Abstract
Raman spectra of Ni2SiO4 spinel (O 7 h Z=8) have been measured in the temperature range from 20 to 600 °C and the Raman active vibrations (A 1g +E g +3F 2g ) have been assigned. A calculation of the optically active lattice vibrations of this spinel has been made, assuming a potential function which combines general valence and short range force constants. The values of the force constants at 20 and 500 °C have been calculated from the vibrational frequencies of the observed Raman spectra and infrared (IR) spectral data.
The Ni spinel at 20 °C has a prominently small Si-O bond stretching force constant of K(SiO)=2.356 ∼ 2.680 md/Å and a large Ni-O bond stretching constant of K(NiO)=0.843 ∼ 1.062 md/Å and these force constants at 500 °C decrease to K(SiO)=2.327 ∼ 2.494 md/Å and K(NiO)=0.861 ∼ 0.990 md/Å. The Si-O bond is noticeably weakened at high temperatures, despite the small thermal expantion from 1.657 Å (20 °C) to 1.660 Å (500 °C).
These changes of the interatomic force constants of the spinel at high temperatures are in accord with the thermal structure changes observed by X-ray diffraction study. The weakened Si-O bond is consistent with the fact that Si atoms in the spinel lattice can diffuse at significant rates at elevated temperature.
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Yamanaka, T., Ishii, M. Raman scattering and lattice vibrations of Ni2SiO4 spinel at elevated temperature. Phys Chem Minerals 13, 156–160 (1986). https://doi.org/10.1007/BF00308157
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DOI: https://doi.org/10.1007/BF00308157