Local structure and phase composition of Neodymium-Zircon solid solution (NdxZr1-xSiO4-x/2)

To address the structural stability of host materials for immobilizing radioactive actinides in nuclear waste management applications, the present study is focused on the effect of various concentrations of Nd substitution on structural properties of synthetic zircon (NdxZr1-xSiO4-x/2). To achieve this, both pure and Nd-substituted zircon powders were prepared using the solid-state synthesis route. Rietveld refinement of X-ray Diffraction (XRD) data was employed to investigate the impact of various Nd substitutions on the phase composition of the zircon (ZrSiO4) crystal structure. This refined data was then utilized as input for the analysis of X-ray absorption spectroscopy (XAS) data. The results were further supported by observations from Raman spectroscopy, which indicated the substitution of Zr by Nd. In this work, we present an analysis of both regimes of XAS i.e. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Qualitative analysis of XANES data suggests that disorder in the samples increases with higher levels of Nd doping. Additionally, EXAFS analysis around Zr absorption edge also confirms an increased disorder in the system with higher Nd doping levels. However, EXAFS fitting around Nd edge indicated that disorder induced changes are more prominent and Nd–O bond is elongated as compared to Zr–O bond. This disorder in the system escalates at a Nd concentration of 10 atomic % (at %). An important finding of this study is the phase composition analysis using Rietveld refinement of XRD data. While XAS provided an insight into the changes in the local structure, the overall crystal structure remained unaffected even at a high doping of 10 at %. This work provides a comprehensive local structure analysis on this system. Such analysis would help in understanding the structural stability of the system and to determining the maximum loading of actinides in the host zircon for potential nuclear waste management applications. XRD and EXAFS data of representative sample with Nd doping in NdxZr1-xSiO4-x/2. [Display omitted] •Nd substitution effect on structural properties of NdxZr1-xSiO4-x/2 was studied.•Samples were synthesized using high temperature solid state synthesis route.•Phase composition of NdxZr1-xSiO4-x/2 was obtained from Rietveld refinement.•First ever report on local structural analysis by XANES and EXAFS.•These techniques revealed disorder in local structure at higher Nd doping.