Lanthanum tungstates with a La/W atomic ratio between 6 and 4.8 have been synthesized as polycrystalline materials using the freeze-drying wet-chemical precursor method. Our results show that a single phase material is obtained when the La/W ratio is between 5.3 and 5.7 (T = 1500 degrees C). Outside this compositional range, segregation of either La(2)O(3) (La/W > or = 5.8) or La(6)W(2)O(15) (La/W < or = 5.2) are found. We have solved the crystal structure for the composition with a La/W nominal atomic ratio of 5.6 by combining powder X-ray and powder neutron diffraction techniques. This structure substantially differs from that previously reported for Ln(6)WO(12) (Ln = Y, Ho). The main differences between the two structure types are the crystal symmetry, the different coordination environment of the cations and the formula unit. The formula unit can be written as La(6.63)W(1.17)O(13.43) (Z = 4; calculated density = 6.395 g/cm(3)), well in accordance with the diffraction techniques, He-pycnometry and electron probe microanalysis. These materials can be described as a face centred cubic structure with space group F43m. Lattice parameters vary between 11.173 and 11.188 A, depending on composition. Dense ceramic materials are obtained at 1400 degrees C, and microanalyses measurements indicate that no significant tungsten evaporation occurs compared to the nominal values. Compositions with La(2)O(3) segregation show similar conductivity values as the single phase ones, but those containing segregation of W-rich phases show a considerable drop in conductivity with increasing content of the secondary phase.

The apatite La10 - x □ x (Ge5.5Al0.5O24)O2.75 - 1.5 x (10 − x = 9.80, 9.75, 9.67, 9.60, 9.50, and 9.40) series has been prepared and the single phase existence range has been established, 9.75 ≥ 10 − x ≥ 9.45. The hexagonal crystal structures of La9.5□0.5(Ge5.5Al0.5O24)O2 have been determined at room temperature, 500 °C, and 900 °C from neutron powder diffraction data using the Rietveld method. The room-temperature unit cell parameters were a = 9.9206(4) Å, c = 7.2893(3) Å, V = 621.29(6) Å3, and Z = 1, and this refinement converged to R WP = 3.03 and R F = 1.30%. The most important structural result is the presence of interstitial oxygen ion associated with vacancies at the apatite oxide anions channels. Oxide ion conductivities have been measured by impedance spectroscopy. La9.5□0.5(Ge5.5Al0.5O24)O2 shows very high oxide conductivity, 0.16(1) S·cm-1 at 800 °C, with negligible electronic contribution. The ionic transport number, obtained by combination of impedance and ion-blocking data, is higher than 0.99 in the studied oxygen partial pressure range, 0.21 to 10-20 atm.

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