A further investigation of the complex M3 murataite structure using Hf substitution and STEM-EELS techniques

Abstract

Keywords: M3-type murataite; fluorite-type supercell structure; powder X-ray diffraction (PXRD); high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM); scanning transmission electron microscopy electron energy-loss spectroscopy (STEM-EELS).Supporting information: this article has supporting information at journals.iucr.org/bMany members of the complex crystalline fluorite supercell structures (e.g. zirconolite, pyrochlore and murataite polytypes) have been considered/studied for possible long-term radioactive-waste immobilization. The eight-coordinated sites in these crystals are of particular importance because they are preferred for the accommodation of trivalent rare earths and actinides present in radioactive waste from fuel element processing. The fluorite-type supercell structures include the murataites, M3, M5, M7, M8, having those numbers of repeating fluorite sub-cell units. One simple technique, as shown here, namely the substitution of Hf into the Zr site, is very helpful for structural analysis in these very complex cases in order to further illuminate the site preference of the Zr ion. Three M3 murataite samples, Ca-Mn-Ti-Zr-Al-Fe-O (regular M3), Ca-Ti-Zr-Al-Fe-O (Mn-free M3) and Ca-Mn-Ti-Hf-Al-Fe-O (Hf-substituted M3) are investigated and, through techniques described for larger cells, show that the Zr is very likely not to be hosted in the [6] Ti site in the M3 murataite structure, as suggested by Pakhomova et al. [(2013), Z. Kristallogr. Cryst. Mater. 228, 151-156], but more likely replaces the [8] Ca1 site and less likely the [8] Ca2 site. This adjusted site preference for each cation from the powder X-ray diffraction (PXRD) and scanning transmission electron microscopy electron energy-loss spectroscopy (STEM-EELS) methods, agrees well with the high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image. research papers Acta Cryst. (2019). B75, 442-448 Maki and Morgan Further investigation of M3 murataite structure 447

Thermodynamics of Fluorite-Structured Oxides Relevant to Nuclear Energy: A Review

“…Another notable fluorite derivative is the murataite structure (Figure b). It has been thoroughly studied by various groups − and proposed as a possible waste form. Atomic positions of this structure conform to the space group F m and a general formula of M 23 O 43 .…”