Thermodynamic properties of LiNiO2, LiCoO2, and LiMnO2 using density-functional theory.

The formation energies of LiCoO2, LiNiO2 and LiMnO2 were calculated using a combination of adequately selected Hess cycles and DFT computations. Several exchange-correlation functionals were tested and PBE for solids (PBEsol) turned out to be the most accurate. The enthalpies of formation at 0 K are -168.0 kJ mol at-1 for LiCoO2, -173.2 kJ mol at-1 for LiNiO2, -209.9 kJ mol at-1 for o-LiMnO2 and -208.8 kJ mol at-1 for r-LiMnO2. In comparison to experimental formation energy data, a difference of 1.6 and 0.01 kJ mol at-1 was obtained for LiCoO2 and LiMnO2, respectively. By contrast, a much larger discrepancy, around 24 kJ mol at-1, was obtained for LiNiO2 and confirmed by using an additional and independent Hess cycle. The influence of slight crystallographic distortions associated with magnetism and/or the Jahn-Teller effect on energy was carefully searched for and taken into account, as well as corrections arising from vibrational contributions. Hence, these results should motivate future measurements of the thermodynamic properties of LiNiO2, which are currently scarce. Vibrational contributions to the structural and energetic properties were computed within the harmonic and the quasi-harmonic approximations. The LiCoO2 heat capacity at constant pressure is in excellent agreement with experimental data, with a difference of only 3.3% at 300 K. In the case of LiNiO2 the difference reaches 17% at 300 K, which could also motivate further investigation. The Cp(T) value for the orthorhombic phase o-LiMnO2, for which no previous data were available, was computed. Structural properties such as specific mass, bulk modulus and coefficient of thermal expansion are presented.

A spectroscopic hike in the U-O phase diagram.

The U-O phase diagram is of paramount interest for nuclear-related applications and has therefore been extensively studied. Experimental data have been gathered to feed the thermodynamic calculations and achieve an optimization of the U-O system modelling. Although considered as well established, a critical assessment of this large body of experimental data is necessary, especially in light of the recent development of new techniques applicable to actinide materials. Here we show how in situ X-ray absorption near-edge structure (XANES) is suitable and relevant for phase diagram determination. New experimental data points have been collected using this method and discussed in regard to the available data. Comparing our experimental data with thermodynamic calculations, we observe that the current version of the U-O phase diagram misses some experimental data in specific domains. This lack of experimental data generates inaccuracy in the model, which can be overcome using in situ XANES. Indeed, as shown in the paper, this method is suitable for collecting experimental data in non-ambient conditions and for multiphasic systems.

Structural and Thermodynamic Investigation of the Perovskite Ba2NaMoO5.5.

Neutron diffraction, X-ray absorption spectroscopy (XAS), and Raman spectroscopy measurements of the quaternary perovskite phase Ba2NaMoO5.5 have been performed in this work. The cubic crystal structure in space group Fm3̅m has been refined using the Rietveld method. X-ray absorption near-edge structure spectroscopy (XANES) measurements at the Mo K-edge have confirmed the hexavalent state of molybdenum. The local structure of the molybdenum octahedra has been studied in detail using extended X-ray absorption fine structure (EXAFS) spectroscopy. The Mo-O and Mo-Ba distances have been compared to the neutron diffraction data with good agreement. The coefficient of thermal expansion measured in the temperature range of 303-923 K, using high temperature X-ray diffraction (HT-XRD) (αV = 55.8 × 10-6 K), has been determined to be ∼2 times higher than that of the barium molybdates BaMoO3 and BaMoO4. Moreover, no phase transition nor melting have been observed, neither by HT-XRD nor Raman spectroscopy nor differential scanning calorimetry, up to 1473 K. Furthermore, the standard enthalpy of formation (ΔfHm°) for Ba2NaMoO5.5(cr) has been determined to be -(2524.75 ± 4.15) kJ mol-1 at 298.15 K, using solution calorimetry. Finally, the margin for safe operation of sodium-cooled fast reactors (SFRs) has been assessed by calculating the threshold oxygen potential needed, in liquid sodium, to form the quaternary compound, following an interaction between irradiated mixed oxide (U,Pu)O2 fuel and sodium coolant.

Insight into the Am-O Phase Equilibria: A Thermodynamic Study Coupling High-Temperature XRD and CALPHAD Modeling.

In the frame of minor actinide transmutation, americium can be diluted in UO2 and (U, Pu)O2 fuels burned in fast neutron reactors. The first mandatory step to foresee the influence of Am on the in-reactor behavior of transmutation targets or fuel is to have fundamental knowledge of the Am-O binary system and, in particular, of the AmO2-x phase. In this study, we coupled HT-XRD (high-temperature X-ray diffraction) experiments with CALPHAD thermodynamic modeling to provide new insights into the structural properties and phase equilibria in the AmO2-x-AmO1.61+x-Am2O3 domain. Because of this approach, we were able for the first time to assess the relationships between temperature, lattice parameter, and hypostoichiometry for fcc AmO2-x. We showed the presence of a hyperstoichiometric existence domain for the bcc AmO1.61+x phase and the absence of a miscibility gap in the fcc AmO2-x phase, contrary to previous representations of the phase diagram. Finally, with the new experimental data, a new CALPHAD thermodynamic model of the Am-O system was developed, and an improved version of the phase diagram is presented.