Intriguing spin-lattice interactions in EuTiO3.

During the last decade the cubic perovskite oxide EuTiO3 (ETO) has attracted enormous novel research activities due to possible multiferroicity, hidden magnetism far above its Néel temperature at TN = 5.5 K, structural instability at TS = 282 K, possible application as magneto-electric optic device, and strong spin-lattice coupling. Here we address a novel highlight of this compound by showing that well below TS a further structural phase transition occurs below 210 K without the application of an external magnetic field, and by questioning the assumed tetragonal symmetry of the structure below TS where tiny deviations from true tetragonality are observed by birefringence and XRD measurements. It is suggested that the competition in the second nearest neighbor spin-spin interaction modulated by the lattice dynamics is at the origin of these new observations.

Micro-Raman and FTIR studies of synthetic and natural apatites.

B-type synthetic carbonate hydroxyapatite (CHAp), natural carbonate fluorapatite (CFAp) and silicon-substituted hydroxyapatite (SiHAp) have been studied by using micro-Raman and infrared (IR) spectroscopy. It was found that while B-type carbonate substitution predominates in carbonate apatites (CAps), A-type is also detected. B-type carbonate substitution causes a broadening of the v(1) P-O stretching mode that is associated with the atomic disorder and lowering of the local symmetry in CAps from C(6h)(2) to C(3h). An approximately 15 cm(-1) shift of the v(3c) PO(4) stretching IR mode was observed upon decarbonation of the CFAp. Such shift which was confirmed by lattice dynamics calculations points out that the P-O bond lengths on the mirror plane increase when carbonate leaves the apatite structure. The present results support the substitution mechanism proposed on the basis of neutron powder diffraction studies of the same samples whereby carbonate substitutes on the mirror plane of the phosphate tetrahedron. The intensity ratios of the v(2) IR CO(3) and v(1) PO(4) bands in samples of various carbonate contents provide a measure of the degree of carbonation for CAps.