This paper is dedicated to the adaptation of the Weak Acid Resin process (WAR) to the elaboration of uranium-americium mixed oxide microspheres as precursors for the fabrication of Americium Bearing Blankets (AmBB). It describes successive developments of WAR process from lanthanide simple oxide synthesis to actinide(s) bearing mixed oxide preparation. Recent studies demonstrated the scientific feasibility of the preparation of a dense uranium-americium mixed oxide pellets with 10 at% of Am vs heavy metal and with 95 % of theoretical density (TD) from those innovative microsphere precursors.

The sintering behavior of green pellets obtained from nanostructured Ce0.8Gd0.2O1.9 submillimetric microspheres is studied in the present paper. Corresponding shrinkage rate curve shows a two-step densification in dynamic conditions, with the presence of two successive extrema, at 1200 K and 1500 K. To fully understand this non-common densification behavior, an iterative study was performed. Multiple characterizations point out multiscale organization of the matter with temperature giving rise to differential sintering stages of two different particle size classes. Concerning 1200 K-first shrinkage rate maximum, it corresponds to the densification of nanometric aggregates of crystallites into submicrometric pre-sintered aggregates, resulting in a specific porous microstructure with residual open porosity. As-generated porosity combined with submicron size of pre-sintered aggregates thus prevent from a homogeneous sintering illustrated by a single maximum shrinkage rate. Finally, the second maximum shrinkage rate at 1500 K can then be associated to optimal temperature for submicrometric particles sintering.

In view of aspects such as the leaching behavior of spent nuclear fuel stored in an oxidative environment as well as the potential intermixing of fission products (Pu and minor actinides) with U 3 O 8 as the most stable uranium oxide, the latter is tested by fixing an aqueous solutions of UO 2 2+ and Am 3+ cations in a 90:10 atomic ratio at a weak-acidic ion-exchanger resin.

U3O8 is considered to be the most stable phase for uranium oxide. Its structural properties must be accurately understood to foresee and manage aspects such as its leaching behavior when spent nuclear fuel is stored in an oxidative environment. Moreover, as fuel irradiation causes the formation of fission products and activation products such as plutonium and minor actinides, it is probable that U3O8 will be mixed with other chemical elements under real conditions of oxidation. The storage issue can be extended to americium transmutation, where the irradiated compounds are mixed oxides composed of uranium and americium. This study thus focused on determining the structural properties of a solid solution containing uranium and trivalent americium (U/AM ratio = 90/10) and synthesized so as to obtain conventional U3O8 oxide. This paper presents the possibility of combining trivalent americium with uranium in a U3O8 mixed oxide for the first time, despite the high valence and atomic ratio differences, and proposes novel structural arrangements. X-ray diffraction measurements reveal americium substitution in U3O8 uranium cationic sites, leading to phase transformation into a U3O8 high-temperature structure and general lattice swelling. X-ray absorption near-edge spectroscopy and extended X-ray absorption fine structure experiments highlight an excess of U+VI organized in uranyl units as the main consequence of accommodation.

Mixed uranium-americium oxides are one of the materials envisaged for Americium Bearing Blankets dedicated to transmutation in fast neutron reactors. Conversion and fabrication processes are currently developed to make those materials in the form of dense and homogeneous oxide ceramic pellets or dense granulates incorporating uranium and americium. Their development points out the need of a simplified and optimized process which could lower hazards linked to dust generation of highly contaminating and irradiating compounds and facilitate material transfer in remote handling operations. This reason motivated the development of innovative “dustless” route such as the Weak Acid Resin route (WAR) which provides the oxide precursors in the form of sub-millimeter-sized microspheres with optimal flowability and limits dust generation during conversion and fabrication steps. This study is thus devoted to the synthesis of mixed uranium-americium oxide microspheres by the WAR process and to the characterization of such precursors. This work also deals with their application to the fabrication of dense or porous pellets and with their potential use as dense spherules to make Sphere-Pac fuel.

(Uranium + americium) mixed oxides are considered as potential targets for americium transmutation in fast neutron reactors. Their thermophysical properties and notably their melting behaviour have not been assessed properly although required in order to evaluate the safety of these compounds under irradiation. In this study, we measured via laser heating, the melting points under inert atmosphere (Ar) of U1-xAmxO2 +/-delta samples with x = 0.10, 0.15, 0.20. The obtained melting/solidification temperatures, measured here, indicate that under the current experimental conditions in the investigated AmO2 content range, the solidus line of the (UO2 + AmO2) system follows with very good agreement the ideal solution behaviour. Accordingly, the observed liquidus formation temperature decreases from (3130 +/- 20) K for pure UO2 to (3051 +/- 28) K for U0.8Am0.2O2 +/-delta. The melted and quenched materials have been characterised by combining X-ray diffraction and X-ray absorption spectroscopy. (C) 2016 The Authors. Published by Elsevier Ltd.

The use of CRMP (Calcined Resin Microsphere Pelletization) process for AmBB (Americium Bearing Blankets) fabrication is today a key research axis in americium transmutation domain, where its very high activity requires minimization of powder dissemination. In this aim, the use of oxide microspheres as compaction precursors is a promising clean alternative to powder metallurgy. Understanding the different steps of densification during CRMP pellet sintering thus appears as fundamental to obtain final materials with the specific features required for AmBB. The densification curve recorded in dynamic conditions shows different sintering steps. A first decrease of shrinkage rate happens at low temperature, around 1100 K. This phenomenon is not normally observed in the sintering of conventional powders. Chemical and microstructural studies were performed on (U,Am)O2 and also on (Ce,Gd)O2 surrogate compound to highlight the causes of this low-temperature sintering step. Multiscale reorganization finally appears as the sole explanation, through the sintering of nanometric aggregate present in the green pellet and related to the morphology of the starting microspheres employed as pelletization precursors.

Uranium–americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U1−xAmxO2±δ samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U1−xAmxO2±δ leads to the formation of similar fluorite solid solution indicating the presence of Am+III and U+V in equimolar proportions.

This study is devoted to the synthesis and the characterization of porous metal oxide microsphere from metal loaded ion exchange resin. Their application concerns the fabrication of uranium-americium oxide pellets using the powder-free process called Calcined Resin Microsphere Pelletization (CRMP). Those mixed oxide ceramics are one of the materials envisaged for americium transmutation in sodium fast neutron reactors. The advantage of such microsphere precursor compared to classical oxide powder is the diminution of the risk of fine dissemination which can be critical for the handling of highly radioactive powders such as americium based oxides and the improvement of flowability for the filling of compaction chamber. Those millimetric oxide microspheres incorporating uranium and americium were synthesized and characterizations showed a very porous microstructure very brittle in nature which occurred to be adapted to shaping by compaction. Studies allowed to determine an optimal heat treatment with calcination temperature comprised between 700–800 °C and temperature rate lower than 2 °C/min. Oxide Precursors were die-pressed into pellets and then sintered under air to form regular ceramic pellets of 95% of theoretical density (TD) and of homogeneous microstructure. This study validated thus the scientific feasibility of the CRMP process to prepare bearing americium target in a powder free manner.

Transmutation of americium in heterogeneous mode through the use of U1-xAmxO2±δ ceramic pellets, also known as Americium Bearing Blankets (AmBB), has become a major research axis. Nevertheless, in order to consider future large-scale deployment, the processes involved in AmBB fabrication have to minimize fine particle dissemination, due to the presence of americium, which considerably increases the risk of contamination. New synthesis routes avoiding the use of pulverulent precursors are thus currently under development, such as the Calcined Resin Microsphere Pelletization (CRMP) process. It is based on the use of weak-acid resin (WAR) microspheres as precursors, loaded with actinide cations. After two specific calcinations under controlled atmospheres, resin microspheres are converted into oxide microspheres composed of a monophasic U1-xAmxO2±δ phase. Understanding the different mechanisms during thermal conversion, that lead to the release of organic matter and the formation of a solid solution, appear essential. By combining in situ techniques such as XRD and XAS, it has become possible to identify the key temperatures for oxide formation, and the corresponding oxidation states taken by uranium and americium during mineralization. This paper thus presents the first results on the mineralization of (U,Am) loaded resin microspheres into a solid solution, through in situ XAS analysis correlated with HT-XRD.

In the current nano-sized material revolution, the main limitations to a large-scale deployment of nanomaterials involve health concerns related to nano-dissemination via air. Developing new chemical routes benefiting from nano-size advantages while avoiding their hazards could overcome these limitations. Addressing this need, a chemical route leading to soft nano-particle agglomerates, i.e., macroscopic precursors presenting the ability to be decomposed into nano-sized materials, was developed and applied to Ce0.8Gd0.2O2−δ. Using cerium/gadolinium-loaded ion exchange resin, the Ce0.8Gd0.2O2−δ solid solution formation as a function of temperature was studied in-situ through X-ray diffraction, X-ray absorption spectroscopy and Raman spectroscopy. Temperatures corresponding to the organic skeleton decomposition and to the mixed oxide crystallization were identified. An optimal heat treatment, leading to nanostructured soft agglomerates, was established. Microsphere processing capabilities were evaluated and particle size distribution measurements were recorded. A very low fracture strength was calculated, and a nanometric particle size distribution (170nm) was determined.

Mixed oxides are used as nuclear fuels and are notably envisaged for future fuel cycles including plutonium and minor actinide recycling. In this context, processes are being developed for the fabrication of uranium–americium mixed-oxide compounds for transmutation. The purpose of these processes is not only the compliance with fuel specifications in terms of density and homogeneity, but also the simplification of the process for its industrialization as well as lowering dust generation. In this paper, the use of a U0.85Am0.15O2±δ powder synthesized by oxalate co-conversion as a precursor for dense fuel fabrications is assessed. This study notably focuses on sintering, which yielded pellets up to 96% of the theoretical density, taking advantage of the high reactivity and homogeneity of the powder. As-obtained pellets were further characterized to be compared to those obtained via processes based on the UMACS (Uranium Minor Actinide Conventional Sintering) process. This comparison highlights several advantages of co-converted powder as a precursor for simplified processes that generate little dust.