Thermal expansion of the nuclear fuel-sodium reaction product Na3(U0.84(2),Na0.16(2))O4 - Structural mechanism and comparison with related sodium-metal ternary oxides

Na3.16(2)UV,VI0.84(2)O4 is obtained from the reaction of sodium with uranium dioxide under oxygen potential conditions typical of a sodium-cooled fast nuclear reactor. In the event of a breach of the steel cladding, it would be the dominant reaction product forming at the rim of the mixed (U,Pu)O2 fuel pellets. High-temperature X-ray diffraction measurements show that a distortion of the uranium environment in Na3.16(2)UV,VI0.84(2)O4 results in a strongly anisotropic thermal expansion. A comparison with several related sodium metallates Nan-2Mn+On-1 - including Na3SbO4 and Na3TaO4, whose crystal structures are reported for the first time - has allowed us to assess the role played in the lattice expansion by the Mn+ cation radius and the Na/M ratio. On this basis, the thermomechanical behavior of the title compound is discussed, along with those of several related double oxides of sodium and actinide elements, surrogate elements, or fission products.