experiments showed that the total oxygen content in the alloy decreased from about 650 ppm to 350 ppm when 3.5 wt per cent Ca was added to the Ti-30Ni (wt per cent) alloy. Alternatively, the effect of flux composition in the CaF2-MgCl2 flux on the oxygen content was also investigated at 1623 K. Therefore, the effect of binary flux systems on the deoxidation ability was compared at 1623 K. According to the results, the flux system with 80 per centCaF2– 20 per centMgCl2 exhibited the best deoxidation capability, ie total oxygen content in the alloy reduced from 1450 to 550 ppm.

Aug 21, 2024

By E Jak, M Shevchenko, E Nekhoroshev, D Shishin

In the field of pyrometallurgy, the presence of multiple molten phases with distinct chemical compositions, such as slags, mattes, speiss liquids, metals and molten salts, is a well-known phenomenon. These phases exhibit strongly non-ideal solution behaviour and are mutually miscible to varying degrees. To describe these complex molten liquids, the Modified Quasichemical Model (MQM) has proven effective and has been applied to numerous binary, ternary and several higher-order multicomponent systems related to pyrometallurgy. In recent decades, the complexity of high-temperature processes has escalated due to increased impurity concentrations in primary ores, the incorporation of recycled consumer products and the integration of metallurgical plants through by-product and waste exchanges. To address these issues, PYROSEARCH laboratory has been developing large 20-component thermodynamic database using a generalised CALPHAD (CALculation of PHAse Diagrams) methodology integrated with experimental investigations. Over the past decade, strategic decisions were made balancing the ability to generate experimental data, prediction power, accuracy, stability of calculations, as well as computational time, which are discussed in the paper. Examples provided for issues of >3 liquid immiscibility, non-ionic behaviour and exaggerated ‘sharp’ enthalpies of mixing in silicate slags, dealing with multiple oxidation states, as well as comparative analysis of pair and quadruplet approximation in MQM.

Aug 21, 2024

By Q Shu, T Deng, B Yan, B Song, D Wang

In view of the lack of phase equilibria data of vanadium-bearing oxide system and the desirability of them for design or optimisation of vanadium extraction process, the phase equilibria relationships of V2O3-FeO-SiO2-CaO(15 mass per cent) system were determined experimentally and then an isothermal section phase diagram of this system was constructed. Totally, 81 samples of different composition were equilibrated at 1623 K for 48 hours in iron crucible under Ar atmosphere. The equilibrated samples were quenched quickly in cold water, and then the phase constituents of all the samples were identified by X-ray diffraction (XRD) combined with electron probe microanalysis (EPMA) measurements.

Aug 21, 2024

By A D. Pradana, D R. Pradana, Y H. Putra, Z Zulhan, T Hidayat

The high temperature processing of nickel laterite ore is currently dominated by the Rotary Kiln- Electric Furnace (RKEF) technology. The ratio of SiO2/MgO (S/M) in the ore is one of the critical parameters that determines the success of the RKEF process. Incompatible S/M ratios in the ore can cause aggressive chemical interaction between the slag and MgO refractory. The slag-refractory interaction at conditions relevant to nickel laterite ore smelting was investigated in the present study. Synthetic mixtures representing the slag compositions of nickel laterite ore smelting were prepared by mixing MgO, SiO2, Al2O3, CaO, Fe2O3, and Fe and heating the mixtures in steel containers at 1300°C under an argon atmosphere for 3 hrs. Pure MgO crucible were used as containment material in the melting process of the mixtures to represent the MgO refractory. The kinetics of the slagrefractory reaction were investigated using samples with selected initial S/M ratios of 2.0 and 3.0 (wt/wt) (with constant CaO = 3 wt per cent, Al2O3 = 5 wt per cent, FeO = 10 wt per cent) by performing melting at 1500°C in MgO crucibles for 5, 30, and 120 mins under an argon atmosphere. The effect of the S/M ratio in slag on the slag-refractory interaction was also investigated by performing melting of mixtures with different initial S/M ratios of 1.75, 2.0, 2.5, and 3.0 (wt/wt) in MgO crucibles at 1500°C for 120 mins under an argon atmosphere. After the melting process, each sample was quenched in water, mounted in resin, ground, polished, and coated. The interaction between the slags and MgO refractory was then evaluated by analysing the polished samples using a scanning electron microscope equipped with an energy dispersive spectroscopy (SEM-EDS). Thermodynamic simulations using FactSage™ 8.0 thermochemical software were performed based on the experimental slag compositions, refractory, and conditions to support the evaluation process. The results show that a higher S/M ratio in slag leads to a higher tendency for the refractory component to dissolve into the slag. A higher S/M ratio in slag also leads to an increasing extent of solid-state diffusion of iron oxide into the remaining refractory grains. The dissolution of MgO into the slag is rapid; the MgO concentration in the final slag increased by 2.4 wt per cent and 5.7 wt per cent at initial S/M ratios of 2.0 and 3.0 wt/wt, respectively, within 5 and 30 mins of the melting process.

Aug 21, 2024

By Q Zhuo, P C. Pistorius, M N. Al-Harbi

A likely increasingly important pathway for future low-carbon ironmaking and steelmaking is the combination of gas-based direct reduction with electric furnace steelmaking (DRI-EAF route), or with electric smelting (DRI-ESF route). In the DRI-EAF route, the gangue that is present in the iron ore is fluxed and removed as slag in the melting (steelmaking) step. This is in contrast with integrated steelmaking, in which the gangue is removed as part of blast furnace ironmaking. For DRI-EAF steelmaking, the amount and composition of slag depend on the iron ore composition, flux additions and iron yield. Slag volume and composition affect phosphorus removal, foaming behaviour and the process energy requirements. In this work, heat data from a year of DRI-EAF production was analysed to test whether the expected relationship between slag volume and electricity consumption for EAF steelmaking was observed. The data include slag analyses (one sample per shift), and heatlevel information on all inputs, final steel temperature and dissolved oxygen concentration, electricity consumption, tapped steel mass and tap-to-tap time. In analysing the data, the slag volume was estimated from the assayed slag CaO concentration and CaO inputs to the EAF. The expected effect of slag volume on steelmaking energy consumption was calculated with a mass and energy balance, considering the heat of mixing of the slag. The calculated energy requirement of slag formation is in line with previous estimates reported in the literature.

Aug 21, 2024

By G Cao, Y R. Cui, J X. Zhao, H P. Gui, G H. Wang, Z M. Wang, M M. Ren, B Li

Pyro-metallurgy is still the main process for lead production and a lot of lead direct smelting processes have been developed in recent years. All the processes will experience two steps in common. The first is the oxidisation of PbS to PbO and then reduction from PbO to Pb, furthermore, from ZnO to Zn. So, the composition of melts, especially the slag composition at reduction step change continuously. Up to now, there are few systematic results on the slag physical-chemical properties with its composition change. In this work, the typical lead direct smelting processes were analysed from theoretical and practical standpoints. The full-period slag composition and slag melting point change were compared. Especially, to the PbO and ZnO reduction steps, based on the full-period slag composition change, the slag properties were predicted. Based on dust composition and test results, the mechanism of Pb compound evaporation and its effect on practice and measurement of high PbO bearing slag physical-chemical property is discussed. It is suggested that to restrain the evaporation in practice and to obtain more accurate measurement results of physicochemical properties of smelting slag are the key problem not only to set high efficiency, energy saving process, but also to environmental pollution control.

Aug 21, 2024

By M G. Shaw, M A. Rhamdhani, S P. Singh, A R. Duffy, B Eisenbart, A K. Shukla, G A. Brooks

The field of astrometallurgy is a growing area of study. Metal production on the Moon is likely to begin in less than a decade as major space agencies such as NASA (National Aeronautics and Space Administration) and CNSA (China National Space Administration) are preparing to construct permanent lunar bases. The utilisation of regolith to generate oxygen and metals is expected to be important in the development of a sustainable lunar habitat. This paper provides an overview of potential metallurgical processing methods for lunar conditions, emphasising the impact of lunar factors on slag chemistry. The interaction between regolith and the extracted metals, as well as their impact on slag composition and refractory performance, are critical considerations in metal production on the lunar surface. The initial research on lunar metallurgical technologies is focused on oxygen extraction and Fe-Si alloys are reported as the by-products of these processes. This paper delves into the fundamental thermodynamics associated with the carbothermic reduction of lunar regolith. Thermodynamic analysis using the FactSage™ ver 8.2 software package indicates that the Fe-Si alloy can be produced as a metallic product from the lunar regolith at temperatures ranging from 1400°C to 1600°C under terrestrial conditions. However, under ultra-high vacuum conditions (3 × 10-15 bar) on the Moon, the required operating temperature for producing ferrosilicon would be significantly reduced. Thermodynamic modelling results indicate that under lunar vacuum conditions, Fe-Si alloys only exist as solid phases at lower temperatures below 650°C. At higher temperatures, both Fe and Si are expected to be present in the gas phase. In this work, the carbothermic reduction of the Lunar Mare Simulant (LMS-1) is conducted under terrestrial conditions. The findings indicate that the process can readily yield Fe-Si alloys with 7–10 wt per cent Si at 1600°C. Additionally, energy dispersive spectroscopy (EDS) analysis of the resulting Fe-Si alloy indicates the presence of phosphorus up to 1 wt per cent.

Aug 21, 2024