Rudy J. M. Konings

Structural Properties and Charge Distribution of the Sodium Uranium, Neptunium, and Plutonium Ternary Oxides: A Combined X-ray Diffraction and XANES Study

The charge distributions in α-Na2UO4, Na3NpO4, α-Na2NpO4, Na4NpO5, Na5NpO6, Na2PuO3, Na4PuO5, and Na5PuO6 are investigated in this work using X-ray absorption near-edge structure (XANES) spectroscopy at the U-L3, Np-L3, and Pu-L3 edges. In addition, a Rietveld refinement of monoclinic Na2PuO3, in space group C2/c, is reported for the first time, and the existence of the isostructural Na2NpO3 phase is revealed. In contrast to measurements in solution, the number of published XANES data for neptunium and plutonium solid phases with a valence state higher than IV is very limited. The present results cover a wide range of oxidation states, namely, IV to VII, and can serve as reference for future investigations. The sodium actinide series show a variety of local coordination geometries, and correlations between the shape of the XANES spectra and the local structural environments are discussed herein.

X-ray Diffraction, Mössbauer Spectroscopy, Magnetic Susceptibility, and Specific Heat Investigations of Na4NpO5 and Na5NpO6.

The hexavalent and heptavalent sodium neptunate compounds Na4NpO5 and Na5NpO6 have been investigated using X-ray powder diffraction, Mössbauer spectroscopy, magnetic susceptibility, and specific heat measurements. Na4NpO5 has tetragonal symmetry in the space group I4/m, while Na5NpO6 adopts a monoclinic unit cell in the space group C2/m. Both structures have been refined for the first time using the Rietveld method. The valence states of neptunium in these two compounds, i.e., Np(VI) and Np(VII), respectively, have been confirmed by the isomer shift values of their Mössbauer spectra. The local structural properties obtained from the X-ray refinements have also been related to the quadrupole coupling constants and asymmetry parameters determined from the Mössbauer studies. The absence of magnetic ordering has been confirmed for Na4NpO5. However, specific heat measurements at low temperatures have suggested the existence of a Schottky-type anomaly at around 7 K in this Np(VI) phase.

Properties of the high burnup structure in nuclear light water reactor fuel

Abstract The formation of the high burnup structure (HBS) is possibly the most significant example of the restructuring processes affecting commercial nuclear fuel in-pile. The HBS forms at the relatively cold outer rim of the fuel pellet, where the local burnup is 2–3 times higher than the average pellet burnup, under the combined effects of irradiation and thermo-mechanical conditions determined by the power regime and the fuel rod configuration. The main features of the transformation are the subdivision of the original fuel grains into new sub-micron grains, the relocation of the fission gas into newly formed intergranular pores, and the absence of large concentrations of extended defects in the fuel matrix inside the subdivided grains. The characterization of the newly formed structure and its impact on thermo-physical or mechanical properties is a key requirement to ensure that high burnup fuel operates within the safety margins. This paper presents a synthesis of the main findings from extensive studies performed at JRC-Karlsruhe during the last 25 years to determine properties and behaviour of the HBS. In particular, microstructural features, thermal transport, fission gas behaviour, and thermo-mechanical properties of the HBS will be discussed. The main conclusion of the experimental studies is that the HBS does not compromise the safety of nuclear fuel during normal operations.

Laser-heating and Radiance Spectrometry for the Study of Nuclear Materials in Conditions Simulating a Nuclear Power Plant Accident

Major and severe accidents have occurred three times in nuclear power plants (NPPs), at Three Mile Island (USA, 1979), Chernobyl (former USSR, 1986) and Fukushima (Japan, 2011). Research on the causes, dynamics, and consequences of these mishaps has been performed in a few laboratories worldwide in the last three decades. Common goals of such research activities are: the prevention of these kinds of accidents, both in existing and potential new nuclear power plants; the minimization of their eventual consequences; and ultimately, a full understanding of the real risks connected with NPPs. At the European Commission Joint Research Centres Institute for Transuranium Elements, a laser-heating and fast radiance spectro-pyrometry facility is used for the laboratory simulation, on a small scale, of NPP core meltdown, the most common type of severe accident (SA) that can occur in a nuclear reactor as a consequence of a failure of the cooling system. This simulation tool permits fast and effective high-temperature measurements on real nuclear materials, such as plutonium and minor actinide-containing fission fuel samples. In this respect, and in its capability to produce large amount of data concerning materials under extreme conditions, the current experimental approach is certainly unique. For current and future concepts of NPP, example results are presented on the melting behavior of some different types of nuclear fuels: uranium-plutonium oxides, carbides, and nitrides. Results on the high-temperature interaction of oxide fuels with containment materials are also briefly shown.

Thermodynamic data to model the interaction between coolant and fuel in gen IV sodium cooled fast reactors

Understanding the behaviour of nuclear fuels in various environments is vital to the design and safe operation of nuclear reactors. While this is true if the reactor is operating within its design specification, it is even more so if accidents occur and the fuel is exposed to unexpected temperatures, pressures or chemical environments. It is clearly hazardous and costly to explore all such scenarios experimentally and therefore it is necessary to undertake modelling where possible using well-grounded theoretical approaches. This paper will show examples of where calculations of chemical and phase equilibria have been applied successfully to the long term storage of nuclear waste, phase formation during core meltdown and prediction of fission product release into the atmosphere. It will also highlight the development of thermodynamic data carried out during the European Metrology Research Project Metrofission required to model the potential interaction between the coolant, nuclear fuel, containment materials and atmosphere of a sodium cooled fast reactor.

A New Look at the Structural and Magnetic Properties of Potassium Neptunate K2NpO4 Combining XRD, XANES Spectroscopy, and Low-Temperature Heat Capacity

The physicochemical properties of the potassium neptunate K2NpO4 have been investigated in this work using X-ray diffraction, X-ray absorption near edge structure (XANES) spectroscopy at the Np-L3 edge, and low-temperature heat capacity measurements. A Rietveld refinement of the crystal structure is reported for the first time. The Np(VI) valence state has been confirmed by the XANES data, and the absorption edge threshold of the XANES spectrum has been correlated to the Mössbauer isomer shift value reported in the literature. The standard entropy and heat capacity of K2NpO4 have been derived at 298.15 K from the low-temperature heat capacity data. The latter suggest the existence of a magnetic ordering transition around 25.9 K, most probably of the ferromagnetic type.