Insight Into Disorder, Stress and Strain of Radiation Damaged Pyrochlores: A Possible Mechanism for the Appearance of Defect Fluorite.

We have examined the irradiation response of a titanate and zirconate pyrochlore-both of which are well studied in the literature individually-in an attempt to define the appearance of defect fluorite in zirconate pyrochlores. To our knowledge this study is unique in that it attempts to discover the mechanism of formation by a comparison of the different systems exposed to the same conditions and then examined via a range of techniques that cover a wide length scale. The conditions of approximately 1 displacement per atom via He2+ ions were used to simulate long term waste storage conditions as outlined by previous results from Ewing in a large enough sample volume to allow for neutron diffraction, as not attempted previously. The titanate sample, used as a baseline comparison since it readily becomes amorphous under these conditions behaved as expected. In contrast, the zirconate sample accumulates tensile stress in the absence of detectable strain. We propose this is analogous to the lanthanide zirconate pyrochlores examined by Simeone et al. where they reported the appearance of defect fluorite diffraction patterns due to a reduction in grain size. Radiation damage and stress results in the grains breaking into even smaller crystallites, thus creating even smaller coherent diffraction domains. An (ErNd)2(ZrTi)2O7 pyrochlore was synthesized to examine which mechanism might dominate, amorphization or stress/strain build up. Although strain was detected in the pristine sample via Synchrotron X-ray diffraction it was not of sufficient quality to perform a full analysis on.

Synthesis and Structure of Oxygen Deficient Lead-Technetium Pyrochlore, the First Example of a Valence V Technetium Oxide.

The structure of lead-technetium pyrochlore has been refined in space group F d 3 ¯ m with a = 10.36584(2) Å using a combination of synchrotron X-ray and neutron powder diffraction data and confirmed via Electron Diffraction. The oxide is found to be oxygen deficient with a stoichiometry of Pb2Tc2O7-d. Displacive disorder of the Pb cations is evident from the refinements, as has been observed in Bi2Tc2O7-d. X-ray absorption spectroscopic measurements at the Tc K-edge demonstrate the valence of the Tc is greater than 4.0 as anticipated from the refined oxygen stoichiometry. Raman spectroscopy confirms the presence of disorder leading us to conclude that this pyrochlore is the first example of a valence V technetium oxide.

Modelling of reusable target materials for the production of fission produced 99Mo using MCNP6.2 and CINDER90.

Current fission-based methods of 99Mo production require single use uranium targets which leads to spent uranium waste. This waste could be reduced if a target is developed that does not require dissolution so that it can be reused for multiple production runs. MCNP6.2 was used to model reusable targets of 20% and 1% enrichment for activity produced, target efficiency and burnup. The 1% enriched target was found to be much more efficient but had a lower activity produced compared to the 20% enriched target. The ideal target design for 99Mo production that optimises efficiency and reusability and reduces the self-shielding effect of UO2 was found to be a target that is made from 1% enriched UO2 with density as high as allowable for sufficient yields, efficient 99Mo extraction and having an irradiation time of 5 days, with the target able to be re-irradiated and re-processed 2-4 times.

Structures and Phase Transitions in Pertechnetates.

The temperature dependence of the structures of four pertechnetates (ATcO4 A = Ag, Tl, Rb, Cs) from 90 K to their melting points is described. Synchrotron X-ray diffraction measurements show that RbTcO4 undergoes a I41/a to I41/amd transition near 530 K that is associated with a change in the orientation of the TcO4- tetrahedra about the scheelite b axis. AgTcO4 also exhibits a tetragonal scheelite type structure, and this is retained between 90 and 750 K, above which it melted. CsTcO4 has an orthorhombic pseudo-scheelite structure at room temperature and this undergoes a first-order orthorhombic to tetragonal transformation (Pnma to I41/a) near 430 K. TlTcO4 is isostructural with CsTcO4 at 90 K, but the orthorhombic to tetragonal transformation proceeds via an intermediate orthorhombic phase. The different behavior found here and described previously for the analogous Re oxide TlReO4 highlights the differences in the chemistry of these two systems.

Development of LEU-based targets for radiopharmaceutical manufacturing: A review.

99Mo is an essential medical isotope that comprises of at least 70% of radioactive procedures globally. Currently an essential component of 99Mo manufacturing is the uranium target from which 99Mo is produced by fission. As the world moves towards low enriched uranium (LEU) targets due to non-proliferation concerns it is becoming of interest to find methods to increase the efficiency of the LEU targets in order to reduce the ever increasing nuclear waste levels of which a long term solution for disposal or treatment has yet to be satisfactorily found. Advantages and disadvantages of various target designs are investigated and discussed along current disposal and reprocessing methods. The idea of a reusable target is introduced as a way forward in reducing the nuclear waste burden for future generations.

The Quantification of Radiation Damage in Orthophosphates Using Confocal µ-Luminescence Spectroscopy of Nd3.

In this study, we present a new concept based on the steady-state, laser-induced photoluminescence of Nd3+, which aims at a direct determination of the amorphous fraction f a in monazite- and xenotime-type orthophosphates on a micrometer scale. Polycrystalline, cold-pressed, sintered LaPO4, and YPO4 ceramics were exposed to quadruple Au-ion irradiation with ion energies 35 MeV (50% of the respective total fluence), 22 MeV (21%), 14 MeV (16%), and 7 MeV (13%). Total irradiation fluences were varied in the range 1.6 × 1013-6.5 × 1013 ions/cm2. Ion-irradiation resulted in amorphization and damage accumulation unto a depth of ~5 µm below the irradiated surfaces. The amorphous fraction created was quantified by means of surface-sensitive grazing-incidence X-ray diffraction and photoluminescence spectroscopy using state-of-the-art confocal spectrometers with spatial resolution in the µm range. Monazite-type LaPO4 was found to be more susceptible to ion-irradiation induced damage accumulation than xenotime-type YPO4. Transmission electron microscopy of lamella cut from irradiated surfaces with the focused-ion beam technique confirmed damage depth-profiles with those obtained from PL hyperspectral mapping. Potential analytical advantages that arise from an improved characterization and quantification of radiation damage (i.e., f a) on the µm-scale are discussed.

Comparing results of X-ray diffraction, µ-Raman spectroscopy and neutron diffraction when identifying chemical phases in seized nuclear material, during a comparative nuclear forensics exercise.

This work presents the results for identification of chemical phases obtained by several laboratories as a part of an international nuclear forensic round-robin exercise. In this work powder X-ray diffraction (p-XRD) is regarded as the reference technique. Neutron diffraction produced a superior high-angle diffraction pattern relative to p-XRD. Requiring only small amounts of sample, µ-Raman spectroscopy was used for the first time in this context as a potentially complementary technique to p-XRD. The chemical phases were identified as pure UO2 in two materials, and as a mixture of UO2, U3O8 and an intermediate species U3O7 in the third material.

The Effect of Milling Time on the Microstructural Characteristics and Strengthening Mechanisms of NiMo-SiC Alloys Prepared via Powder Metallurgy.

A new generation of alloys, which rely on a combination of various strengthening mechanisms, has been developed for application in molten salt nuclear reactors. In the current study, a battery of dispersion and precipitation-strengthened (DPS) NiMo-based alloys containing varying amounts of SiC (0.5-2.5 wt %) were prepared from Ni-Mo-SiC powder mixture via a mechanical alloying (MA) route followed by spark plasma sintering (SPS) and rapid cooling. Neutron Powder Diffraction (NPD), Electron Back Scattering Diffraction (EBSD), and Transmission Electron Microscopy (TEM) were employed in the characterization of the microstructural properties of these in-house prepared NiMo-SiC DPS alloys. The study showed that uniformly-dispersed SiC particles provide dispersion strengthening, the precipitation of nano-scale Ni3Si particles provides precipitation strengthening, and the solid-solution of Mo in the Ni matrix provides solid-solution strengthening. It was further shown that the milling time has significant effects on the microstructural characteristics of these alloys. Increased milling time seems to limit the grain growth of the NiMo matrix by producing well-dispersed Mo2C particles during sintering. The amount of grain boundaries greatly increases the Hall-Petch strengthening, resulting in significantly higher strength in the case of 48-h-milled NiMo-SiC DPS alloys compared with the 8-h-milled alloys. However, it was also shown that the total elongation is considerably reduced in the 48-h-milled NiMo-SiC DPS alloy due to high porosity. The porosity is a result of cold welding of the powder mixture during the extended milling process.

Thermal Expansion Behavior in TcO2. Toward Breaking the Tc-Tc Bond.

The structure of TcO2 between 25 and 1000 °C has been determined in situ using X-ray powder diffraction methods and is found to remain monoclinic in space group P21/c. Thermal expansion in TcO2 is highly anisotropic, with negative thermal expansion of the b axis observed above 700 °C. This is the result of an anomalous expansion along the a axis that is a consequence of weakening of the Tc-Tc bonds.

Intricate disorder in defect fluorite/pyrochlore: a concord of chemistry and crystallography.

Intuitively scientists accept that order can emerge from disorder and a significant amount of effort has been devoted over many years to demonstrate this. In metallic alloys and oxides, disorder at the atomic scale is the result of occupation at equivalent atomic positions by different atoms which leads to the material exhibiting a fully random or modulated scattering pattern. This arrangement has a substantial influence on the material's properties, for example ionic conductivity. However it is generally accepted that oxides, such as defect fluorite as used for nuclear waste immobilization matrices and fuel cells, are the result of disorder at the atomic scale. To investigate how order at the atomic scale induces disorder at a larger scale length, we have applied different techniques to study the atomic composition of a homogeneous La 2 Zr 2 O 7 pyrochlore, a textbook example of such a structure. Here we demonstrate that a pyrochlore, which is considered to be defect fluorite, is the result of intricate disorder due to a random distribution of fully ordered nano-domains. Our investigation provides new insight into the order disorder transformations in complex materials with regards to domain formation, resulting in a concord of chemistry with crystallography illustrating that order can induce disorder.

The role of π-bonding on the high temperature structure of the double perovskites Ba2CaUO6 and BaSrCaUO6.

The high temperature structural behaviour of the uranium perovskites Ba2CaUO6 and BaSrCaUO6 has been investigated using a combination of synchrotron X-ray and neutron powder diffraction. Ba2CaUO6 undergoes a complex sequence of structures associated with the progressive loss of cooperative octahedral tilting: P21/n → I2/m → I2/m → I4/m → Fm3[combining macron]m. The observation of the intermediate tetragonal structure, I4/m, in this, contrasts with the previously reported rhombohedral R3[combining macron] intermediate formed by the Ba2SrUO6 oxide. The importance of π-bonding in determining the structural sequence is discussed.

An unconventional method for measuring the Tc L3-edge of technetium compounds.

Tc L3-edge XANES spectra have been collected on powder samples of SrTcO3 (octahedral Tc(4+)) and NH4TcO4 (tetrahedral Tc(7+)) immobilized in an epoxy resin. Features in the Tc L3-edge XANES spectra are compared with the pre-edge feature of the Tc K-edge as well as other 4d transition metal L3-edges. Evidence of crystal field splitting is obvious in the Tc L3-edge, which is sensitive to the coordination number and oxidation state of the Tc cation. The Tc L3 absorption edge energy difference between SrTcO3 (Tc(4+)) and NH4TcO4 (Tc(7+)) shows that the energy shift at the Tc L3-edge is an effective tool for studying changes in the oxidation states of technetium compounds. The Tc L3-edge spectra are compared with those obtained from Mo and Ru oxide standards with various oxidation states and coordination environments. Most importantly, fitting the Tc L3-edge to component peaks can provide direct evidence of crystal field splitting that cannot be obtained from the Tc K-edge.

Novel rattling of K atoms in aluminium-doped defect pyrochlore tungstate.

Rattling dynamics have been identified as fundamental to superconductivity in defect pyrochlore osmates and aluminium vanadium intermetallics, as well as low thermal conductivity in clathrates and filled skutterudites. Combining inelastic neutron scattering (INS) measurements and ab initio molecular dynamics (MD) simulations, we use a new approach to investigate rattling in the Al-doped defect pyrochlore tungstates: AAl0.33W1.67O6 (A = K, Rb, Cs). We find that although all the alkali metals rattle, the rattling of the K atoms is unique, not only among the tungstates but also among the analogous defect osmates, KOs2O6 and RbOs2O6. Detailed analysis of the MD trajectories reveals that two unique features set the K dynamics apart from the rest, namely, (1) quasi one-dimensional local diffusion within a cage, and (2) vibration at a range of frequencies. The local diffusion is driven by strongly anharmonic local potentials around the K atoms exhibiting a double-well structure in the direction of maximum displacement, which is also the direction of local diffusion. On the other hand, vibration at a range of frequencies is a consequence of the strong anisotropy in the local potentials around the K atoms as revealed by directional magnitude spectra. We present evidence to show that it is the smaller size rather than the smaller mass of the K rattler which leads to the unusual dynamics. Finally, we suggest that the occurrence of local diffusion and vibration at a range of frequencies in the dynamics of a single rattler, as found here for the K atoms, may open new possibilities for phonon engineering in thermoelectric materials.

The Effect of a Rapid Heating Rate, Mechanical Vibration and Surfactant Chemistry on the Structure-Property Relationships of Epoxy/Clay Nanocomposites.

The role of processing conditions and intercalant chemistry in montmorillonite clays on the dispersion, morphology and mechanical properties of two epoxy/clay nanocomposite systems was investigated in this paper. This work highlights the importance of employing complementary techniques (X-ray diffraction, small angle X-ray scattering, optical microscopy and transmission electron microscopy) to correlate nanomorphology to macroscale properties. Materials were prepared using an out of autoclave manufacturing process equipped to generate rapid heating rates and mechanical vibration. The results suggested that the quaternary ammonium surfactant on C30B clay reacted with the epoxy during cure, while the primary ammonium surfactant (I.30E) catalysed the polymerisation reaction. These effects led to important differences in nanocomposite clay morphologies. The use of mechanical vibration at 4 Hz prior to matrix gelation was found to facilitate clay dispersion and to reduce the area fraction of I.30E clay agglomerates in addition to increasing flexural strength by over 40%.

Electroacoustic isoelectric point determinations of bauxite refinery residues: different neutralization techniques and minor mineral effects.

Bauxite refinery residue (BRR) is a highly caustic, iron hydroxide-rich byproduct from alumina production. Some chemical treatments of BRR reduce soluble alkalinity and lower residue pH (to values <10) and generate a modified BRR (MBRR). MBRR has excellent acid neutralizing (ANC) and trace-metal adsorption capacities, making it particularly useful in environmental remediation. However, soluble ANC makes standard acid-base isoelectric point (IEP) determination difficult. Consequently, the IEP of a BRR and five MBRR derivatives (sulfuric acid-, carbon dioxide-, seawater-, a hybrid neutralization, i.e, partial CO(2) neutralization followed by seawater, and an activated-seawater-neutralized MBRR) were determined using electroacoustic techniques. Residues showed three significantly different groups of IEPs (p < 0.05) based around the neutralization used. Where the primary mineral assemblage is effectively unchanged, the IEPs were not significantly different from BRR (pH 6.6-6.9). However, neutralizations generating neoformational minerals (alkalinity precipitation) significantly increased the IEP to pH 8.1, whereas activation (a removal of some primary mineralogy) significantly lowered the IEP to pH 6.2. Moreover, surface charging curves show that surfaces remain in the ±30 mV surface charge instability range, which provides an explanation as to why MBRRs remove trace metals and oxyanions over a broad pH range, often simultaneously. Importantly, this work shows that minor mineral components in complex mineral systems may have a disproportionate effect on the observable bulk IEP. Furthermore, this work shows the appropriateness of electroacoustic techniques in investigating samples with significant soluble mineral components (e.g., ANC).

Formation and stability of Pb-, Zn- & Cu-PO4 phases at low temperatures: implications for heavy metal fixation in polar environments.

Low temperatures and frequent soil freeze-thaw in polar environments present challenges for the immobilisation of metals. To address these challenges we investigated the chemical forms of Pb, Zn and Cu in an Antarctic landfill, examined in vitro reaction kinetics of these metals and orthophosphate at 2 and 22 °C for up to 185 days, and subjected the products to freeze-thaw. Reaction products at both temperatures were similar, but the rate of production varied, with Cu-PO(4) phases forming faster, and the Zn- and Pb-PO(4) phases slower at 2 °C. All metal-orthophosphate phases produced were stable during a 2.5 h freeze-thaw cycle to -30 °C. Metal immobilisation using orthophosphate can be successful in polar regions, but treatments will need to consider differing mineral stabilities and reaction rates at low temperatures.

Structure and cation ordering in spinel-type TcCo2O4. An example of a trivalent technetium oxide.

The structure of TcCo(2)O(4) has been determined using a combination of synchrotron X-ray and neutron powder diffraction methods. It has an inverse spinel structure where the Tc occupies the octahedral sites. Both the refined Tc-O distance and X-ray absorption spectra suggest the Tc is predominantly trivalent.

Structural phase transitions and magnetic order in SrTcO3.

The structure of the perovskite SrTcO(3) has been investigated using both synchrotron X-ray and neutron powder diffraction. At room temperature SrTcO(3) is orthorhombic as a consequence of cooperative tilting of the corner sharing TcO(6) octahedra. The tilts are sequentially removed as the sample is heated with the oxide displaying the sequence of structres Pnma→Imma→I4/mcm→Pm ̅3m. Neutron powder diffraction data collected in the temperature range 4-1023 K indicate that SrTcO(3) has G-type antiferromagnetic structure, in which each Tc moment is antiparallel to its six nearest neighbours, below ∼1000 K. The magnetic structure is collinear antiferromagnetic with the technetium moments parallel to c-axis and can be described by the propagation vector k = [0,0,0] and the basis vector (0,0,A(z)). The same magnetic structure is observed in each of the four crystal structures.

High temperature magnetic ordering in the 4d perovskite SrTcO3.

We present evidence for possibly the highest magnetic ordering temperature in any compound without 3d transition elements. Neutron powder diffraction measurements, at both time-of-flight and constant wavelength sources, were performed on two independently prepared SrTcO3 powders. SrTcO3 adopts a distorted perovskite structure with G-type antiferromagnetic ordering and has a moment of 1.87(4)µB per Tc cation at room temperature with an extraordinarily high Néel point close to 750 °C. Electronic structure calculations reveal extensive mixing between the technetium 4d states and oxygen states proximal to the Fermi level. This hybridization leads to a close relationship between magnetic ordering temperature and moment formation in SrTcO3.