Effect of White Mud Addition on Desulfurization Rate of Molten Steel

Fluorspar (CaF2) is commonly used to control the fluidity of slag in ladle-refining of steel. However, because it is desirable to reduce CaF2 consumption because of its environmental impacts, the industrial waste material such as white mud (WM) was investigated as a potential substitute for fluorspar. Steel sample (Fe-0.3C-0.9Mn-0.3Si-0.03Al-0.05S, mass pct) was melted in a high-frequency induction furnace, followed by additions of ladle slag (CaO-Al2O3-SiO2-5MgO-xCaF2, CaO/Al2O3=3, x = 0 to 10 mass pct) and fluxing agent (WM) at 1823 K (1550 °C). The desulfurization experiments were carried out by reducing CaF2 content in the ladle slag and increasing the addition of WM. Ladle slag with added WM showed an overall mass transfer coefficient of sulfur (kO) equivalent to or higher than that of conventional 10 mass pct CaF2-containing ladle slag. In a slag melting experiment based on DIN 51730 standard, the melting rate of mixed slag increased with the amount of WM added, which is considered to have a positive effect on the initial desulfurization rate. In addition, adding WM provided sulfide capacity of the slag equivalent to that of CaF2-containing slag. Consequently, the use of WM yielded slag having $$k_{{\text{O}}}$$ k O equivalent to or higher than that of conventional ladle slag with 10 pct CaF2, and thus, WM shows promise as a partial replacement for fluorspar.

Desulfurization Behavior of Incoloy® 825 Superalloy by CaO-Al2O3-MgO-TiO2 Slag

Ni-based superalloy, which has excellent high-temperature strength and corrosion resistance, is mainly used in aviation materials, high-performance internal combustion engines, and turbines for thermal and nuclear power generation. For this reason, refining the impurities in Ni-based superalloys is a very important technical task. Nevertheless, the original technology for the melting and refining of Ni-based superalloys is still insufficient. Therefore, in this study, the effect of the CaO-Al2O3-MgO-TiO2 slag on the removal efficiency of an impurity element sulfur in Incoloy® 825 superalloy, one of the representative Ni-based superalloys, was investigated. The desulfurization behavior according to the change of TiO2 content and CaO/Al2O3 (=C/A, basicity) ratio as experimental variables was observed at 1773 K (1500 °C). Although the TiO2 content in the slag increases to 15 mass pct, the mass transfer coefficient of sulfur in molten alloy showed a constant value. Alternatively, under the condition of C/A > 1.0 of slag, the mass transfer coefficient of sulfur showed a constant value, whereas under the condition of C/A < 1.0, the mass transfer coefficient of sulfur greatly decreased as CaO decreased. Hence, in the desulfurization of Incoloy® 825 superalloy using the CaO-Al2O3-MgO-TiO2 slag, the TiO2 content in the slag does not have a considerable effect on the desulfurization rate and desulfurization mechanism (metal phase mass transfer controlled regime), but the basicity of the slag has a significant effect on desulfurization mechanism. When the slag basicity decreases below the critical level, i.e., C/A < 1.0, which is corresponding to sulfur distribution ratio, Ls < 200, it was confirmed that the desulfurization mechanism shifts from the metal phase mass transfer-controlled regime to the slag phase mass transfer-controlled regime due to the variation in the physicochemical properties of the slag such as viscosity and sulfide capacity. In addition, the different desulfurization rates between steel and Ni alloy melts were discussed by employing the diffusivity of sulfur in both systems.

Application of ionic theory to calculate sulfide capacity of slags

The article considers the issues of sulfur removal in the ladle-furnace unit. The sulfur distribution coefficient depends on sulfide capacity of the slag, sulfur activity coefficient, oxidizing potential of the medium and equilibrium constant. The sulfide capacity CS of slags is one of the most important characteristics of refining capacity of the slags used in extra-furnace steel processing. One of the factors affecting the sulfide capacity is temperature. The formula was proposed showing the dependence of sulfide capacity on the optical basicity and temperature, in the temperature range of 1650 – 1400 °C and when the optical basicity Λ is not more than 0.75; the error of the presented formula does not exceed 6 %. The formula for calculating the optical basicity is proposed, which takes into account the influence of basic, acidic oxides and amphoteric oxide Al2O3. It is shown that slags, completely consisting of a homogeneous phase, have an increased optical basicity of aluminum oxide. Heterogeneous slags have a reduced optical basicity of Al2O3 in comparison with homogeneous slags. Perhaps, this fact can be explained by the fact that in homogeneous slags there is a deficiency of the basic oxide CaO and in the conditions under consideration Al2O3 compound begins to exhibit more basic properties than acidic ones, thus, in homogeneous slags, the optical basicity of aluminum oxide is increased and approaches optical basicity of CaO oxide. Calculations carried out on the basis of real heats have shown that with an increase in the content of Al2O3 oxide in the slag, its optical basicity decreases. Known value of the optical basicity makes it possible to determine sulfide capacity of the slag, sulfur distribution coefficient between metal and slag, and, accordingly, final sulfur content in the metal. The research results have shown that it is advisable to apply the ionic theory of slags for the sulfide capacity determination.