The compound BaZn2Si2O7 shows a high coefficient of thermal expansion up to a temperature of 280 °C, then a transition to a high temperature phase is observed. This high temperature phase exhibits negative thermal expansion. If Ba2+ is successively replaced by Sr2+, a new phase with a structure, similar to that of the high temperature phase of BaZn2Si2O7, forms. At the composition Ba0.8Sr0.2Zn2Si2O7, this new phase is completely stabilized. The crystal structure was determined with single crystal X-ray diffraction using the composition Ba0.6Sr0.4Zn2Si2O7, which crystallizes in the orthorhombic space group Cmcm. The negative thermal expansion is a result of motions and distortions inside the crystal lattice, especially inside the chains of ZnO4 tetrahedra. Dilatometry and high temperature X-ray powder diffraction were used to verify the negative thermal expansion. Coefficients of thermal expansion partially smaller than −10·10−6 K−1 were measured.
The compound BaZn2Si2O7 shows a highly positive coefficient of thermal expansion. At a temperature of 280 °C, it transforms to a high temperature phase, which exhibits a coefficient of thermal expansion near zero. The partial replacement of Ba(2+) against Sr(2+) leads to a decrease of the phase transition temperature. If more than 10% of Ba(2+) are replaced by Sr(2+), the high-temperature phase is completely stable at room temperature and consequently, the thermal expansion is near zero or negative. The effect of the Sr(2+)/Ba(2+)-ratio on the phase transition temperature and the thermal expansion behavior is measured using high-temperature X-ray diffraction up to 1000 °C. The Sr(2+)/Ba(2+)-ratio strongly affects the overall thermal expansion as well as the anisotropy. The latter increases with decreasing Sr-concentration. The strong differences in the thermal expansion behavior between phases with the structure of the low-temperature phase and the high-temperature phase of BaZn2Si2O7 can be explained by a comparison of the ZnO4-chains inside these two crystal structures.
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