Study on the Zirconolite Solidification of Simulated Np/Pu Radioactive Incineration Ash

High level waste is nuclear energy generated during the application process ,which is the greatest and the most difficult to management the waste. Proper treatment and disposal of it has already become a worldwide problem, and has become one of the key factors of restricting nuclear energy for sustainable development. Zirconolite (CaZrTi2O7) is one of the most stable mineral on the Earth and actinide major parasitic phase, therefore, it is widely used to solidify actinides separated from high level radioactive waste. In this paper, the zirconolite solid solution was synthesized by high temperature solid-stated method using a particular composition of simulated Np/Pu radioactive incineration ash (SRIA). The phase composition has been investigated by X-ray diffraction (XRD), the calcined temperature gained according to thermogravimetry scanning calorimeter (TG-DSC) analysis. Anti-leaching performance has also been researched with MCC-1 method. Results show that CaZrTi2O7 can load 40% SRIA, the accumulated leaching fraction of Ca is only about 10-4 cm in 28 days at 90 ℃, the concentrations of Zr , Ti and other noble metal ions were all less than detectability of ICP-MS, the leaching rate , normalization leaching rate, and accumulated leaching fraction of all Zr , Ti and other noble ions were 10-8 cm/d, 10-8 g/cm2·d and 10-7 cm, the results indicate that the zirconolite solidification has excellent chemical durability.

Solid-state reaction synthesis and chemical stability studies in Nd-doped zirconolite-rich ceramics

In this study, Nd-bearing zirconolite-rich ceramics were prepared by solid-state reaction process using CaF2,ZrO2, Ti,TiO2, Fe2 O3 and Nd2O3 as the raw materials. Neodymium was used as trivalent actinide surrogate and designed to substitute the Ca and Zr sites of zirconolite with general stoichiometry of Ca1-xZr1-xNd2 xTi2O7（0≤x≤0.3）. Density of Fe-Nd-O sample reaches a maximum value of 4.13 g/cm^2 after being sintered at 1325 ℃ for 42 h. Three major phases, namely zirconolite, perovskite and pseudobrookite, are observed in all these samples. The EDX result shows that Nd2O3 can be successfully incorporated into the lattice structure of the prepared zirconolite-rich minerals and replace the Ca sites of zirconolite and perovskite with Fe3＋ as the charge-compensating ion. Furthermore, the thermal conductivities are all in the range of 1.51-1.67 W/（m·K）. The normalized elemental leaching rates of Ca and Nd in the Fe-Nd-0.2 sample keep in low values of 6.20 × 10^-2 and 4.86 × 10^-4 g/（m^2·d） after 42 d.

Combustion synthesis and characterizations of Sm2O3 doped zirconolite-rich waste forms with CuO as oxidant

Zirconolite is one of the most important matrix materials for nuclear waste immobilization.In this study,Sm was employed as the surrogate of trivalent actinides.Sm-doped zirconolite-rich waste forms were readily prepared by combustion synthesis(CS)using CuO as the oxidant.Two different schemes with or without Al2O3 as the charge compensator were carried out simultaneously.The results demonstrate that Al2O3 addition results in complex phase composition.On the other hand,the samples without Al2O3 addition show desirable products of zirconolite and pyrochlore.The EDX analysis shows that Sm is concurrently incorporated into the Ca and Zr sites of zirconolite,which transforms to pyrochlore structure with high Sm2O3 contents.The aqueous durability of representative Sm-doped sample(Sm-0.6)was investigated.The 42 days normalized leaching rate of Sm is as low as 6.41×10-7 g/(m2 d),which exhibits high durability of Sm-doped sample.

Combustion synthesis of Hf-doped zirconolite-rich composite waste forms and the aqueous durability

Zirconolite is recognized as one of the most durable waste matrices for the disposal of high-level radioactive wastes(HLWs).In this study,HfO2 was employed as the surrogate of tetravalent actinides.Hf-bearing zirconolite-based composite waste forms(CaZr1–xHfxTi2O7)were rapidly prepared by combustion synthesis(CS)using CuO as the oxidant,where quick pressing(QP)was introduced to obtain densified samples.Similar as solid state reaction process,the Zr site of zirconolite can be totally occupied by Hf(x=1.0)under the CS reaction.The original 2M zirconolite structure was maintained and a small amount of perovskite impurity phase was generated in the final products.The aqueous durability of representative sample(Cu-Hf-0.6)was tested,where the 42-day normalized leaching rates(LRi)of Ca,Cu,and Hf are 0.25,3.10×10–2,and 1.11×10–8 g·m–2·d–1.

SIMS Pb/Pb dating of Zr-rich minerals in lunar meteorites Miller Range 05035 and LaPaz Icefield 02224:Implications for the petrogenesis of mare basalt

Miller Range (MIL) 05035 and LaPaz Icefield (LAP) 02224 are unbrecciated lunar basalt meteorites. In this report, we studied their petrography and mineralogy and made in situ uranogenic Pb/Pb dating of Zr-rich minerals. Petrography and mineralogy of these two lunar meteorites are consistent with previous investigations. The zirconolite Pb/Pb age of MIL 05035 is 3851±8 Ma (2σ), in excellent agreement with previous reports. This age suggests that MIL 05035 could be paired with Asuka 881757, a low-Ti mare basalt meteorite. The magmatic event related to MIL 05035 was probably due to the late heavy impact bom- bardment on the moon around 3.9 Ga. One baddeleyite grain in LAP 02224 shows a large variation of Pb/Pb age, from 3109±29 to 3547±21 Ma (2σ), much older than the whole-rock age of the same meteorite (~3.02±0.03 Ga). The other baddeleyite grain in LAP 02224 has an age of 3005±17 Ma (2σ). The result indicates that the minimum crystallization age of LAP 02224 is ~3.55 Ga and the younger ages could reflect late thermal disturbance on U-Pb system.

Phase relations,microstructure,and valence transition studies on CaZr1-xCexTi2O7(0.0≤x≤1.0)system

In this study, Ce-doped zirconolite was synthesized through high-temperature solid-state reaction at 1250 ℃ in air for 96 h. The crystal phase, microstructure and valence transition were studied by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and X-ray photoelectron spectroscopy （XPS）. Phase relations of CaZrl xCexTi207 systems were determined by XRD analyses and Rietveld refinements. Four different phases are identified, namely zirconolite, perovskite, pyrochlore, and cerianite. The phase transformation （2M-zirconolite → 4M-zirconolite →Ce-pyrochlore） is caused by cations rearrangement as cerium content increases. The solubility limit of cerium ions in CaZrl .xCexTi207 system is estimated to be approximately 0.80. Under sintering air atmosphere, partial reduction of Ce^4＋ in Ce^3＋ is detected in Ce 3d XPS soectra, and the ratio of Ce^3＋ and Ce^4＋ significantly decreases as cerium content increases.