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High temperature powder X-ray diffraction measurements of Ba 3  R B 3 O 9  ( R =Sm–Yb, and Y) were carried out at temperatures ranging from room temperature to just below the corresponding melting temperatures (1,200–1,300 °C). No phase transition was found for the H-type phase ( R3  ‾    $\overline 3 $   ) with  R =Sm–Tb and the L-type phase ( P 6 3  cm) with  R =Tm–Yb. On the other hand, phase transition from the L phase to the H phase was observed for  R =Dy–Er, and Y at around 1,100–1,200 °C. The obtained axial thermal expansion coefficient (ATEC) of the  a -axis was larger than that of the  c -axis for the H phase, and the ATEC of the  c -axis was larger than that of the  a -axis for the L phase. The observed anisotropic nature of ATEC is attributed to the distribution of the BO 3  anionic group with rigid boron–oxygen bonding in the structures of the H and L phases.

Phase Transition and Thermal Expansion of Ba 3 R B 3 O 9 ( R = Sm–Yb, and Y)