Structural origin of the anisotropic and isotropic thermal expansion of K2NiF4-type oxides

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American Chemical Society
K2NiF4-type LaSrAlO4 and Sr2TiO4 exhibit anisotropic and isotropic thermal expansion, respectively; however, their structural origin is unknown. To address this unresolved issue, the crystal structure and thermal expansion of LaSrAlO4 and Sr2TiO4 have been investigated through high-temperature neutron and synchrotron X-ray powder diffraction experiments and ab initio electronic calculations. The thermal expansion coefficient (TEC) along the c-axis (αc) being higher than that along the a-axis (αa) of LaSrAlO4 [αc = 1.882(4)αa] is mainly ascribed to the TEC of the interatomic distance between Al and apical oxygen O2 α(Al–O2) being higher than that between Al and equatorial oxygen O1 α(Al–O1) [α(Al–O2) = 2.41(18)α(Al–O1)]. The higher α(Al–O2) is attributed to the Al–O2 bond being longer and weaker than the Al–O1 bond. Thus, the minimum electron density and bond valence of the Al–O2 bond are lower than those of the Al–O1 bond. For Sr2TiO4, the Ti–O2 interatomic distance, d(Ti–O2), is equal to that of Ti–O1, d(Ti–O1) [d(Ti–O2) = 1.0194(15)d(Ti–O1)], relative to LaSrAlO4 [d(Al–O2) = 1.0932(9)d(Al–O1)]. Therefore, the bond valence and minimum electron density of the Ti–O2 bond are nearly equal to those of the Ti–O1 bond, leading to isotropic thermal expansion of Sr2TiO4 than LaSrAlO4. These results indicate that the anisotropic thermal expansion of K2NiF4-type oxides, A2BO4, is strongly influenced by the anisotropy of B–O chemical bonds. The present study suggests that due to the higher ratio of interatomic distance d(B–O2)/d(B–O1) of A22.5+B3+O4 compared with A22+B4+O4, A22.5+B3+O4 compounds have higher α(B–O2), and A22+B4+O4 materials exhibit smaller α(B–O2), leading to the anisotropic thermal expansion of A22.5+B3+O4 and isotropic thermal expansion of A22+B4+O4. The “true” thermal expansion without the chemical expansion of A2BO4 is higher than that of ABO3 with a similar composition. © 2015 American Chemical Society
Thermal expansion, Neutron diffraction, Oxygen, Oxides, Granular materials, X-ray diffraction
Kawamura, K., Yashima, M., Fujii, K., Omoto, K., Hibino, K., Yamada, S., Hester, J. R., Avdeev, M., Miao, P., Torii, S., & Kamiyama, T. (2015). Structural origin of the anisotropic and isotropic thermal expansion of K2NiF4-type oxides. Inorganic Chemistry, 54(8), 3896–3904. doi:10.1021/acs.inorgchem.5b00102