Synthesis and investigation of neptunium zirconium phosphate, a member of the NZP family: crystal structure, thermal behaviour and Mössbauer spectroscopy studies

Abstract

A new double neptunium zirconium phosphate of the type M_xZr₂(PO₄)₃ (M = Np), crystallizing in the structure type NaZr₂(PO₄)₃ (NZP, NASICON), was synthesized by solid state reactions at high temperatures and characterized by X-ray diffraction, infrared spectroscopy and Mössbauer spectroscopy. The Rietveld refinement of the XRD pattern together with the analysis of the IR spectra of the sample confirmed the space group Pc, the same as that for the lanthanide analogues Ln_0.33Zr₂(PO₄)₃. However, Mössbauer studies revealed the presence of neptunium in the two oxidation states +3 and +4, indicating a two-phase NZP system with different crystallographic environments of the neptunium atoms. The thermal behaviour of the sample was followed up to 1400 °C by thermogravimetric analysis.