Pyrochlores based on the general composition CaLnZrNbO7 (where Ln = La, Nd, Sm, Gd and Ho) have been prepared, and irradiated through the crystalline-amorphous transition, with 1 MeV Kr ions at the IVEM-TANDEM user facility. The obtained critical temperatures show a decrease from La to Gd (∼680 K to ∼230 K), with Ho being resistant to amorphisation at 50K. The results suggest that the amorphisation cross section for these materials is directly related to the Ln component.

Ceramics based on the general compositions CaLnXNbO7 (where Ln = La, Nd and Sm, and X=Zr and Sn) have been prepared, and irradiated with 1 MeV Kr ions at the IVEM-TANDEM user facility. The radiation tolerance of these materials has been found to be less than Zr and Hf equivalents. The results also suggest that the amorphisation cross section for these materials is related to the Ln component, and is similar to those observed for Zr and Hf equivalents.

Thin crystals of La2O3, La2/3TiO3, La2TiO5, and La2Ti2O7 have been irradiated in situ using 1 MeV Kr2+ ions in the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), at the Argonne National Laboratory (ANL). We observed that La2O3 remained crystalline to a fluence greater than 3.1 × 1016 ions cm-2 at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (Tc) of 840 K for La2Ti2O7, 865 K for La2/3TiO3, and 1027 K for La2TiO5. The Tc values observed in this study, together with previous data for TiO2, are discussed with reference to the phase diagrams for La2O3-TiO2 systems and the different local environments within the crystal structures. Results suggest an observable inverse correlation between Tc and melting temperature (Tm) in the two systems.

Radiation damage effects in ceramics, e.g., nuclear waste forms, transmutation targets, and inert matrix fuels, may have important implications for the physical and chemical stability of these materials as the cumulative radiation dose increases over time. A key aspect of scientific research in this area is the ability to understand the fundamental damage mechanisms through the combination of experimental and atomistic modelling techniques. In this paper, we review some of the lessons learned from the significant body of data now available for pyrochlore-defect fluorite based materials, followed by an illustration of the advantages of working on simple compounds with well established interatomic potentials. We conclude the paper with a description of radiation damage processes in the LaxSr1-1.5xTiO3 defect perovskites, a system that includes phase transformations, short-range order effects, and complex defect behavior.

Radiation damage and the effect on physical and chemical properties is an important component in the prediction of the long-term stability of waste form materials. As part of the ongoing goal of increasing the accuracy of long-term predictions of radiation damage, two types of material, based on proposed materials with a waste form application have been irradiated. Results have shown that Y2TiO5 (Y2.67Ti1.33O6.67), and Yb2TiO5 (Yb2.67Ti1.33O6.67), both of which are non-stoichiometric, disordered pyrochlore-based compounds, behave significantly different to the stoichiometric, ordered pyrochlore equivalent. For example the critical temperature, the temperature above which materials remain crystalline during irradiation, is found to decrease from the ordered equivalents, e.g. Y2Ti2O7. A second material based on La2TiO5 has been found to behave differently to both La2/3TiO3 and La2Ti2O7, with a change in Tc of ∼ 200 K.

Garnets, A3B2C3O12, are considered to be potential host phases for the immobilization of high-level nuclear waste as they can accommodate a number of elements of interest, including Zr, Ti and Fe. The naturally occurring garnet, kimzeyite, Ca3(Zr,Ti)2(Si,Al,Fe)3O12, can contain ˜30wt% Zr. An understanding of the radiation tolerance of these materials is crucial to their potential use in nuclear waste immobilization. In this study two synthetic analogues of kimzeyite of composition Ca3Zr2FeAlSiO12 and Ca3Hf2FeAlSiO12 were monitored in situ during irradiation with 1.0 MeV Kr ions using the intermediate voltage electron microscope-Tandem User Facility (IVEM) at Argonne National Laboratory. The structure of these materials was previously determined by neutron diffraction and 57Fe Mössbauer spectroscopy. Ca3Zr2FeAlSiO12 and Ca3Hf2FeAlSiO12 have very similar structural properties with cubic Ia3d symmetry, the only significant difference being the presence of Zr and Hf, respectively, on the 6 coordinated B sites.

Bulk samples of six Ln2TiO5 compounds with Ln = La, Pr, Nd, Eu, Gd and Tb were prepared and characterised. Most of the samples have a phase purity of ∼95% (based on BEI and EDS) with the predominant secondary phase primarily being Ln2Ti2O7. Using XRD, TEM selected area diffraction and high resolution imaging techniques, we have confirmed the results of previous studies which showed that at room temperature Pr2TiO5, Nd2TiO5, Eu2TiO5 and Tb2TiO5 have orthorhombic structures with Pnma symmetry. The structure of Tb2TiO5 was further monitored as a function of temperature. The relevance of Ln2TiO5 compounds to advanced nuclear fuel cycles is discussed.

Thin crystals of rutile, brookite, and anatase were irradiated in-situ with 1.0 MeV Kr using the IVEM-TANDEM facility. Synthetic rutile and cassisterite (SnO2, rutile structure) remained crystalline up to 5 × 1015 ion cm-2 at 50 K. Natural brookite and anatase with low impurity levels became amorphous at 8.1 ± 1.8 × 1014 and 2.3 ± 0.2 × 1014 ions cm-2, respectively, at 50 K. Irradiation at higher temperature revealed Tc = 170 K for brookite and 242 K for anatase. Natural rutile with about 2 wt% impurities became amorphous at 9.4 ± 1.8 × 1014 ions cm-2 at 50 K and has a Tc = 207 K. The available data reveal both a structural effect in the polymorphs with low levels of chemical impurities and a chemical effect in natural rutile specimens containing up to about 1.7 wt% impurities.

Selected area electron diffraction patterns are routinely used to determine the effects of irradiation damage in nuclear materials. Using zone axis orientations, the intensities of Bragg beams change from a dynamical to kinematic-like state due to the presence of amorphous domains in the material. Such changes in beam intensities, together with the increased diffuse scattering from the increasing amorphous fraction, present a major obstacle to the determination of cation or anion disorder in the crystalline fraction.

Synthetic pyrochlore samples Y2Ti2-xSnxO7 (x=0.4, 0.8, 1.2, 1.6), Nd2Zr2O7, Nd2Zr1.2Ti0.8O7, and La1.6Y0.4Hf2O7, were irradiated in-situ using the IVEM-TANDEM microscope facility at the Argonne National Laboratory. The critical temperatures for amorphisation have revealed a dramatic increase in tolerance with increasing Sn content for the Y2Ti2-xSnxO7 series. This change has also found to be linear with increasing Sn content. Nd2Zr1.2Ti0.8O7 and La1.6Y0.4Hf2O7 were both found to amorphise, while Nd2Zr2O7 was found to be stable to high doses (2.5×10^15 ions cm-2). The observed results are presented with respect to previously published results for irradiation stability predictions and structural disorder.

Two systems have been studied La2-xYxZr2O7 and La2-xYxHf2O7, as part of an on-going study of radiation tolerance in nuclear waste forms and related oxide materials. The structural effects of increasing Y content in La based zirconate and hafnate pyrochlores have been studied with neutron diffraction and electron microscopy. Results have shown a difference in structural stability for both the pyrochlore and fluorite phases within each system, including the presence of two-phase regions in both systems. In the zirconate, the two-phase region lies in the range x = 0.9-1.6. This is shifted to higher Y content in the hafnate system and lies in the range of x = 1.5 to approximately 1.8-1.9. In addition to the differences in phase stability, electron diffraction, predominantly down the [110] zone axis, has shown evidence for ordering in the form of structured diffuse scattering within the fluorite phases.

Zirconolite (nominally CaZrTi2O7) is a constituent phase of potential waste forms for the safe immobilisation of actinide wastes. Structural studies of such materials provide important information about cation ordering, lattice parameters, and strain effects, and provide input into the modelling of alpha decay damage and the development of future wasteform designs. A suite of zirconolites based on the replacement of Ti with Nb and Fe has been studied using high resolution neutron diffraction and resonant X-ray diffraction to determine the degree of disorder across the available cation sites. Resonant X-ray diffraction is a unique method which allows the location of certain cations to be determined accurately by taking advantage of the change in scattering power close to an absorption edge (e.g., Nb-K and Zr-K). Using standard X-ray diffraction alone this is not possible and there is little scattering difference between Nb and Zr.

Raman spectroscopy and measured lattice parameters have shown that the exchange of Ti with Nb and Fe has a non-linear effect on the unit cell dimensions and Raman peak positions while retaining the 2M polytype. Mössbauer spectroscopy has shown that the Fe preferentially fills the Ti split (C2) site. The results from this study provide a more complete picture of the cation order-disorder problem and are generally consistent with the behaviour of lattice parameters across the series.

High-throughput synthesis of the ferroelectric solid solution Pb(Zr1−xTix)O3 (PZT) on single Pt/Ti/SiO2/Si substrates was demonstrated using a modified molecular beam epitaxy (MBE) system. The PZT films exhibited a phase transition from rhombohehdral (R) to tetragonal (T) symmetry as a function of Zr:Ti ratio, across the substrate diagonal. This was consistent with the presence of a morphotropic phase boundary (MPB) at a Zr:Ti ratio of 0.64:0.36, different from the value of 0.53:0.47 observed for bulk ceramics. All points on the films exhibited ferroelectric hysteresis loops. The results demonstrate the feasibility of high-throughput MBE for deposition of complex ferroelectric oxides, and pave the way for further materials discovery, in particular Pb-free piezoceramics.

The resistance of Ln2Ti2O7 (Ln=lanthanide) compounds to radiation damage is an important topic in the understanding and development of new materials by which radioactive nuclear waste can safely be immobilised. A model has been developed, from previously published density functional theory and molecular orbital theory simulations of the band structure for Ln2Ti2O7 materials. This model provides a chemical interpretation of radiation stability.