Dissolution rate of Al2O3 into molten CaO–Al2O3–CaF2 flux

Abstract

Dissolution of Al₂O₃ into molten CaO–Al₂O₃–CaF₂, a base system of mould flux for continuous casting of high Al steel, has been investigated by employing a rotating cylinder method. The dissolution rate of an alumina rod into molten CaO–Al₂O₃–CaF₂ flux increased with increase in rotating speed and temperature. The apparent activation energy for mass transport of flux C was calculated to be 255·6 kJ mol^?1. The rate controlling step during the dissolution process of the alumina rod into molten CaO–Al₂O₃–CaF₂ flux was found to be the diffusion of the solute in the flux boundary layer. The dissolution rate of alumina into molten CaO–Al₂O₃–CaF₂ flux increased with increasing CaO/Al₂O₃, and it may be caused by the increase in thermodynamic driving force and the decrease in the viscosity of the flux. When the Al₂O₃ rod was immersed into molten flux, an intermediate compound of CaO.2Al₂O₃ formed firstly and then dissolved into molten flux.     

Experimental measurements and modelling of viscosity in CaO–Al2O3–MgO slag system

Abstract

The viscosity of the CaO–Al₂O₃–MgO slag system has been measured by the rotating cylinder method up to 1823 K. The MgO content was between 0·39 and 11·33 wt-%, and the mass ratio of CaO/Al₂O₃ was between 0·60 and 1·28. The results indicated that both the MgO content and the mass ratio of CaO/Al₂O₃ have an influence on the viscosity of the slag. The effect of the mass ratio of CaO/Al₂O₃ is larger than that of the MgO content. The viscosity decreased with increasing MgO content and then increased. The effect of the mass ratio of CaO/Al₂O₃ on the viscosity was similar. The main mineralogical compositions of the slag were determined by X-ray diffraction, and their effects on viscosity were investigated. The measured results were in good agreement with those given by the Iida model.     

Solidus surface of the equilibrium diagram of the HfO2—Y2O3—La2O3 system

The phase equilibria on the solidus surface of the phase diagram of the HfO ₂−Y₂O₃−La₂O₃ system have been investigated using DTA in helium up to 2500°C, TA with solar energy in air up to 3000°C, X-ray phase analysis, petrography, and electron microscopy. Five solid solution fields based on hexagonal (H) and cubic (C) crystal modifications of Y₂O₃, cubic modifications of HfO₂ with fluorite structure (F), high-temperature cubic modifications of La₂O₃ (X), and crystallization field of the ordered phase La₂Hf₂O₇ with the pyrochlorine (Py) type structure have been found on the solidus surface. The ternary system has three quaternary novariant equilibria of the eutectic (1) and peritectic (2) type. Institute for Problems of Materials Science, Ukraine National Academy of Sciences, Kiev. Translated from Poroshkovaya Metallurgiya, Nos. 5–6(407), pp. 56–65, May–June, 1999.     

Phase diagram of system As2S3–Cu2S–PbS at 773–1173 K

The phase equilibrium of the system As₂S₃–Cu₂S–PbS and its pseudo binaries with low arsenic contents were studied using isothermal equilibrium and quenching experiments at temperatures between 773 and 1173 K. Based on the experimental results, the phase diagrams of these systems have been estimated. Both estimated pseudo binary phase diagrams indicate higher arsenic sulphide solubility into liquid than previously reported in the literature. The liquidus isotherms of the system As₂S₃–Cu₂S–PbS indicate narrow fully molten area widening with increasing temperature between diginite and galena primary phase fields.

On a étudié l’équilibre de phase du système As₂S₃–Cu₂S–PbS et ses pseudos binaires avec de faibles teneurs en arsenic en utilisant des expériences d’équilibre isotherme et de trempe à des températures entre 773 K et 1173 K. On a estimé les diagrammes de phase de ces systèmes en se basant sur les résultats expérimentaux. Les deux diagrammes de phase, pseudos binaires, estimés indiquent une solubilité plus élevée du sulfure d’arsenic dans le liquide que ce qui avait été rapporté auparavant dans la littérature. Les isothermes du liquidus du système As₂S₃–Cu₂S–PbS indiquent une région étroite complètement fondue qui s’élargit avec une augmentation de la température entre les champs de phase primaire de la diginite et de la galène.     

High-temperature phase equilibria of Cu–O–Al2O3 system in air

Phase equilibria of Cu–O–Al₂O₃ system were experimentally investigated in a temperature range of 1100–1400°C under 0.21?atm oxygen pressure. The experiments were conducted employing a high-temperature equilibration and quenching method. Microstructures of the quenched samples were observed with scanning electron microscope. The phase compositions in the samples were analysed with electron probe microanalysis technique. Measured solubility of Al₂O₃ into the molten oxide ranged from 0.0 to 1.8?wt-%. A small solubility of Cu₂O into Al₂O₃ was also observed ranging from 1.20 to 1.58?wt-%.     

Effect of K2O on Phase Relation and Viscosity of the CaO–SiO2—ZnO—FeO–Al2O3 System Slags

Russian Journal of Non-Ferrous Metals - The effect of K2O on phase relation and viscosity of the CaO–SiO2–25 wt % “FeO”–12 wt % ZnO–3 wt % Al2O3 slags...     

Study on electrical conductivity of FexO–CaO–SiO2–Al2O3 slags

The composition dependences of electrical conductivity of Fe_xO–CaO–SiO₂–Al₂O₃ slags at different oxygen potentials and temperatures have been studied experimentally in the present work. From the experimental results, the total electrical conductivity and electronic conductivity for all the slags monotonously decrease as increasing CO/CO₂ ratio from about 0 to 1. With the increase of Fe_xO content, the total electrical conductivity and electronic conductivity increase at a fixed CO/CO₂ ratio. It is also found that the ionic conductivity of all the studied slags increases as increasing the CO/CO₂ ratio, which is resulted from the increase of Fe²⁺ ion concentration. In addition, the temperature dependences of ionic, electronic and total conductivity for different compositions obey the Arrhenius law. The electronic transference number exhibits a strong relationship with oxygen potential, but is independent of temperature.     

Viscosity of CaO–MgO–Al2O3–SiO2 melts containing SiC particles

The influence of SiC particle on viscosity of CaO–MgO–Al₂O₃–SiO₂ melts was investigated by the rotating-cylinder method. It was found that temperature dependence of viscosity could be described by the Arrhenius law for systems with or without SiC particle addition. The activation energies of liquid–solid mixtures were mainly determined by liquid phase. Temperature had little influence on the relative viscosity (defined as the viscosity ratio of solid–liquid mixture to pure liquid). Viscosity and relative viscosity increased as decreasing rotation speed and increasing volume fraction of SiC solid particle. For the same volume fraction of SiC particle, relative viscosity was affected by the liquid slag compositions. The relative viscosity was smaller when composition of liquid slag had a larger CaO/SiO₂ ratio or MgO/Al₂O₃ ratio. Meanwhile, it was found that the smaller SiC particle will lead to a larger relative viscosity.     

Viscosity of low silica CaO–5MgO–Al2O3–SiO2 slags

Abstract

The viscosity of CaO–5MgO–Al₂O₃–SiO₂ slag with low silica was measured by rotating cylinder method up to 1823 K. Slag compositions were chosen based on five different levels of SiO₂ content between 0 and 11·80%. The MgO content was 5·0%. The mass ratio of CaO/Al₂O₃ was varied from 0·66 to 1·95. It was shown that viscosity decreased with increasing temperature and decreased with increasing the mass ratio of CaO/Al₂O₃, following by an increase with further increasing the mass ratio of CaO/Al₂O₃. The viscosity decreased with the NBO/T ratio increasing, and the trend that flow activation energy changes with the NBO/T ratio of slag was the same as the trend that viscosity changes with the NBO/T ratio. Based on the experimental data as the boundary of the homogenous phase region, the mass triangle model was used to calculate the viscosity of low silica region.     

Properties investigation of CaO–Al2O3–SiO2–Li2O–B2O3–Ce2O3 mould flux with different w(CaO)/w(Al2O3) for heat-resistant steel continuous casting

The new CaO–Al₂O₃–SiO₂–Li₂O–B₂O₃–Ce₂O₃ mould flux was devised to realise smooth continuous casting of Ce-bearing heat-resistant steel. The new devised mould flux was based on calcium-aluminate system, so the w(CaO)/w(Al₂O₃) has great influence on the properties of the slag, which is similar to the basicity in the silicate system. The melting temperature, viscous properties, slag structure and crystalline phases with different w(CaO)/w(Al₂O₃) were investigated. The melting temperature of the mould flux could remain relatively steady with w(CaO)/w(Al₂O₃) in the range of 1.0–1.82. The main network former in the new slag was [AlO₄]-tetrahedron. The network formed by [AlO₄]-tetrahedron was destroyed by increasing w(CaO)/w(Al₂O₃), the viscosity decreased consequently. The mould flux show weaker crystallisation tendency with increasing w(CaO)/w(Al₂O₃). When the temperature decreased to 1100°C, the change of the fully crystallised phases with increasing w(CaO)/w(Al₂O₃) was as follows: Li₂O·Al₂O_3?+?2CaO·Al₂O₃·SiO_2?→?Li₂O·Al₂O_3?→?Li₂O·Al₂O_3?+?3CaO·Al₂O_3?+?CaCeAlO₄.     

Kinetics of Na2O evaporation from CaO–Al2O3–SiO2–MgO–TiO2–Na2O slags

The present work is carried out to study the evaporation of Na₂O from CaO–Al₂O₃–SiO₂–TiO₂–MgO–Na₂O slags with high basicity and high alumina in the temperature range of 1500–1560°C. The ratio of evaporation was determined by monitoring the Na₂O content change of the slag melt under isothermal reduction conditions. The results show that the evaporation ratio increases with increasing the temperature. Higher basicity and increasing concentrations of Na₂O, Al₂O₃ are also found to increase the evaporation ratio of Na₂O, while MgO addition only slightly enhances the evaporation ratio. With TiO₂ content increasing, the evaporation ratio first increases and then decreases. The evaporation rate of Na₂O appears to be controlled by chemical reaction at the slag/gas interface in the beginning, followed by a mixed reaction-mass transfer regime, and finally a liquid-phase mass transport step. The apparent activation energy is 134.74?kJ?mol^?1 for the chemical reaction regime and 268.53?kJ?mol^?1 for the liquid-phase mass diffusion step.     

Phase diagram of the system Cu2S–PbS–ZnS at 873–1273 K

An equilibration quenching technique was used in this work to study experimentally the phase relations in the Cu₂S–PbS–ZnS system at the temperature range 873–1273 K. The phase diagrams and optimised thermodynamic data set have been created for the systems PbS–ZnS and Cu₂S–PbS–ZnS with the experimental results of this work and selected data reported in the literature by the CALPHAD (CALculation of PHAse Diagrams) method over the temperature range of 773–1473 K. The obtained thermodynamic dataset allows calculation of the thermodynamic properties and phase equilibria in the PbS–ZnS and Cu₂S–PbS–ZnS systems and shows good agreement with experimental results.

Dans ce travail, on a utilisé une technique de trempe d’équilibration pour étudier expérimentalement les relations de phases du système Cu₂S–PbS–ZnS dans la gamme de température de 873 à 1273 K. Utilisant la méthode CALPHAD (CALculation of PHAse Diagrams), on a créé les diagrammes de phases et l’ensemble de données thermodynamiques optimisées des systèmes PbS–ZnS et Cu₂S–PbS–ZnS, dans la gamme de température de 773 à 1473 K, au moyen des résultats expérimentaux de ce travail et de données choisies rapportées dans la littérature. L’ensemble de données thermodynamiques obtenues permet le calcul des propriétés thermodynamiques et des équilibres de phases des systèmes PbS–ZnS et Cu₂S–PbS–ZnS, qui sont en bon accord avec les données expérimentales.     

Dissolution behaviour of MgO based refractories in CaO–Al2O3–SiO2 slag

Abstract

Magnesium oxide (MgO) based refractories are widely used in secondary refining processes, and their dissolution into refining slag is the primary cause of their shortened lifespan. The dissolution rate was investigated for sintered MgO and commercial MgO–C and MgO–Cr₂O₃ refractories in a synthesised 50CaO–45Al₂O₃–5SiO₂ liquid (mass-%) slag. The change in slag composition was measured after a refractory sample was placed into the molten slag that was stirred by flowing argon gas at 1773?K. The dissolution rate of the sintered MgO was above those of the MgO–C and MgO–Cr₂O₃ refractories under the same gas flowrate, although the dissolution rate of all samples increased as the gas flowrate was increased from 25 to 75?mL·min^??1. The slag containing 5?mass-% FeO considerably promoted the dissolution of the MgO–C refractory because of the oxidation of carbon by FeO. The dissolution of all the refractories was greatly affected by penetration of the liquid slag, with the mass transfer of MgO in the penetrating slag at lower gas flowrates likely being the rate controlling step. At high gas flowrates, Ar bubbles covered the surface and blocked the contact between the liquid slag and the solid phase, reducing the dissolution rate.     

An empirical formula for accurate calculation of liquidus temperature of blast furnace slags in SiO2–Al2O3–CaO–MgO system

Precise numerical simulations of blast furnace (BF) rely on accurate and convenient thermophysical property models of BF slags. Liquidus temperature (T_liq) is one of the most fundamental properties of BF slag, however, the conventional phase equilibrium diagram method for T_liq calculation can be hardly used in numerical simulations. In this work, an accurate and simple empirical formulation suitable for T_liq calculation of BF slags in numerical simulations is established. The model was calibrated by 707 measurement representing 11 primary phase fields in SiO₂–Al₂O₃–CaO–MgO system. The calculated T_liq in present work agrees very well with the measured values, with an average error of only 17.1°C, which is much more accurate than CalPhad method. Present work also suggests that the liquidus region of BF slag at 1500°C should be slightly extended based on the classic phase equilibrium diagram.     

Evaluation of B2O3 as replacement for CaF2 in CaO–Al2O3 based mould flux

In order to develop low fluoride or fluoride free CaO–Al₂O₃ based mould flux for casting high aluminium steel, an investigation was carried out to study the effect of substituting CaF₂ with B₂O₃ on heat transfer and crystallisation behaviour of CaO–Al₂O₃ based mould flux by employing a heat transfer simulator of mould flux and a single hot thermocouple technique. The results showed that addition of CaF₂ promoted heat transfer of CaO–Al₂O₃ based mould flux, which was opposite to the effect of CaF₂ on heat transfer in conventional CaO–SiO₂ based mould flux. Addition of CaF₂ inhibited crystallisation of CaO–Al₂O₃ based mould flux by lowering the start crystallisation temperature and prolonging the incubation time of crystallisation. B₂O₃ showed similar effects to CaF₂ on heat transfer and crystallisation of CaO–Al₂O₃ based mould flux, but its ability to promote heat transfer and suppress crystallisation was stronger than CaF₂. Ca₃B₂O₆ (melting temperature 1480°C) was found as the primary crystalline phase in fluoride free CaO–Al₂O₃ based mould flux compared with the primary crystalline phase Ca₂Al₃O₆F (melting temperature 1507°C) in fluoride bearing (20% CaF₂) CaO–Al₂O₃ based mould flux.     

Solidus Surface and Phase Equilibria in Al2O3 ― ZrO2 ― La2O3 Alloy Crystallization

The projection of the solidus surface in the phase diagram for the Al₂O₃ ZrO₂ La₂O₃ system on the plane of a concentration triangle has been constructed, which consists of seven isothermal three-phase fields corresponding to three nonvariant equilibria of eutectic type and four nonvariant equilibria of peritectic type, as well as four lineated surfaces for the end of crystallization in the binary eutectics. The highest temperature on the solidus surface is 2710°C, and the lowest is 1665°C. No ternary phases and appreciable areas of solid solution are observed. Data on the bounding binary systems, liquidus and solidus surfaces have been used to construct the phase-equilibrium diagram together with a scheme for the reactions in equilibrium crystallization in the Al₂O₃ ZrO₂ La₂O₃ system.