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In the search for novel ceramics for use within nuclear fuel–related applications and nuclear waste-form matrices, a major focus has been on the development of radiation-tolerant materials. Of particular interest in this field have been numerous compounds with either pyrochlore or the related fluorite-type structures. In this study, we look to expand the family of compounds with defect fluorite–type structure. We have fabricated three new compounds; Yb2Sn1.125O5.25, Yb2Sn1.25O5.5, and Yb2Sn1.375O5.75. The compound Yb2Sn1.125O5.25 was determined, via x-ray diffraction, to have the long-range defect fluorite structure, Fm-3 m symmetry, with cell parameter a = 5.17233(1). Further to this, Sm2ZrO5 and Yb2TiO5 compounds were also fabricated and crystal structures characterised. The use of transmission electron microscopy has revealed a much more complex crystal structure than that of the relatively high symmetry fluorite, with the presence of structural modulations being detected. The ion-irradiation response of these compounds was tested via bulk specimen irradiation using 15-MeV gold ions with grazing incidence x-ray diffraction characterisation. The results show that both Sm2ZrO5 and Yb2Sn1.25O5.5 are highly tolerant to ion-irradiation exposure whilst Yb2TiO5 is susceptible to amorphisation. [ABSTRACT FROM AUTHOR]

As part of a broader study of ceramic nuclear waste‐forms, four different lanthanide titanates were fabricated; La0.1Sm0.1Gd0.1Tb0.1Dy0.3Ho0.1Er0.2YbTiO5, Sm0.3Gd0.3Dy0.3Yb1.1TiO5, Sm0.1Gd0.4Dy0.4Yb1.1TiO5, and Sm0.2Gd0.2Dy0.2Yb1.4TiO5. The aim was to produce single‐phase novel materials with cubic symmetry, capable of incorporating a wide variety of cations and with acceptable radiation tolerance. The chemistry flexibility and radiation tolerance are some of the major desirable properties for nuclear waste‐form materials. By using multiple lanthanides the average lanthanide radius can be controlled and consequently the structure, along with properties such as radiation tolerance. The radiation tolerance was assessed using in situ 1 MeV krypton irradiation and transmission electron microscopy characterization. Those materials for which cubic symmetry was achieved displayed better radiation tolerance; a greater critical fluence of ions (Fc) was required for the crystalline to amorphous transition, and a lower temperature was required to maintain crystallinity (Tc) during irradiation. [ABSTRACT FROM AUTHOR]

We refine the crystal structures of a systematic series of compounds with the general composition Ho (x) Yb (2-x) TiO 5 (x = 2, 1.6, 1.2, 1, 0.8, 0.4, 0) and Er 2 TiO 5 and find a transition from defect-pyrochlore to defect-fluorite structure with increasing ytterbium content, decreasing lanthanide radius. Short-range structure modulations consisting of pyrochlore-like nano-domains are systematically characterised using transmission electron microscopy. We test the Kr 2+ 1 MeV ion-irradiation response of Ho 2 TiO 5 , HoYbTiO 5 , Yb 2 TiO 5 , and Er 2 TiO 5 , via the crystalline to amorphous transition observed by using the in-situ TEM approach. The critical dose of amorphisation, D c , was measured at various temperatures and used to calculate the critical temperature for maintaining crystallinity, T c . A trend of lower T c values with decreasing lanthanide radius is found. We describe a new approach for determining T c values using cross-sectional TEM analysis of ex-situ bulk irradiated, 1 MeV Se + , samples; Ho 2 TiO 5 , HoYbTiO 5 and Yb 2 TiO 5 . The results of D c and T c values using the two approaches vary; however the trends across the sample system remain the same. [ABSTRACT FROM AUTHOR]

Pyrochlore Nd 2 Zr 2 O 7 nanoparticles were prepared by complex-precipitation in aqueous media, followed by calcination in MgO matrix and subsequent dissolution processing. A suite of characterization techniques, including X-ray diffraction, Raman, TEM, SEM, dynamic light scattering, and nitrogen sorption, was employed to investigate the structure and particle size of the synthesized nano materials. Results show that calcination at 1200 °C for 20 h forms Nd 2 Zr 2 O 7 with pyrochlore structure. The matrix phase (MgO) had no effect on the formation of pyrochlore phase. The MgO phase was readily removed by dissolution at 0.5 M HNO 3 aqueous solution; and the remaining pyrochlore Nd 2 Zr 2 O 7 nanoparticles had a diameter of approximately 200 nm estimated by TEM and approximately 550 nm determined by light scattering due to slight aggregation. The bulk density of the pelletized powder reached approximately 99% of theoretical value, after uniaxial pressing at 2.0–2.5 MPa and sintering at 1400 °C for 48 h. [ABSTRACT FROM AUTHOR]

A novel soft chemistry route was developed to synthesize Y 2 Hf x Ti 2− x O 7 (0≤ x ≤2.0) oxide solid solution. An aqueous solution containing reactants was produced to ensure the combustion reaction taking place at the molecular level. A suite of characterization techniques, including X-ray diffraction, Raman, transmission electron spectroscopy, as well as X-ray absorption near edge structure (XANES), is employed to investigate the structural and phase changes of the series. Both X-ray and electron diffraction patterns show that the Y 2 Hf x Ti 2− x O 7 system undergoes a clear composition-induced phase transition from ordered pyrochlore to disordered defect-fluorite at x ~1.5. On the other hand, Raman and XANES spectra reveal a gradual evolution of the local structure with the substitution of Hf for Ti. [ABSTRACT FROM AUTHOR]

The incorporation of uranium into gadolinium zirconate (Gd2Zr2O7) is investigated by synchrotron X-ray powder diffraction and X-ray absorption near-edge structure (XANES) spectroscopy. The results suggest that the uranium cation is largely located on the pyrochlore B-site instead of the targeted A-site. Cation disorder in Gd2Zr2O7 and U-doped Gd2Zr2O7 is investigated by positron annihilation lifetime spectroscopy (PALS) which demonstrates the absence of cation vacancies in these systems. This work provides direct evidence for cation antisite (A- and B-site mixing) disorder in U-doped and off-stoichiometric Gd2Zr2O7 pyrochlore. [ABSTRACT FROM AUTHOR]