AbstractOxidative ladle refining (OLR) is the most used refining method in industrial production of metallurgical grade silicon. OLR is performed by purging the liquid alloy with oxygen-enhanced air at 1823 K to 1873 K, reacting with silicon and the primary slag forming impurities to a SiO$$_{2}$$
2
-CaO-Al$$_{2}$$
2
O$$_{3}$$
3
slag. To further increase our capability to control this process, it is paramount to understand how the slag nucleates and forms, and represent it such that it is useful for predicting and controlling the process behavior. This work aims to formulate a comprehensive theoretical description of slag nucleation and formation at nano/microscale using classical macroscale thermodynamics, bridging these spatial regimes. To achieve this, the work argues that silica’s liquid structure allows its nuclei to exhibit “well defined” surfaces. Furthermore, silica is predicted to be highly surface active, so if its concentration is high while the slag nucleus is small, the SiO$$_{2}$$
2
-CaO-Al$$_{2}$$
2
O$$_{3}$$
3
slag should retain silica’s surface properties. An experiment confirmed the surface active nature of silica in the SiO$$_{2}$$
2
-CaO-Al$$_{2}$$
2
O$$_{3}$$
3
system. It was also shown that increasing the slag’s calcia concentration has a greater effect on the interfacial tension between the molten slag and liquid alloy than alumina, confirming industrial observations of the coupling between refining rate and relative alloy/slag composition.
Maximum supercooling studies in Ti39.5Zr39.5Ni21, Ti40Zr30Ni30, and Zr80Pt20 liquids—Connecting liquid structure and the nucleation barrier