In this study, solidified films of CaO-Al₂O₃-BaO-CaF₂-Li₂O-based mold fluxes with different contents of Al₂O₃ addition were acquired by immersing an improved water-cooled copper probe in bulk molten slags. This probe can obtain films with representative structures. Different slag temperatures and probe immersion times were employed to investigate the crystallization process. The crystals in the solidified films were identified using X-ray diffraction, the morphologies of the crystals were observed using optical microscopy and scanning electron microscopy, and the kinetic conditions, especially the activation energy of devitrified crystallization in glassy slags, were calculated and discussed based on the differential scanning calorimetry. The results indicated that after adding extra Al₂O₃, the growing speed and thickness of the solidified films increased, and more time was required for the film thickness to reach a steady state. In addition, fine spinel (MgAl₂O₄) precipitated in the films at the early stage of solidification after adding 10 wt% of extra Al₂O₃. Together with LiAlO₂, spinel (MgAl₂O₄) acted as nuclei for the precipitation of BaAl₂O₄. The apparent activation energy of initial devitrified crystallization decreased from 314.16 KJ/mol (original slag) to 297.32 KJ/mol (5 wt% Al₂O₃ added) and 269.46 KJ/mol (10 wt% Al₂O₃ added). The crystallization ratio of the films also increased after adding extra Al₂O₃.

Novel SiO₂-CaO-CaF₂-R₂O-MgO based synthetic slags (R₂O represents alkali metal oxides) with varied binary basicity values were used with oxygen injection to refine silicon melts and remove Fe from metallurgical-grade silicon. Silicon samples and slags at the silicon-slag interfaces were obtained during refinement. The compositions of the silicon samples were analyzed, and the quenched slag samples and mild cooling slags from the final crucible were inspected using scanning electron microscopy and energy dispersive X-ray spectroscopy. After 15 min of refinement, the Fe removal rate ranged from 52.3 to 60.1 wt%. During the refining process, the Fe-concentrated phase formed within the silicon droplets and was then transferred to the silicon-slag interfaces and wetted with slags. The Fe-concentrated phase at the silicon-slag interface can dissolve directly in the slags. It can also be transferred into the slag phase in the form of droplets, which can be affected by the binary basicity of the slags. Ti removal demonstrated a similar mechanism. Fe-bearing crystals were not detected in the quenched slag samples obtained during refinement, while complex Fe-bearing phases were detected in the final slag. This study demonstrates Fe removal from metallurgical-grade Si using slag refining methods and reveals the removal mechanism during the refinement.