Synthesis and feasibility studies of doping U at Ti site of Y₂Ti₂O₇ as a radioactive waste immobilization matrix

In pursuit of clean and green nuclear energy one of the major challenges is to effectively immobilize the nuclear waste. In this context A(2)B(2)O(7) type pyrochlore owing to its structural flexibility, ability to accommodate ions at both A/B-sites and high radiation tolerance has demonstrated excellent capability to store highly radioactive actinide ions. To fill the major gap area of actinide doping at the B site we have taken up the challenge of doping uranium ions at the Ti site of Y2Ti2O7 type pyrochlore. An yttria titanate (Y2Ti2-xUxO7; x = 0.05, 0.075, 0.1, 0.2, and 0.3) based matrix with uranium doped at the Ti site was synthesized using a simple gel combustion route under an air atmosphere. Rietveld refined X-ray diffraction (XRD) demonstrated that Y2Ti2O7 can accommodate U up to 5 mol% in the Ti site without any phase separation, which was further confirmed using Raman spectroscopy. Y2Ti2O7 based matrices are found to be radiation stable up to 1000 kGy and at the same time they are moderately thermally stable and on a par with the values reported for pyrochlores. Uranium in Y2Ti2O7 stabilizes in +6 oxidation state in the form of uranyl ion distributed near and far off from titanium vacancies with distinct excited state lifetime. This work could provide a smart and strategic way for selecting a suitable advanced ceramic matrix for immobilization of high level waste with additional and important information on solubility limit, actinide speciation, radiation/thermal stability, actinide concentration, etc.