Surface thermodynamics of yttrium titanate pyrochlore nanomaterials

Nanocrystalline pyrochlore materials have been investigated for their enhanced radiation tolerance as ceramic nuclear waste hosts. In this work, we study the thermodynamic driving force of nano-scale materials for radiation resistance. The size dependent thermodynamic properties of a series of Y2Ti2O7 nanoparticles were investigated. Samples were synthesized by a sol-gel method and characterized by synchrotron X-ray diffraction, BET analysis, and thermogravimetric analysis. The surface and interface enthalpies of Y2Ti2O7 were determined by high temperature oxide melt drop solution calorimetry to be 4.07 J m-2 and 3.04 J m-2, respectively. The experimentally obtained surface energy is in good agreement with computationally derived average surface energies for yttrium and other rare-earth titanate pyrochlores. Theoretical links between nanoparticle stability, surface energy, and radiation resistance of pyrochlore materials were then explored. Critical particle size can be determined with known surface energy. The surface enthalpy of yttrium titanate pyrochlores was determined to be 4.07 +/- 0.32 J m-2 by calorimetry, and the lower limit of critical particle size for this is around 5.0 nm.