Bi0.5Na0.5TiO3 (BNT) and (Bi0.5Na0.5)(1-x)BaxTiO3 (BNBT; 0.02 <= x(Ba)(melt) <= 0.12) single crystals were grown by the Top Seeded Solution Growth (TSSG) method under conditions near to the thermodynamic equilibrium. The driving force for the crystallization process is only given by the controlled evaporation of the volatile components Bi2O3 and Na2O. The Ba-segregation coefficient in the BNBT-system was determined to be approximate to 0.56 on the basis of EMPA measurements on single crystals grown from melts with a different Ba-content. Congruent melting of BNT is clearly indicated by DSC measurements at 1291 degrees C. BNBT behaves in a similar way whereas melting temperatures are lowered with increasing x(Ba), c(p)(T) calculations and heating/cooling polarizing microscopy was performed for the investigation of the complex domain state behavior during the phase transitions in BNT. (C) 2014 Elsevier B.V. All rights reserved.