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.

A series of uranium-containing gadolinium zirconate samples have been fabricated at 1723 K in air. X-ray diffraction and Raman spectroscopy have confirmed pyrochlore or defect fluorite structures, while diffuse reflectance, X-ray absorption near edge structure and X-ray photoelectron spectroscopies indicate a predominantly U6+ oxidation state, even when Ca2+ was added to charge balance for U4+. The results demonstrate the potential of gadolinium zirconates as host materials for actinides.

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.

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.

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.

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.

We have characterized thermally annealed perovskite (CaTiO3) surfaces, both before and after aqueous dissolution testing, using scanning electron microscopy, cross-sectional transmission electron microscopy, x-ray photoelectron spectroscopy, and atomic force microscopy. It was shown that mechanical damage caused by polishing was essentially removed at the CaTiO3 surface by subsequent annealing; such annealed samples were used to study the intrinsic dissolution behavior of perovskite in deionized water at RT, 90 °C, and 150 °C. Our results indicate that, although mechanical damage caused higher Ca release initially, it did not affect the long-term Ca dissolution rate. However, the removal of surface damage by annealing did lead to the subsequent spatial ordering of the alteration product, which was identified as anatase (TiO2) by both x-ray and electron diffraction, on CaTiO3 surfaces after dissolution testing at150 °C. The effect of Ca2+ in the leachant on the dissolution reaction of perovskite at 150 °C was also investigated, and the results suggest that under repository conditions, the release of Ca from perovskite is likely to be significantly slower if Ca2+ is present in ground water.

Extended abstract of a paper presented at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, August 1–5, 2004.

Nd-bearing zirconolite was leached at 90°C for 6 months in 0.001M citric acid, and also in deionised water, to determine the effect of organic-bearing solutions on durability. The pH of the citric acid solution was adjusted to 5 using KOH, approximating that of the water in the parallel tests, to avoid the influence of pH on chemical durability of the zirconolite.

Releases were incongruent in the tests carried out in water. Release rates of Ti, Zr and Nd were comparatively very low (commonly too low to be measured) over the first 80 days of leaching. Rates for Ca and Al were 2 to 4 orders of magnitude higher than Ti, Zr and Nd over this same period. At about 80 days, there was an anomalous decrease in pH from 6 to 4 which enhanced release rates of Ti and Nd in particular. There was development of titania crystals, and the suggestion of hydrolysed titania, on the surface after 6 months. Thermodynamic equilibrium between the leachates and hydrolysed species on the surface of the zirconolite may be the key to apparent cessation of alteration, at least during thefirst 80 days of leaching.

By contrast, zirconolite leached in 0.001M citric acid maintained release rates of Ti, Zr and Nd 2 to 4 orders of magnitude greater than those in water for the first 80 days, values sustained, within an order of magnitude, for the remainder of the leach tests. Releases were congruent. The surface of the zirconolite showed no signs of secondary phase development. This suggests complexation by citrate ions prevented control by hydrolysed species on zirconolite solubility.

Static dissolution tests on Nd-bearing zirconolite were conducted in deionized water at 150°C for up to 6 months. Surfaces, both before and after aqueous dissolutions, were examined using X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Individual submicron-sized crystals wereobserved only on some zirconolite grains after hydrothermal treatment for one week, and were identified as brookite (possibly plus anatase) by Transmission Electron Microscopy (TEM). The number of secondary crystals present on the zirconolite surface was, however, reduced significantly after 6 months of durability testing. The results of electron microscopy studies are consistent with those obtained from XPS in that the average Ca and Ti concentrations of the top surface layer (< 5 nm) decreased slightly with respect to Zr, while the average Al concentration increased after durability testing.

Nickel is a commonly used wetting agent in alloyed Au–Ge ohmic contacts to n-GaAs, resulting in uniformity improvements to the morphology and contact resistance. In order to study the role of Ni in Ni–Ge–Au alloys, we have fabricated samples with varying Ni content and characterized them using electron microbeam techniques. Our data indicate the amount of Ni in the alloy affects the microstructure and composition, the morphology of the metal/GaAs interface, and the amount of GaAs consumed during the alloy reaction. Also, the dopant distribution into the GaAs is heterogeneous depending on the alloy microstructure.

Eight perovskites of different compositions and pre-existing vacancy contents were irradiated with 1.5 MeV Kr+ ions using the HVEM-Tandem User Facility at Argonne National Laboratory. The critical dose of 1.5 MeV Kr+ ions for amorphisation (Dc) of NaNbO3, SrTiO3 and two natural perovskites varies with composition and may decrease with Na content. The D,c values of 5 members of the solid solution series from SrTiO3 to La0.67TiO3 do not exhibit a simple relationship with vacancy content: In particular, Dc(Sr0 7La0.2TiO3) is extraordinarily high (>170 × 1014 ions cm−2) compared to those of the other (Sr, La)-perovskites in the series, which have Dc values between 2.4 and 11 × 1014 ions cm−2.

Eight perovskites of different compositions and pre-existing vacancy contents were irradiated with 1.5 MeV Kr+ ions using the HVEM-Tandem User Facility at Argonne National Laboratory. The critical dose of 1.5 MeV Kr+ ions for amorphisation (Dc) of NaNbO3, SrTiO3 and two natural perovskites varies with composition and may decrease with Na content. The Dc values of 5 members of the solid solution series from SrTiO3 to La0.67TiO3 do not exhibit a simple relationship with vacancy content: In particular, Dc(Sr0.7La0.2TiO3) is extraordinarily high (>170 × 1014 ions cm−2) compared to those of the other (Sr, La)-perovskites in the series, which have Dc, values between 2.4 and 11×1014 ions cm−2.

Dose-age relationships have been determined by analytical and transmission electron microscopy (AEM and TEM) for the onset dose and critical amorphization dose of a suite of natural zirconolites. Together with a preliminary investigation of the thermal histories of the zirconolite-bearing rocks, the results indicate that valid estimates of D0 (intercept dose at t = 0) and K (annealing rate constant) are obtained and that the host rocks experienced temperatures on the order of 100-200 °C averaged over time. The natural samples are therefore best suited as radiation damage analogues for waste forms stored under deep borehole conditions where temperatures of 100-450 °C are expected. Our results indicate that the critical amorphization (or saturation) dose of zirconolite will increase by a factor of approximately 2 or more as a result of storage at elevated temperature. The effect of long-term annealing on the critical amorphization dose is only important for times in excess of 107-108 years due to the low annealing rate constant of 10−9/yr.

Synroc is a candidate waste form for the immobilisation of high level radioactive waste (HLW)[1]. It is polyphase titanate ceramic principally comprised of zirconolite, hollandite perovskite and rutile (nominally CaZrTi2O7, (BaxCsy)[(Ti3+, Al)2x+y(Ti4+)8−2x−y]O16), CaTiO3 and TiO2 respectively). Waste species substitute into the three former phases. In particular, actinides (ACTs) substitute onto the Ca and Zr sites in zirconolite and the Ca site in perovskite. Consequently over time, these phases will suffer alpha-recoil and alpha particle damage while hollandite and rutile will suffer alpha particle damage. The effect of radiation damage on the structure and consequently on the durability of Synroc's constituent phases is important to predictive modelling of Synroc's behaviour in the repository environment and risk assessment.

Synroc containing 20 wt% simulated high level waste (HLW) was subjected to two sets of leach tests at 150°C where the leachant was and was not replaced during the test (replacement and non-replacement testing). The leachant was a KH-phthalate buffered solution (pH 4.2). Samples were characterised before and after leach testing using SEM, AEM and SIMS. Elemental concentrations in leachates were measured using ICP-MS. In concert with the findings of i) a dissolution study of perovskite in a flowing leachant and ii) a previous Synroc dissolution study (wherein Synroc containing 10 wt% simulated HLW was subjected to periodic replacement, leach testing in deionised water at 150°C), the results of this study show that when the leachant replacement frequency is varied from 7 d to the duration of the test, there is no effect on leach rate or leaching mechanisms.

Synroc-C containing 10wt% simulated PW-4b-D HLW including 0.62 wt% 239Pu was subjected to MCC-1 type leach tests at 70°C in deionised water, silicate and carbonate leachates for 53 d and deionised water for 2472 d. The normalised total (i.e. unfiltered leachate + vessel wall) Pu leach rates in deionised water, silicate and carbonate leachates for periods up to 53 d were found to be of the order of 10-5, 10-4 and 10-4 g m-2 d-1 respectively. After 2472 d, the differential, normalised, Pu leach rate in deionised water dropped to ∼5 × 10-6 (total) and ∼5 × 10-8 (solution - after filtration through a 1000NMW filter) g m-2 d-1. SEM and AEM were used to characterise our starting material and investigate the secondary phases on the surfaces of leached Synroc-C discs. Calculated and measured normalised Pu leach rates are compared and the partitioning of Pu between zirconolite and perovskite is discussed.

Np-doped Synroc was subjected to modified MCC-1 leach tests in demineralised water at 70°C. Normalised total differential Np leach rates were about 10−4 g m−2 d−1 initially, decreased to about 10−5 g m−2 d−1 after 60 days and stayed approximately constant for periods totalling up to 2283 d. Scanning electron microscope (SEM) and analytical transmission electron microscope (AEM) examination of discs leached for periods totalling 56 d or longer showed that they were covered with crystalline anatase, brookite and ilmenite. The crystalline secondary phases initially nucleated in polishing scratches and on perovskite grains. However, after leaching for a total of 422 d most of the surface was covered. None of the secondary phases contained observable amounts of Np (< 0.2 wt%). These data are discussed in relation to previous work.