Composition and Mobility of Ionic Ensembles in Slags for Steel Refining in the Ladle–Furnace Unit

Abstract

High-lime synthetic slags for refining steels in the ladle–furnace unit are investigated. The content of the slag mixtures is as follows: 60 wt % CaO, 7 and 8 wt % MgO, 7–23 wt % Al₂O₃, and 9–18 wt % SiO₂, with additions of 8 wt % CaF₃ and 5–15 wt % Na₂O. Polymer theory is used to calculate the composition of the anionic subsystem in the slag melts. The log-mean polymerization constants K ^*_p for multicomponent melts are calculated from the known polymerization constants in binary systems. It is found that K ^*_p ≈ 10^–3–10^–2 in the range 1500–1600°C. In that range, the melt’s degree of polymerization is 3 × 10^–4–8 × 10^–3. In the most polymerized melt, the ionic content of the dimers Si₂O ^6-₇ and Al₂O ^8-₇ is no more than 0.1 and 1.5% of the values for the corresponding monomers. Therefore, we assume, with an error of about 2%, that the structural units of the anionic subsystem are monomers AlO ^5-₄ and SiO ^4-₄ simple O^2– and F^– ions (slag 7). The cationic subsystem consists of Ca²⁺, Mg²⁺, Na⁺, and Al³⁺ ions in octahedral coordination with oxygen (less than 3% of all the Al atoms). In all the melts, the concentrations of free oxygen ions O^2– and Ca²⁺ ions are similar. In half the cases, the content of O^2– ions is greater than the content of Ca²⁺ ions. The mean mobility U and self-diffusion coefficient D for all the cations are calculated from data for the electrical conductivity and the density. With increase in temperature from 1500 to 1600°C, U and D increase by 50 and 60%, respectively, in all the slags. With increase in the mutual substitution of the components in the slag mixtures M = n(Na₂O, CaF₂)/n(Al₂O₃ + SiO₂), mol/mol, at 1600°C, U increases from 1.14 × 10^–8 to 1.46 × 10^–8 m²/(V s) for slags 1–6 (0 ≤ M ≤ 1.1) and from 1.01 × 10^–8 to 1.66 × 10^–8 m²/(V s) for slags 7–10 (0.25 ≤ M ≤ 0.65). Correspondingly, D increases from 9.2 × 10^–10 to 12.8 × 10^–10 m²/s for slags 1–6 and from 8.2 × 10^–10 to 14.3 × 10^–10 m²/s for slags 7–10. The temperature dependence of U and D may be approximated by an Arrhenius equation with activation energies E _U and E _D . With increase in M in the given ranges, E _U declines from 146 to 100 kJ/mol (slags 1–6) and from 124.5 to 109 kJ/mol (slags 7–10). Likewise, E _D declines from 159 to 116.5 kJ/mol (slags 1–6) and from 139.5 to 124 kJ/mol (slags 7–10). The mean values of E _U and E _D correlate with the mean distance between the cations in the melts. On the basis of the proposed alternative model of the conductivity, the O^2– ions may also transfer electric charge. Preliminary estimates show that the oxygen transport number at 1600°C may exceed 0.1 in some slags.