The solidification behavior of materials with general formula XB₂O₄(X=Ca, Sr, Ba) has been investigated by differential thermal analysis (DTA). The melts of these materials are found to undergo large supercooling, which is strongly dependent on the atmosphere provided during the thermal cycle. The DTA plot of BaB₂O₄ shows the presence of a single exotherm, implying normal freezing behavior of the material. In contrast, for CaB₂O₄or SrB₂O₄ two exotherms are observed, suggesting their solidification behavior to be complex in nature.