579 research outputs found
Hot isostatically pressed zirconolite wasteforms for actinide immobilisation
In order to demonstrate the deployment of Hot Isostatic Pressing (HIP) for the immobilisation of Pu stocks and residues, a series of active and inactive zirconolite formulations have been processed and characterised. In this instance, Ce, U, and Th have been applied as chemical surrogates for Pu4+. A range of formulations targeting isovalent Zr4+ site substitution (i.e. to simulate CaZr1-xPuxTi2O7) have been processed by HIP and characterised by powder X-ray diffraction, and scanning electron microscopy, in order to determine surrogate partitioning between the host zirconolite phase, and accessory phases that may have formed during the HIP process
Investigation of the effect of milling duration on a Ce-Gd doped zirconolite phase assemblage synthesised by hot isostatic pressing
Zirconolite is a candidate ceramic wasteform under consideration for the immobilisation of the UK civil PuO2 inventory. In the present work, a baseline dual-substituted zirconolite with the target composition (Ca0.783Gd0.017Ce0.2)(Zr0.883Gd0.017Ce0.1)(Ti1.6Al0.4)O7 was fabricated by hot isostatic pressing (HIPing). In order to optimise the microstructure properties and improve the obtained yield of the zirconolite phase, a range of planetary ball milling parameters were investigated prior to consolidation by HIP. This included milling the batched oxide precursors at 400 rpm for up to 120 min, the pre-milling of CeO2 (PuO2 surrogate) to reduce the particle size and using a CeO2 source with finer particle size (<5 ”m). The HIPed zirconolite product consisted of both zirconolite-2M and zirconolite-3T polytypes in varying proportions; however, an additional perovskite phase was obtained in varying quantities as a secondary phase. Ce L3-edge X-ray absorption spectroscopy was utilised to determine the Ce oxidation state. In this study, the ideal milling parameter for the fabrication of zirconolite waste forms was defined as 60 min at 400 rpm
Influence of transition metal charge compensation species on phase assemblage in zirconolite ceramics for Pu immobilisation
Immobilisation of Pu in a zirconolite matrix (CaZrTi2O7) is a viable pathway to disposition. A-site substitution, in which Pu4+ is accommodated into the Ca2+ site in zirconolite, coupled with sufficient trivalent M3+/Ti4+ substitution (where M3+ = Fe, Al, Cr), has been systematically evaluated using Ce4+ as a structural analogue for Pu4+. A broadly similar phase assemblage of zirconolite-2M and minor perovskite was observed when targeting low levels of Ce incorporation. As the targeted Ce fraction was elevated, secondary phase formation was influenced by choice of M3+ species. Co-incorporation of Ce/Fe resulted in the stabilisation of a minor Ce-containing perovskite phase at high wasteloading, whereas considerable phase segregation was observed for Cr3+ incorporation. The most favourable substitution approach appeared to be achieved with the use of Al3+, as no perovskite or free CeO2 was observed. However, high temperature treatments of Al containing specimens resulted in the formation of a secondary Ce-containing hibonite phase
Review of zirconolite crystal chemistry and aqueous durability
Zirconolite (CaZrTi2O7) has been identified as a candidate ceramic wasteform for the immobilisation and disposal of Pu inventories, for which there is no foreseen future use. Here, we provide an overview of relevant zirconolite solid solution chemistry with respect to Ce, U and Pu incorporation, alongside a summary of the available literature on zirconolite aqueous durability. The zirconolite phase may accommodate a wide variety of tri- and tetravalent actinide and rare-earth dopants through isovalent and heterovalent solid solution, e.g. CaZr1âxPuxTi2O7 or Ca1âxPuxZrTi2â2xFe2xO7. The progressive incorporation of actinides within the zirconolite-2M parent structure is accommodated through the formation of zirconolite polytypoids, such as zirconolite-4M or 3T, depending on the choice of substitution regime and processing route. A variety of standardised durability tests have demonstrated that the zirconolite phase exhibits exceptional chemical durability, with release rates of constituent elements typically <10â5 gmâ2·dâ1. Further work is required to understand the extent to which polytype formation and surrogate choice influence the dissolution behaviour of zirconolite wasteforms
Anomalous diffusion, Localization, Aging and Sub-aging effects in trap models at very low temperature
We study in details the dynamics of the one dimensional symmetric trap model,
via a real-space renormalization procedure which becomes exact in the limit of
zero temperature. In this limit, the diffusion front in each sample consists in
two delta peaks, which are completely out of equilibrium with each other. The
statistics of the positions and weights of these delta peaks over the samples
allows to obtain explicit results for all observables in the limit .
We first compute disorder averages of one-time observables, such as the
diffusion front, the thermal width, the localization parameters, the
two-particle correlation function, and the generating function of thermal
cumulants of the position. We then study aging and sub-aging effects : our
approach reproduces very simply the two different aging exponents and yields
explicit forms for scaling functions of the various two-time correlations. We
also extend the RSRG method to include systematic corrections to the previous
zero temperature procedure via a series expansion in . We then consider the
generalized trap model with parameter and obtain that the
large scale effective model at low temperature does not depend on in
any dimension, so that the only observables sensitive to are those
that measure the `local persistence', such as the probability to remain exactly
in the same trap during a time interval. Finally, we extend our approach at a
scaling level for the trap model in and obtain the two relevant time
scales for aging properties.Comment: 33 pages, 3 eps figure
Phase evolution in the CaZrTi2O7âDy2Ti2O7 system : a potential host phase for minor actinide immobilization
Zirconolite is considered to be a suitable wasteform material for the immobilization of Pu and other minor actinide species produced through advanced nuclear separations. Here, we present a comprehensive investigation of Dy3+ incorporation within the self-charge balancing zirconolite Ca1âxZr1âxDy2xTi2O7 solid solution, with the view to simulate trivalent minor actinide immobilization. Compositions in the substitution range 0.10 †x †1.00 (Îx = 0.10) were fabricated by a conventional mixed oxide synthesis, with a two-step sintering regime at 1400 °C in air for 48 h. Three distinct coexisting phase fields were identified, with single-phase zirconolite-2M identified only for x = 0.10. A structural transformation from zirconolite-2M to zirconolite-4M occurred in the range 0.20 †x †0.30, while a mixed-phase assemblage of zirconolite-4M and cubic pyrochlore was evident at Dy concentrations 0.40 †x †0.50. Compositions for which x â„ 0.60 were consistent with single-phase pyrochlore. The formation of zirconolite-4M and pyrochlore polytype phases, with increasing Dy content, was confirmed by high-resolution transmission electron microscopy, coupled with selected area electron diffraction. Analysis of the Dy L3-edge XANES region confirmed that Dy was present uniformly as Dy3+, remaining analogous to Am3+. Fitting of the EXAFS region was consistent with Dy3+ cations distributed across both Ca2+ and Zr4+ sites in both zirconolite-2M and 4M, in agreement with the targeted self-compensating substitution scheme, whereas Dy3+ was 8-fold coordinated in the pyrochlore structure. The observed phase fields were contextualized within the existing literature, demonstrating that phase transitions in CaZrTi2O7âREE3+Ti2O7 binary solid solutions are fundamentally controlled by the ratio of ionic radius of REE3+ cations
Annual Research Review: interparental conflict and youth psychopathology: an evidence review and practice focused update
The quality of the interparental relationship is recognized as an important influence on child and adolescent psychopathology. Historically, clinically-oriented research on this topic has focused on the impacts of parental divorce and domestic violence as primary interparental relationship influences on child outcomes, to the relative neglect of dimensional or qualitative features of the couple/interparental relationship for youth (child and adolescent) psychopathology. Recent research has highlighted that children are affected by attributes of interparental conflict, specifically how parents express and manage conflicts in their relationship, across a continuum of expressed severity and negativity â ranging from silence to violence. Further, new evidence highlights that childrenâs emotional, behavioral, social, academic outcomes and future interpersonal relationships are adversely affected by conflict between parents/carers whether adults are living together or not (i.e. married or separated), or where children are or are not genetically related to their rearing parents (e.g. adoption). We review evidence and present an integrated theoretical model, highlighting how children are affected by interparental conflict and what this evidence base means for effective intervention and prevention program development, as well as the development of possible cost-benefit models. Additionally, we review policy implications of this research and highlight some very recent examples of UK-based policy focusing on addressing the interparental relationship and its impact on youth psychopathology
Synthesis and characterisation of HIP Ca0.80Ce0.20ZrTi1.60Cr0.40O7 zirconolite and observations of the ceramicâcanister interface
A sample of zirconolite with nominal composition Ca0.80Ce0.20ZrTi1.60Cr0.40O7 was processed via Hot Isostatic Pressing (HIP), with a dwell temperature and pressure of 1320 °C/100 MPa maintained for 4 h. The produced wasteform was characterised by powder XRD, SEMâEDS, Ce L3 and Cr K-edge XANES. A significant portion of the Ce inventory did not fully partition within the zirconolite phase, instead remaining as CeO2 within the microstructure. Inspection of the stainless steelâceramic interface detailed the presence of an interaction region dominated by a Cr-rich oxide layer. No significant Cr or Fe migration was observed, although a greater concentration of perovskite was observed at the periphery, relative to the bulk ceramic matrix. The X-ray absorption features of Cr remained analogous with Cr3+ accommodation within TiO6 octahedra in the zirconolite matrix. The absorption edge of Ce was comprised of contributions from zirconolite-2M and unincorporated CeO2, with an average oxidation state of Ce3.9+. As zirconolite-2M accounted forâ>â92 wt% of the overall phase assemblage, it is clear that the dominant oxidation state of Ce in this phase was Ce4+
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