RESUMEN
Chemical quality control of nuclear fuel, particularly the determination of Pu and U contents by chemical methods, results in analytical acidic aqueous waste solutions from which Pu and U must be recovered efficiently for the remediation of radioactive wastes. Reported methods involve several complicated steps requiring addition of chemical oxidants/reductants for valence adjustments and generation of secondary wastes, thereby making the recovery process cumbersome. Herein, we report a novel two-step electrochemical approach for Pu and U recovery from acidic aqueous waste solutions containing different metallic impurities (Fe, Cr, Mn, Cd, Al, Ni, Co, Zn, and Mg) by bulk electrolysis using a Pt gauze electrode. Pu and U are recovered from these waste solutions in a two-step process: (i) bulk electrolysis of the mixed solution at a constant potential of 0.1 V vs Ag/AgCl/3 M KCl that results in the reduction of PuO22+ to Pu3+ followed by the precipitation of Pu3+ as K2(K0.5Pu0.5)(SO4)2, which is then filtered and separated and (ii) the filtrate solution is again subjected to bulk electrolysis at a constant potential of -0.35 V vs Ag/AgCl/3 M KCl resulting in the reduction of UO22+ to U4+. The U4+ is then precipitated as K2(K0.67U0.33)(SO4)2, which is filtered and separated, leading to a Pu- and U-free aqueous acidic waste solutions. Biamperometry shows that 97.8% and 99.1% recovery of Pu and U, respectively, is possible, and emission spectrometry confirms the purity of K2(K0.5Pu0.5)(SO4)2 and K2(K0.67U0.33)(SO4)2. Because of its operational simplicity, potential for remote handling, and excellent extraction efficiency, the present methodology can easily replace traditional methods for the recovery of Pu and U from acidic aqueous waste solutions.
RESUMEN
In pursuit of clean and green nuclear energy one of the major challenges is to effectively immobilize the nuclear waste. In this context A2B2O7 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.
RESUMEN
Double perovskite antimonates of the type BaLaMSbO6 (M=Mg, Ca) were synthesized by a standard solid-state route. The compounds were characterized by X-ray crystallography and the structures were refined using Rietveld method. BaLaMgSbO6 and BaLaCaSbO6 crystallized in monoclinic space groups (I2/m) and (P21 /n), respectively. In both compounds, La occupied the A-site of perovskite, which is 12-coordinated as compared to Ba2 LaSbO6 where La ion shifts to the B-site octahedral coordination due to the larger size of Ba as compared with Mg and Ca. The samples were further characterized using FTIR and the frequency of the octahedral vibration is correlated to the electronegativity of the B-site ions. Photoluminescence study of the title compounds and Ba2 LaSbO6 was carried out upon doping with 2â atom% Eu3+ ion, which confirmed that Eu3+ occupies distorted 12-coordinated A-site in BaLaMSbO6 (M=Mg, Ca) and symmetrical octahedral B-site in Ba2 LaSbO6 . Furthermore, the emission spectrum corresponding to each Eu3+ ion at different crystal site was successfully isolated through a TRES study. This site selective occupancy of Eu3+ ion also has a direct impact on the light emission, which was found to change from orange to red in a dark room in the order Ba2 LaSbO6 : EuâBaLaCaSbO6 : EuâBaLaMgSbO6 : Eu. Such an outcome will have high impact in designing new commercial Eu3+ ion doped phosphor materials and tailoring of their optical properties.
RESUMEN
A one-third lanthanum deficiency was created in Ba2LaM5+O6 compounds (LaM compounds) to form Ba2La2/3M5+O5.5 compounds (La2/3M compounds) for M = Nb, Sb, and Bi. The compounds were prepared by a gel-combustion method using citric acid as a fuel. All the compounds were characterized by powder X-ray diffraction (XRD). The XRD analysis showed that the space group of the La2/3M compounds remains the same for the Bi and Sb samples when compared to the reported LaM compounds, except for the Nb sample. La2/3Nb and La2/3Sb adopt a rhombohedral structure with the space group R3[combining macron], whereas La2/3Bi adopts a monoclinic structure with the space group I2/m. As the positron annihilation spectroscopy (PALS) technique is sensitive to cation deficiency, it was used to detect the presence of cation vacancies in the samples, which are formed due to the decrease in the lanthanum concentration. The PALS analyses indicated that the absence of cation deficiency in the La2/3M compounds is similar to that observed in the LaM compound. Thus, the crystal structure of the La2/3M compound was modeled, such that the cation deficiency at the La site is filled by Ba2+ and M5+ ions, and the crystal structure formula is given as Ba2(La0.727Ba0.182M0.091)MO6. This model was confirmed by Rietveld refinement of the XRD data. The emission spectra of Eu3+ showed a strong dependence on its local site symmetry in the host material, in which it is being doped and this can be used as a spectroscopic probe for detecting any differences in the symmetry. Comparison of the local symmetry around La3+ cation was studied using photoluminescence (PL) by doping 2 atom% Eu3+ in LaM and La2/3M compounds. Infrared spectroscopy (IRS) analyses were also carried out for LaM and La2/3M compounds. There was complete agreement between the PL and IRS results and they were also in concordance with the predicted crystal structure model. Interestingly in these La2/3M compounds, the equilibrium structure prefers large Ba2+ ion to occupy the octahedral B-site rather than forming an octahedral vacancy at that site, making these perovskite compounds rare and novel in their class.
RESUMEN
The preparation and characterization of Sb-doped Bi(2)UO(6) solid solutions, in a limited composition range, is reported for the first time. The solid solutions were prepared by solid-state reactions of Bi(2)O(3), Sb(2)O(3) and U(3)O(8) in the required stoichiometry. The reaction products were characterized by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements at the Bi and U L(3) edges. The XRD patterns indicate the precipitation of additional phases in the samples when Sb doping exceeds 4 at%. The chemical shifts of the Bi absorption edges in the samples, determined from the XANES spectra, show a systematic variation only up to 4 at% of Sb doping and support the results of XRD measurements. These observations are further supported by the local structure parameters obtained by analysis of the EXAFS spectra. The local structure of U is found to remain unchanged upon Sb doping indicating that Sb(+3) ions replace Bi(+3) during the doping of Bi(2)UO(6) by Sb.
