Fantin, A.; Scherb, T.; Seeger, J.; Schumacher, G.; Gerhards, U.; Ivanova, M.; Meulenberg, W.; Dittmeyer, R.; Banhart, J.: Crystal structure of Re-substituted lanthanum tungstate La5.4W1-yReyO12-δ (0 ≤ y ≤ 0.2) studied by neutron diffraction. Journal of Applied Crystallography 49 (2016), p. 1544-1560
10.1107/S1600576716011523

Abstract:
A precise determination of sample composition and water uptake of La6-xWO12-δ (0.4 ≤ x ≤ 0.8) and Re-substituted La5.4W1-yReyO12-δ (0 ≤ y ≤ 0.2) lanthanum tungstate is carried out. Sample compositions and water uptake were determined by electron probe micro-analysis and thermogravimetry, respectively. A single-phase region of Re-substituted lanthanum tungstates is reported. The crystal structure of two selected specimens produced by the citrate-complexation route based on the Pechini method, namely La5.4WO12-δ and La5.4W0.8Re0.2O12-δ, was investigated by neutron diffraction in the temperature range 1.5 K ≤ T ≤ 1200 K. The structural model for lanthanum tungstates is validated, according to which the Wyckoff site shared by La and W (Fm3 ̅m space group, 24d site) is split with half site occupancies (Fm3 ̅m space group, 48h site). Substitution of W by up to 20 mol. % Re does not change the lattice structure, and Re atoms substitute W statistically in both 4a and 48h Wyckoff sites of the Fm3 ̅m space group as shown by combining the average neutron scattering length procedure, thermogravimetry and electron probe micro-analysis. Using the Willis and Pryor approach to anisotropic displacement parameters it is shown that the remaining static disorder in the unit cell found in La5.4WO12-δ and La5.4W0.8Re0.2O12-δ structures is comparable, when the Fm3 ̅m space group with split 48h site is employed. Through the estimation of the Debye temperature for both compounds, extracted from the analysis of thermal expansion coefficients and from the Willis and Pryor approach, anion anharmonic vibrations such in yttria-stabilized zirconia are proven to exist in LaWO for the first time.