THERMAL PROPERTIES AND HOMOGENITY RANGE OF Bi24+xCo2-xO39 CERAMICS

Samples with different Bi2O3/Co2O3 ratio were prepared by ceramic route. Based on the results of DTA, XRD and SEM – EDX a section of phase diagram of the Bi–Co–O diagram in air atmosphere was calculated using the FactSage software. The sillenite structure of Bi24+xCo2-xO39 was confirmed and described. The Rietveld analysis confirmed SEM – EDX results. The heat capacity and enthalpy increments of Bi24Co2O39 were measured by differential scanning calorimetry (DSC) from 258 K to 355 K and by the drop calorimetry from 573 K to 973 K. Above room temperature the temperature dependence of the molar heat capacity in the form Cpm = (1467.87 + 0.299410 · T – 15888378 · T-2) J K-1 mol-1 was derived by least-squares method from the experimental data

First principles calculations of oxygen adsorption on the UN (001) surface

Fabrication, handling and disposal of nuclear fuel materials require comprehensive knowledge of their surface morphology and reactivity. Due to unavoidable contact with air components (even at low partial pressures), UN samples contain considerable amount of oxygen impurities affecting fuel properties. The basic properties of O atoms adsorbed on the UN(001) surface are simulated here combining the two first principles calculation methods based on the plane wave basis set and that of the localized atomic orbitals.Comment: 9 page

Ab initio modeling of oxygen impurity atom incorporation into uranium mononitride surface and subsurface vacancies

The incorporation of oxygen atoms has been simulated into either nitrogen or uranium vacancy at the UN(001) surface, sub-surface or central layers. For calculations on the corresponding slab models both the relativistic pseudopotentials and the method of projector augmented-waves (PAW) as implemented in the VASP computer code have been used. The energies of O atom incorporation and solution within the defective UN surface have been calculated and discussed. For different configurations of oxygen ions at vacancies within the UN(001) slab, the calculated density of states and electronic charge re-distribution was analyzed. Considerable energetic preference of O atom incorporation into the N-vacancy as compared to U-vacancy indicates that the observed oxidation of UN is determined mainly by the interaction of oxygen atoms with the surface and sub-surface N vacancies resulting in their capture by the vacancies and formation of O-U bonds with the nearest uranium atoms. Keywords: Density functional calculations, uranium mononitride, surface, defects, N and U vacancie

Chemisorption of a molecular oxygen on the UN (001) surface: ab initio calculations

The results of DFT GGA calculations on oxygen molecules adsorbed upon the (001) surface of uranium mononitride (UN) are presented and discussed. We demonstrate that O2 molecules oriented parallel to the substrate can dissociate either (i) spontaneously when the molecular center lies above the surface hollow site or atop N ion, (ii) with the activation barrier when a molecule sits atop the surface U ion. This explains fast UN oxidation in air

Non-linear electrical response in a charge/orbital ordered Pr⁡0.63\Pr_{0.63}Ca0.37_{0.37}MnO3_3 crystal : the charge density wave analogy

Non-linear conduction in a charge-ordered manganese oxide Pr$_{0.63}$Ca$_{0.37}$MnO$_3$ is reported. To interpret such a feature, it is usually proposed that a breakdown of the charge or orbitally ordered state is induced by the current. The system behaves in such a way that the bias current may generate metallic paths giving rise to resistivity drop. One can describe this feature by considering the coexistence of localized and delocalized electron states with independent paths of conduction. This situation is reminiscent of what occurs in charge density wave systems where a similar non-linear conduction is also observed. In the light of recent experimental results suggesting the development of charge density waves in charge and orbitally ordered manganese oxides, a phenomenological model for charge density waves motion is used to describe the non-linear conduction in Pr$_{0.63}$Ca$_{0.37}$MnO$_3$. In such a framework, the non-linear conduction arises from the motion of the charge density waves condensate which carries a net electrical current.Comment: 13 pages, 6 figure

Calculation of Enthalpies of Formation of Actinides Nitrides

We report on the results of ab initio electronic structure calculation of total energies of AnN (An = Ac, . . . ,Am), the respective elemental An-metals and the nitrogen molecule using density functional theory (FP APW + lo method and generalized gradient approximation). The obtained energies are further complemented by low temperature heat capacity data and the enthalpies of formation DfH0 298 are eventually evaluated. While the cohesive energies of AnN reveal an increasing dependence on atomic number from ThN to AmN – a trend similar to that of An-metals – the subtle differences between AnN and An result in enthalpies of formation which show strong negative irregularities at ThN and PaN from a linear downward trend. These are ascribed to substantial covalent contribution of 6d and 5f electrons to chemical bonding.JRC.E.4-Nuclear fuel

Calculation of Enthalpies of Formation of Actinides Nitrides.

Abstract not availableJRC.E-Institute for Transuranium Elements (Karlsruhe

High Temperature Heat Capacity of Nd2Zr2O7 and La2Zr2O7 Pyrochlores

he enthalpy increment measurements were performed using drop calorimetry on two lanthanide zirconates Ln2Zr2O7, Ln = La, Nd, with pyrochlore structure. The temperature dependence of heat capacity in the range (298 to 1550) K was derived by simultaneous linear regression of the measured enthalpies combined with the heat capacity data around ambient temperature. The obtained heat capacity CpT is compared to the limit of constant volume lattice Cv calculated from the analysis of low temperature specific heat data using a combined Debye–Einstein harmonic approximation model.JRC.E.4-Nuclear fuel