Infrared thermography provides an option for characterising surface reactions and their effects on the solidification of steel under different gas atmospheres. In this work, infrared thermography has been used during solidification of Twin Induced Plasticity (TWIP) steel in argon, carbon dioxide and nitrogen atmospheres using a confocal scanning laser microscope (CSLM). It was found that surface reactions resulted in a solid oxide film (in carbon dioxide) and decarburisation, along with surface graphite formation (in nitrogen). In both cases the emissivity and, hence, the cooling rate of the steel was affected in distinct ways. Differences in nucleation conditions (free surface in argon compared to surface oxide/graphite in carbon dioxide/nitrogen) as well as chemical composition changes (decarburisation) affected the liquidus and solidus temperatures, which were detected by thermal imaging from the thermal profile measured.