Role of self-irradiation defects on the ageing of 239PuCoGa5

6 pages, 18 referencesInternational audienceLow-temperature accumulation and annealing experiments, in conjunction with electrical resistivity and critical current density measurements, were used to study the ageing of the actinide superconductor PuCoGa5. These measurements reveal that 2-nm sized non-superconducting point-like regions are the main damage formed during room temperature ageing; smaller point-like defect were irrelevant to transport properties. Defect sizes and densities deduced from experiment agree with Transmission Electron Micoscopy observations

Probing magnetism in the vortex phase of PuCoGa5 by X-ray magnetic circular dichroism

We have measured X-ray magnetic circular dichroism (XMCD) spectra at the Pu M4;5 absorption edges from a newly-prepared high-quality single crystal of the heavy fermion superconductor 242PuCoGa5, exhibiting a critical temperature Tc = 18.7 K. The experiment probes the vortex phase below Tc and shows that an external magnetic field induces a Pu 5f magnetic moment at 2 K equal to the temperature-independent moment measured in the normal phase up to 300 K by a SQUID device. This observation is in agreement with theoretical models claiming that the Pu atoms in PuCoGa5 have a nonmagnetic singlet ground state resulting from the hybridization of the conduction electrons with the intermediate-valence 5f electronic shell. Unexpectedly, XMCD spectra show that the orbital component of the 5f magnetic moment increases significantly between 30 and 2 K; the antiparallel spin component increases as well, leaving the total moment practically constant. We suggest that this indicates a low-temperature breakdown of the complete Kondo-like screening of the local 5f moment.JRC.G.I.5-Advanced Nuclear Knowledg

Tris‐{hydridotris(1‐pyrazolyl)borato}actinide Complexes: Synthesis, Spectroscopy, Crystal Structure, Bonding Properties and Magnetic Behaviour

The isostructural compounds of the trivalent actinides uranium, neptunium, plutonium, americium, and curium with the hydridotris(1-pyrazolyl)borato (Tp) ligand An[η$_{3}$-HB(N$_{2}$C$_{3}$H$_{3}$)$_{3}$]$_{3}$ (AnTp$_{3}$) have been obtained through several synthetic routes. Structural, spectroscopic (absorption, infrared, laser fluorescence) and magnetic characterisation of the compounds were performed in combination with crystal field, density functional theory (DFT) and relativistic multiconfigurational calculations. The covalent bonding interactions were analysed in terms of the natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) models

Tris‐{hydridotris(1‐pyrazolyl)borato}actinide Complexes: Synthesis, Spectroscopy, Crystal Structure, Bonding Properties and Magnetic Behaviour

The isostructural compounds of the trivalent actinides uranium, neptunium, plutonium, americium, and curium with the hydridotris(1-pyrazolyl)borato (Tp) ligand An[η$_{3}$-HB(N$_{2}$C$_{3}$H$_{3}$)$_{3}$]$_{3}$ (AnTp$_{3}$) have been obtained through several synthetic routes. Structural, spectroscopic (absorption, infrared, laser fluorescence) and magnetic characterisation of the compounds were performed in combination with crystal field, density functional theory (DFT) and relativistic multiconfigurational calculations. The covalent bonding interactions were analysed in terms of the natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) models

Muon spin rotation measurements of the superfluid density in fresh and aged superconducting PuCoGa5_5

We have measured the temperature dependence and magnitude of the superfluid density $\rho_{\rm s}(T)$ via the magnetic field penetration depth $\lambda(T)$ in PuCoGa$_5$ (nominal critical temperature $T_{c0} = 18.5$ K) using the muon spin rotation technique in order to investigate the symmetry of the order parameter, and to study the effects of aging on the superconducting properties of a radioactive material. The same single crystals were measured after 25 days ($T_c = 18.25$ K) and 400 days ($T_c = 15.0$ K) of aging at room temperature. The temperature dependence of the superfluid density is well described in both materials by a model using d-wave gap symmetry. The magnitude of the muon spin relaxation rate $\sigma$ in the aged sample, $\sigma\propto 1/\lambda^2\propto\rho_s/m^*$, where $m^*$ is the effective mass, is reduced by about 70% compared to fresh sample. This indicates that the scattering from self-irradiation induced defects is not in the limit of the conventional Abrikosov-Gor'kov pair-breaking theory, but rather in the limit of short coherence length (about 2 nm in PuCoGa$_5$) superconductivity.Comment: 11 page

Radiation Effects in Americium Ceramic Compounds

Along with uranium dioxide, mixed oxides play an essential role as fuels for present or next generation nuclear reactors. Although their production has been studied extensively, the methods applied currently result in materials that are usually not homogeneous at an atomic scale. To improve the quality of the powders (homogeneity and sintering properties), the hydrothermal decomposition of oxalate method was investigated. Preliminary attempts for the (Th,Pu)O2, (Np,Pu)O2 and (Th,Np,Pu)O2 systems were reported elswhere. The procedure allowed the production of nanometric powders of U1-xPuxO2 solid solution in the full composition range. Partial oxidation of U(IV) to U(V) was observed, while plutonium was assumed to maintain its tetravalent oxidation state. Thanks to the low-temperature of the synthesis, such mixed oxides were used as reagents for the fabrication of more complicated systems. The aliovalent americium, which has a preference for the trivalent oxidation state, can be accommodated in the UO2 fluorite structure by charge compensation with U(V) only in limited amounts. Still, the feasibility of the method has been demonstrated for an Am-content relevant to transmutation fuels. Thus, U1-xAmxO2 (x = 0.1 and 0.2) and U0.75Pu0.20Am0.05 nanosized powders were produced by hydrothermal decomposition of the corresponding mixed oxalate. Typical oxidation states detected for the cations were U(IV)/U(V) for nanometric and sintered materials, respectively, where both exhibit mixed and Am(III)/Am(IV) oxidation state. Their sintering ability was tested and the volumetric expansion was measured by powder XRD as a function of storage time. A low swelling with no indications of amorphization has been derived over a period of four years

Organometallic neptunium(III) complexes

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal–ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements

Superconductivity in transuranium elements and compounds

We present here an overview of the properties of transuranium superconductors, but also of the (non-superconducting) transuranium analogues of uranium superconductors. We briefly review superconductivity in actinide elements and uranium compounds and focus in particular on the PuTX5(T=Co, Rh; X=Ga, In) series, the largest superconducting system in actinides and NpPd5Al2, the so far unique neptunium superconductor. The effects of chemical substitution, ageing and pressure on the properties of transuranium superconductors are also discussed.JRC.E.6-Actinide researc