XANES (X-ray absorption near-edge structure) spectra of the Ti K-edges of ATiO3 (A = Ca and Sr), A2TiO4 (A = Mg and Fe), TiO2 rutile and TiO2 anatase were measured in the temperature range 20-900 K. Ti atoms for all samples were located in TiO6 octahedral sites. The absorption intensity invariant point (AIIP) was found to be between the pre-edge and post-edge. After the AIIP, amplitudes damped due to Debye-Waller factor effects with temperature. Amplitudes in the pre-edge region increased with temperature normally by thermal vibration. Use of the AIIP peak intensity as a standard point enables a quantitative comparison of the intensity of the pre-edge peaks in various titanium compounds over a wide temperature range.
A variable-temperature single-crystal X-ray diffraction study of a synthetic BaTiO3 perovskite has been performed over the temperature range 298-778 K. A transition from a tetragonal (P4mm) to a cubic (Pm3m) phase has been revealed near 413 K. In the non-centrosymmetric P4mm symmetry group, both Ti and O atoms are displaced along the c-axis in opposite directions with regard to the Ba position fixed at the origin, so that Ti(4+) and Ba(2+) cations occupy off-center positions in the TiO6 and BaO12 polyhedra, respectively. Smooth temperature-dependent changes of the atomic coordinates become discontinuous with the phase transition. Our observations imply that the cations remain off-center even in the high-temperature cubic phase. The temperature dependence of the mean-square displacements of Ti in the cubic phase includes a significant static component which means that Ti atoms are statistically distributed in the off-center positions.
The Ti and Zr K‐edge X‐ray absorption near edge structure (XANES) spectra of ATiO3 (A = Sr, Ba, and Pb) and PbZrO3 perovskite‐type compounds have been measured in the temperature range 20–900 K. Quantitative comparison is performed in a wide temperature range to clarify how the intensities of the pre‐edge peaks and shoulders change with temperature. In the ferro‐ and antiferroelectric tetragonal phases, the intensities of some of the peaks and shoulders decrease with increasing temperature and the peak‐top energies shift to the higher energy side. The shift can be explained by the position and decrease (increase for SrTiO3) of the D2 peak in the difference spectra. The peak‐top position of the pre‐edge peak in XANES does not always represent the true energy for independent transition to an orbital because several orbitals with similar energies overlap. The tetragonal SrTiO3 phase shows the same behavior as ferroelectric P4mm tetragonal BaTiO3 and PbTiO3 perovskite. The temperature dependence of the shoulder is also an important index. The presence of a phase with local polar tetragonal strain is important in materials and the Earth's constituent solid solutions. The existence of ferro‐ and antiferroelectricity can be determined by temperature‐dependent XANES measurements.
The local structure of iron in tektites from six strewn fields, and impact -and non -impact -related glass were studied using the Fe K -edge X -ray absorption near edge structure (XANES) and extended X -ray absorption fine structure (EXAFS) techniques, in order to obtain quantitative data on Fe -O bond length and Fe coordination number. X -ray absorption fine structure (XAFS) spectra and Fe -O bonds in standard minerals such as hematite, fayalite, and magnetite were compared. The degree of oxidation was measured based on the valencies of iron in the samples. Tektites contain a greater proportion of ferrous than ferric iron [0.04 (1) /ƩFe] are higher than that in tektites. Based on the measured Fe -O distance, it was inferred that 4 -and 5 -coordinated Fe exist in tektites, whereas volcanic glass contains 5 -and 6 -coordinated Fe. Impact -related glass possesses various local structures caused by the combination of 4 -, 5 -, and 6 -coordinated Fe. During formation, tektites experience high temperatures and a reducing atmosphere when they were ejected into the outer space. In contrast, the impact -related glass, which was ejected into the atmosphere or which remained close to the crater, experienced a more complex environment, with air pressure, density, and temperature varying across the atmospheric layers. Thus, impact -related glass presents more complicated oxidation states and structure compared to tektites. Volcanic glass, on the other hand, has a relatively stable redox condition; and thus, it undergoes only a small change in the degree of oxidation. This study indicates that the local structure and oxidation state of Fe may change due to the environment that the glass experienced during its formation. These different kinds of natural glass can be distinguished from each other using the study of the local structure.
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