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 CaB2O4 or SrB2O4 two exotherms are observed, suggesting their solidification behavior to be complex in nature. (C) 2002 Published by Elsevier Science B.V.