Relationship between thermal conductivity and structure of alkaline earth (Ca, Mg) aluminoborosilicate melts

The thermal conductivity of mold flux is crucial for optimising the productivity and quality of steels. This study investigates the thermal conductivity of molten oxides, including CaO-BO1.5-AlO1.5 (CBA), CaO-BO1.5-AlO1.5-SiO2 (CBAS), and CaO-MgO-BO1.5-AlO1.5 (CMBA) melts, using a hot wire method. Additionally, their structure is examined using Raman spectrometry and magic angle spinning nuclear magnetic resonance (MAS-NMR) to explore their relationship. Furthermore, first-principles calculations are employed to assess the covalency of each bond in the melts for a more quantitative analysis of their relationship. The study confirms that an increase in the CaO concentration of the CaO-BO1.5-AlO1.5 melts reduces the amount of bridging oxygen and consequently decreases thermal conductivity. The covalency of the B[4]-O bond is highest, especially when the second-nearest-neighbour Al atoms transition from Al[6] to Al[4], forming the AlB3O7 structure with B[4]. The relationship between thermal conductivity and the structure of CaO-BO1.5-AlO1.5-SiO2 melts can be quantitatively assessed using the degree of polymerisation of the network structure and the variation of covalency as indicators. Furthermore, replacing CaO with MgO in the CaO-MgO-BO1.5-AlO1.5 melts reveals a mixed alkaline earth effect on thermal conductivity.