Alkali rare-earth double phosphates have been studied for use as long-wavelength scintillators for gamma-ray detection using Si photodiodes. These compounds exhibit layered crystal structures, built from roughly hexagonal atomic layers in the sequence lanthanide, phosphate-alkali, alkali, alkali-phosphate. Details of the crystal symmetry depend on the relative sizes of the rare-earth and alkali metal ions. Single-crystal X-ray diffraction (SXRD) has been used to study these structures at room temperature for K3RE(PO4) 2 (where RE = Lu-Ce, Y, and Sc). The compound K3Lu(PO 4)2 crystallizes with a hexagonal unit cell, space group P-3. The Lu ion is six-coordinated to the oxygen atoms of the phosphate groups. Two lower-temperature phases of K3Lu(PO4) 2 were observed and characterized. The lower-temperature transition results in an increase in coordination of the Lu ion to seven fold. This new structure is isostructural with the room-temperature form of K3Yb(PO 4)2. High-temperature powder neutron diffraction and high-temperature powder XRD have revealed a large thermal expansion anisotropy for K3Lu(PO4)2. The K3RE(PO 4)2 formation enthalpies were determined using high-temperature oxide-melt solution calorimetry. The formation enthalpy from oxides becomes more exothermic with increasing rare-earth radius.; Rare-earth titanates, RE2Ti2O7 (where RE = a rare-earth), with the pyrochlore structure are currently being studied for use as potential nuclear, actinide-rich waste forms. Single-crystals were synthesized using a high-temperature flux technique and characterized using single-crystal X-ray diffraction. The cubic lattice parameters display an approximately linear correlation with the RE-site cation radius. The Sm and Eu titanates exhibit a covalency increase between the REO8 and TiO6 polyhedra resulting in a deviation from the increasing linear lattice parameter through the series. Gd2Ti2O7 exhibits the lowest 48f oxygen positional parameter, an effect that can be attributed to the 4f7 half-filled f-orbital sub-shell of Gd3+. The coefficient of thermal expansion (CTE) for the rare-earth titanate series is approximately linear, and it has a range of 10.1--11.2 x 10-6°C-1 . High-temperature oxide melt solution calorimetry was used to investigate the thermochemical properties of the series. The trend of the ionic radius of the RE3+ cation vs. DeltaHf-ox at 25°C is non-linear and approximately parallels the increasing "resistance" to ion-beam-induced amorphization as rRE/rTi decreases.
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