Cationic Order-Disorder in Double Scheelite Type Oxides: the Case Study of Fergusonite La2SiMoO8.

Up to now, the possible occurrence of a cationic ordering on the tetrahedral sublattices of stoichiometric double scheelite-type oxides was not settled, with somewhat contradictory X-ray diffraction and optical measurements [Blasse, G. J. Inorg. Nucl. Chem. 1968, 30, 2091]. Using two different synthesis routes, both ordered and disordered forms of fergusonite La2SiMoO8 were prepared. The crystal structure of the ordered form was determined using powder X-ray and neutron diffraction, which clearly evidence a tridimensional ordering between [SiO4] and [MoO4] tetrahedra. The crystal chemistry of ordered double sheelite-type LaIII2(SiIVO4)(MoVIO4) can be seen as an intermediate between those of simple regular scheelite or fergusonite LnIII(NbVO4) and of ordered triple scheelite BiIII3(FeIIIO4)(MoVIO4)2. The structure of the disordered La2SiMoO8 phase was analyzed using powder X-ray diffraction. A few small and larger diffraction peaks or bumps are observed in addition to the sharper peaks of a simple fergusonite cell. DIFFaX and FAULTS programs helped showing that these faint peaks originate from stacking faults between 2D ordered layers. The intermediate 2D-3D nature of SiO4/MoO4 ordering in seemingly disordered compounds might explain the previous discrepancy between optical and X-ray diffraction measurements.

Reduction Kinetics of La2Mo2O9 and Phase Evolution during Reduction and Reoxidation.

An amorphous reduced form of oxide ion conductor La2Mo2O9 had been proposed as sulfur-tolerant anode material for solid oxide fuel cell, but its oxygen content was not known. In this paper, we investigate the reduction kinetics by diluted hydrogen of La2Mo2O9 to amorphous, and the oxygen range of the amorphous form. The reduction kinetics is studied as a function of the powder specific surface area and of the temperature, on powders synthesized by solid state reaction and by polyol process using two different solvents. The reduction process was carried out by TGA under 10% H2 diluted in argon, and its kinetics is analyzed and modeled. As expected, small particles and high temperature lead to higher reduction rates. Several reduction steps were identified by XRD during the process. At 700 °C La2Mo2O9 is directly reduced into the amorphous phase La2Mo2O7-y, whereas at 760 °C reduction occurs through an intermediate crystallized La7Mo7O30 (≅ La2Mo2O8.57) phase before amorphization. In both cases, further reduction of La2Mo2O6.2 amorphous phase leads to an exsolution of metallic molybdenum and a molybdenum deficiency in the amorphous phase. Reoxidation of amorphous La2Mo2O7-y was studied by TGA, DTA and XRD. At low temperature in air, the reduced compounds are reoxidized while remaining amorphous. The annealing for 60 h at 350 °C in air of reduced La2Mo2O6.66, obtained beforehand by solid state reaction, gives an amorphous phase with composition La2Mo2O8.85. The existence domain of the reduced amorphous phase in terms of oxygen content therefore ranges at least from O6.2 to O8.85, thus including the composition La2Mo2O8.50 of the amorphous surface layer at the origin of a huge increase of ionic conductivity recently reported in nanowires of La2Mo2O9.

Synthesis and structure resolution of RbLaF4.

The synthesis and structure resolution of RbLaF(4) are described. RbLaF(4) is synthesized by solid-state reaction between RbF and LaF(3) at 425 °C under a nonoxidizing atmosphere. Its crystal structure has been resolved by combining neutron and synchrotron powder diffraction data refinements (Pnma,a = 6.46281(2) Å, b = 3.86498(1) Å, c = 16.17629(4) Å, Z = 4). One-dimensional (87)Rb, (139)La, and (19)F MAS NMR spectra have been recorded and are in agreement with the proposed structural model. Assignment of the (19)F resonances is performed on the basis of both (19)F-(139)La J-coupling multiplet patterns observed in a heteronuclear DQ-filtered J-resolved spectrum and (19)F-(87)Rb HMQC MAS experiments. DFT calculations of both the (19)F isotropic chemical shieldings and the (87)Rb, (139)La electric field gradient tensors using the GIPAW and PAW methods implemented in the CASTEP code are in good agreement with the experimental values and support the proposed structural model. Finally, the conductivity of RbLaF(4) and luminescence properties of Eu-doped LaRbF(4) are investigated.

NMR investigations of Li(+) ion dynamics in the NASICON ionic conductors [Formula: see text].

NMR studies of (7)Li and (31)P nuclei are reported in the 150-900 K temperature range for the [Formula: see text] NASICON compounds with x = 0.8, 0.7, 0.6 and 0.3. Magic angle spinning (MAS mode) experiments were performed at room temperature on the (7)Li and (31)P nuclei. The linewidth and the spin lattice relaxation times of these nuclei are studied versus temperature in the static mode. The spectra recorded in the MAS mode show that the (7)Li ions occupy three chemical sites, the occupation of which being very sensitive to the x values but not sensitive to the coexistence of the two varieties [Formula: see text] and [Formula: see text] observed at room temperature in compounds with x≤0.5. On the other hand, the (31)P nucleus MAS spectra are very sensitive to lithium content but also to the variety coexistence. T(1) measurements were performed in a static mode on the (7)Li and (31)P nuclei. In all the compounds, the (7)Li spin lattice relaxation time exhibits two branches with several minima, indicating the complex dynamics for this ion. One of these minima appears in the same temperature range as the minimum of the (31)P nucleus T(1), strongly suggesting a cross-relaxation process between these nuclei. T(1ρ) measurements on (7)Li (static mode) allow us to show a slow motion different from the one probed by the T(1). The analysis of the T(1ρ) behaviour with temperature and composition allows us to ascribe the motion probed by this time to the oxygen ion motion which monitors the opening and closing of the lithium pathways. A qualitative interpretation of the (7)Li  T(1) results is done; it takes into account the cross-relaxation phenomena between (31)P and (7)Li and quadrupolar fluctuations.

Investigation of Polyol Process for the Synthesis of Highly Pure BiFeO3 Ovoid-Like Shape Nanostructured Powders.

Exclusive and unprecedented interest was accorded in this paper to the synthesis of BiFeO3 nanopowders by the polyol process. The synthesis protocol was explored and adjusted to control the purity and the grain size of the final product. The optimum parameters were carefully established and an average crystallite size of about 40 nm was obtained. XRD and Mössbauer measurements proved the high purity of the synthesized nanostructurated powders and confirmed the persistence of the rhombohedral R3c symmetry. The first studies on the magnetic properties show a noticeable widening of the hysteresis loop despite the remaining cycloidal magnetic structure, promoting the enhancement of the ferromagnetic order and consequently the magnetoelectric coupling compared to micrometric size powders.

Double NASICON-type cell: ordered Nd3+ distribution in Li0.2Nd0.8/3Zr2(PO4)3.

The NASICON compound Li(0.2)Nd(0.8/3)Zr(2)(PO(4))(3), synthesized by a sol-gel process, has been structurally characterized by TEM and powder diffraction (neutron and X-ray). It crystallizes in the space group R3[combining macron] (No. 148): at room temperature, the Nd(3+) ions present an ordered distribution in the [Zr(2)(PO(4))(3)](-) network which leads to a doubling of the classical c parameter (a = 8.7160(3) A, c = 46.105(1) A). Above 600 degrees C, Nd(3+) diffusion occurs leading at 1000 degrees C to the loss of the supercell. This reversible cationic diffusion in a preserved 3D [Zr(2)(PO(4))(3)](-) network is followed through thermal X-ray diffraction. Ionic conductivity measurements have been undertaken by impedance spectroscopy, while some results concerning the sintering of the NASICON compound are given.