Aqueous Synthesis of Technetium-Doped Titanium Dioxide by Direct Oxidation of Titanium Powder, a Precursor for Ceramic Nuclear Waste Forms

摘要

Technetium-99 (Tc) is a problematic fission product that complicates the long-term disposal of nuclear waste due to its long half-life, high fission yield, and the environmental mobility of pertechnetate, its stable form in aerobic environments. One approach to preventing Tc contamination is through incorporation into durable waste forms based on weathering resistant minerals such as rutile (titanium dioxide). Here, the incorporation of technetium into titanium dioxide by means of simple, aqueous chemistry - direct oxidation of titanium powder in the presence of ammonium fluoride - is achieved. X-ray absorption fine structure spectroscopy and diffuse reflectance spectroscopy indicate that Tc(W) replaces Ti(IV) within the structure. Rather than being incorporated as isolated Tc(IV) ions, Tc is present as pairs of edge-sharing Tc(IV) octahedra similar to molecular Tc(IV) complexes such as [(H(2)EDTA)Tc-IV (mu-O)(2). Technetium-doped TiO2 was suspended in deionized water under aerobic conditions, and the Tc leached under these conditions was followed for 8 months. The normalized release rate of Tc (LRTC) from the TiO2 particles is low (3 X 10(-6) g m(-2) d(-1)), which illustrates the potential utility of TiO2 as waste form. However, the small size of the as-prepared TiO2 nanoparticles results in an estimated retention of Tc of 10(4) years, which is only a fraction of the half-life of Tc (2.1 X 10(5) years).