Abstract:
In this paper, the mixed oxides of non-radioactive lanthanides were prepared in order to simulate the mixed oxides of minor actinides, as their chemical properties are similar. CeO
2-based mixed oxides Ce
1-xLn
xO
2-x/2 with Ln=Nd or Sm and
x∈[0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1] were prepared through calcination of the oxalate precursors (Ce
1-xLn
x)
2(C
2O
4)
3•10H
2O elaborated by coprecipitation method which led to a homogeneous distribution of cations in the mixed oxides. For the characterization, the infrared spectroscopy, Raman spectroscopy, X-ray diffraction and thermo-gravimetric analysis were applied for the oxalate precursors. Then investigations of the crystalline structure of these oxides Ce
1-xLn
xO
2-x/2 were carried out by X-ray diffraction. Typical fluorite
Fm-3m structure is observed for relatively low Ln
3+ contents (
x≤0.4 for Nd and
x≤0.3 for Sm), then a cubic
Ia-3 structure is observed (
x≥0.5 for Nd and
x≥0.4 for Sm). In addition, the Rietveld method was used for refining the unit cell parameters of Ce
1-xLn
xO
2-x/2. The variation of the unit cell parameters in different series is found to follow a quadratic relation as a result of combination between increasing cationic radius and decreasing O-O repulsion caused by oxygen vacancies.