Chemical thermodynamic representation of AmO2−x

The AmO_2−x solid solution data set for the dependence of the oxygen potential on the composition, x, and temperature was retrieved from the literature and represented by a thermodynamic model. The data set was analysed by least-squares using equations derived from the classical thermodynamic theory for the solid solution of a solute in a solvent. Two representations of the AmO_2−x data were used, namely the Am_5/4O₂–AmO₂ and AmO_3/2–AmO₂ solid solution. No significant difference was found between the two, and the Am_5/4O₂–AmO₂ solution was preferred on the basis of the phase diagram. From the results the Gibbs energy of formation of Am_5/4O₂ has been derived.     

Phase diagram and thermodynamic properties of the system MnCl2-UCl4, prediction and investigation results

The MnCl₂-UCl₄ system was studied employing differential thermal analysis, common thermal analysis and high-temperature cryometry. From the results obtained, both the phase diagram and the thermodynamic characteristics of liquid phases of the system have been determined. The results were discussed in terms of regularities found in the phase equilibria of binary salt systems with common anion and compared with those for other systems of the type MCl_n-UCl₄. It appeared that the results confirmed earlier predictions on the title system.     

Thermodynamic properties of the O-U system. II - Critical assessment of the stability and composition range of the oxides UO2+x, U4O9−y and U3O8−z

The published data concerned with the determination of the composition ranges of uranium oxides, UO_2+x, U₄O_9−y and U₃O_8−z, which have been determined using thermogravimetric, X-ray diffraction and electrochemical techniques are critically assessed. U₄O₉ and U₃O₈ have quite small domains of composition and the assessment of such data has carefully considered the uncertainties in the experimental determinations. In addition, the thermodynamic properties of U₄O₉ and U₃O₈, enthalpies of formation and transformation, entropies, and thermal capacities are analyzed and selected to build a primary data base for compounds.     

Thermodynamics of the O-U system. I - Oxygen chemical potential critical assessment in the UO2-U3O8 composition range

A critical assessment of oxygen chemical potential of UO_2+x, U₄O₉ and U₃O₈ oxide non-stoichiometric phases as well as of diphasic related domains has been performed in order to build up primary input data files used in a further optimization procedure of thermodynamic and phase diagram data for the uranium-oxygen system in the UO₂-UO₃ composition range. Owing to the fact that original data are very numerous, more than 500 publications, a twofold process is used for the assessment - (i) first a critical selection of data is performed for each method of measurement together with a careful estimate of their uncertainties, (ii) second a reduction of the total number of data on the basis of a chart with fixed intervals of temperature and composition that allows a comparison to be made of the results from the various experiments. Results are presented for chemical potentials of oxygen with their associated uncertainties.     

Thermodynamic studies on SrThO3(s)

The Gibbs energy of formation of SrThO₃(s) has been determined using e.m.f. and manometric techniques. In the e.m.f. method, two fluoride cells have been constructed to determine Δ_fG⁰_m(SrThO₃,s,T) using CaF₂(s) as a solid electrolyte. The cells used are:

     

Vapour pressure and standard enthalpy of sublimation of H3BO3

A horizontal thermal analysis instrument was adapted as a transpiration apparatus for the measurement of vapour pressure of solid boric acid, H₃BO₃. The experimental parameters necessary for establishing a dynamic isothermal congruent vapourisation equilibrium of H₃BO₃ were identified. Using these optimized transpiration experiments, the vapour pressures were measured in the temperature range 326-363 K. The temperature dependence of the measured values of vapour pressures could be expressed using the expression, log(p/Pa) = 26.83(±0.09) − 9094(±246)/T (K). The standard enthalpy of sublimation, , of H₃BO₃ was estimated to be 174.1 ± 4.7 kJ mol⁻¹ at the mean temperature of the present measurements, viz., 345 K.     

Elastic and electronic properties and stability of SrThO3, SrZrO3 and ThO2 from first principles

First-principle calculations in the framework of the full-potential linearized-augmented-plane-wave method (FLAPW, as implemented into the WIEN-2k code) have been performed to understand the structural, elastic, cohesive and electronic properties of the meta-stable cubic strontium thorate SrThO₃. The optimized lattice parameters, elastic parameters, formation energies, densities of states, band structures and charge density distributions are obtained and discussed in comparison with those of cubic SrZrO₃ and ThO₂.     

Progress in the thermodynamic modelling of the O-U binary system

The fuel of civil nuclear plants, UO₂, melts at 3120 K. During an hypothetical severe accident, urania, submitted to high temperatures and various oxygen potentials, presents a wide non-stoichiometry range: the melting temperature of UO_2±x, related to oxygen potential, decreases in all cases. In this scenario, urania could react with other materials, firstly zircaloy, and the melting temperature of (U, Zr)O_2±x still decreases. That is why the critical assessment of the O-U binary system including the non-stoichiometry range of urania, is a major step to a correct thermodynamic modelling of multicomponent systems for nuclear safety. The very numerous experimental information has been compiled and analysed. The associate model was used for the liquid phase, and a sublattice model for UO_2±x; U₄O_9−y, U₃O₈ and UO₃ were treated as stoichiometric. Phase diagram and thermodynamic properties have been calculated from the optimised Gibbs energy parameters. The calculated consistency with the experimental ones is quite satisfactory.     

Characterization and densification studies on ThO2-UO2 pellets derived from ThO2 and U3O8 powders

ThO₂ containing around 2-3% ²³³UO₂ is the proposed fuel for the forthcoming Indian Advanced Heavy Water Reactor (AHWR). This fuel is prepared by powder metallurgy technique using ThO₂ and U₃O₈ powders as the starting material. The densification behaviour of the fuel was evaluated using a high temperature dilatometer in four different atmospheres Ar, Ar-8%H₂, CO₂ and air. Air was found to be the best medium for sintering among them. For Ar and Ar-8%H₂ atmospheres, the former gave a slightly higher densification. Thermogravimetric studies carried out on ThO₂-2%U₃O₈ granules in air showed a continuous decrease in weight up to 1500 °C. The effectiveness of U₃O₈ in enhancing the sintering of ThO₂ has been established.     

Formation of columnar and equiaxed grains by the reduction of U3O8 pellets to UO2+x

The reduction of U₃O₈ pellets to UO_2+x has been investigated at 1300 °C in H₂, Ar and CO₂ gas atmospheres by TGA, SEM, and X-ray diffraction. The selected U₃O₈ pellet was prepared by sintering a U₃O₈ powder compact. The TGA results show that the reduction rate is fastest in H₂ gas, and X-ray diffraction indicates that U₃O₈ reduces to UO_2+x without any intermediate phase. The reduced pellet, UO_2+x, has a special grain structure that consists of equiaxed grains at the surface, columnar grains in the middle, and equiaxed grains in the center. The equiaxed grains and columnar grains are much smaller in H₂ gas than in Ar or CO₂ gas. The reducing gases significantly influence the morphology of the grain structure. This difference can be explained in terms of a relation between oxygen potential and critical nucleus size during the reduction.     

Enthalpy measurements of La2Te3O9 and La2Te4O11

Enthalpy increment measurements on La₂Te₃O₉(s) and La₂Te₄O₁₁(s) were carried out using a Calvet micro-calorimeter. The enthalpy values were analyzed using the non-linear curve fitting method. The dependence of enthalpy increments with temperature was given as: H°(T) − H°(298.15 K) (J mol⁻¹) = 360.70T + 0.00409T² + 133.568 × 10⁵/T − 149 923 (373 ? T (K) ? 936) for La₂Te₃O₉ and H°(T) − H°(298.15 K) (J mol⁻¹) = 331.927T + 0.0549T² + 29.3623 × 10⁵/T − 114 587 (373 ? T (K) ? 936) for La₂Te₄O₁₁.     

Chlorination of UO2, PuO2 and rare earth oxides using ZrCl4 in LiCl-KCl eutectic melt

A new chlorination method using ZrCl₄ in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl₄ has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La₂O₃, CeO₂, Nd₂O₃ and Y₂O₃) and actinide oxides (UO₂ and PuO₂) were allowed to react with ZrCl₄ in a LiCl-KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO₂. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl₄ chlorination method, free from corrosive gas, was very simple and useful.     

Heats of formation of (U,Mo)Al3 and U(Al,Si)3

The heats of formation of (U,Mo)Al₃ intermetallic compounds were obtained by measuring the reaction heats of U-Mo/Al dispersion samples by differential scanning calorimetry. Based on literature data for the reaction heats of U₃Si/Al and U₃Si₂/Al dispersion samples, the heats of formation of U(Al,Si)₃ as a function of the Si content were calculated. The heat of formation of (U,Mo)Al₃ becomes less negative as the Mo content increases. Conversely, the heat of formation of U(Al,Si)₃ becomes more negative with increasing Si content.     

Vaporization behavior and Gibbs energy of formation of Rb2ThO3

The thermodynamic stability of rubidium thorate, Rb₂ThO₃(s), was determined from vaporization studies using the Knudsen effusion forward collection technique. Rb₂ThO₃(s) vaporized incongruently and predominantly as Rb₂ThO₃(s)=ThO₂(s) + 2Rb(g) + 1/2 O₂(g). The equilibrium constant K=p_Rb²·p_O2^1/2 was evaluated from the measurement of the effusive flux due to Rb vapor species under the oxygen potential governed by the stoichiometric loss of the chemical component Rb₂O from the thorate phase. The Gibbs energy of formation of Rb₂ThO₃ derived from the measurement and other auxiliary data could be given by the equation, Δ_fG°(Rb₂ThO₃,s)=−1794.7+0.42T ± .     

Thermophysical studies on the binary system UO2(NO3)2·6H2O - Sr(NO3)2

Thermoanalytical (TG-DTA-EGA) and X-ray diffraction measurements have been used to study the reaction between uranyl nitrate hexahydrate and strontium nitrate. The results confirmed the absence of a direct interaction between the two compounds. The presence of strontium nitrate, however, ensured that the extent of hydrolysis and polymerisation of uranyl nitrate hexahydrate during its dehydration and decomposition to UO₃ is significantly reduced. DTA curves recorded in both heating and cooling modes gave evidence to the occurrence of a reaction between molten strontium nitrate and uranium trioxide to form nitrato-complexes of uranium and strontium. X-ray diffraction data on reaction residues obtained at different temperatures and cooled to room temperature also showed evidence for the formation of such complexes. The results obtained indicated an increase in thermal stability of these nitrato-complexes with increase in Sr/U ratio. The complex with an Sr/U ratio of 2.0 is stable up to 660 °C and the complex with Sr/U ratio of 4.0 is stable up to 680 °C. These complexes decompose at higher temperatures to give strontium uranates.     

Thermal variation of the optical absorption of UO2: determination of the small polaron self-energy

The temperature variation of UV-VIS-NIR optical spectra of UO₂ have been investigated from room temperature up to 1173 K with careful in situ oxygen partial pressure control. The deduced optical absorption edge exhibits a strong temperature dependence. Its value decreases from ∼2 eV at room temperature to ∼0.8 eV at 1173 K. Such thermal behaviour is interpreted as the consequence of the existence of a strong electron-phonon coupling (small polaron). In the temperature range 300-1173 K, the model yields a hopping radius of ∼2 Å and a polaron self-energy of E_p=−0.38 eV.     

Understanding of copper precipitation under electron or ion irradiations in FeCu0.1 wt% ferritic alloy by combination of experiments and modelling

This work is dedicated to the understanding of the basic processes involved in the formation of copper enriched clusters in low alloyed FeCu binary system (FeCu0.1 wt%) under irradiation at temperature close to 300 °C. Such an alloy was irradiated with electrons or with ions (Fe⁺ or He⁺) in order to deconvolute the effect of displacement cascades and the associated generation of point defect clusters (ion irradiations), and the super-saturation of mono-vacancies and self-interstitial atoms (electron irradiation). The microstructure of this alloy was characterised by tomographic atom probe. Experimental results were compared with results obtained with cluster dynamic model giving an estimation of the evolution of point defects (free or agglomerated) under irradiation on the one hand and describing homogeneous enhanced precipitation of copper on the other hand. The comparison between the results obtained on the different irradiation conditions and the model suggests that the point defect clusters (dislocation loops and/or nano-voids) created in displacement cascades play a major role in copper clustering in low copper alloy irradiated at 573 K.     

Phase relations in the quaternary Fe-Pu-U-Zr system

The phase diagram in the quaternary Fe-Pu-U-Zr system was established at 923 K in the uranium-rich region to understand better the compatibility between the metal fuel and stainless steel cladding in a fast reactor. The experimental phase relation data obtained in this study was applied to the thermodynamic methodology for construction of the phase diagram. The calculated phase diagram was consistent and well within the experimental data. The applicability of the thermodynamic model to other temperatures was confirmed by comparing the present results of differential thermal analysis with the calculated phase diagrams. These consistencies mean that both the thermodynamic model and the assessed parameters in the binary and ternary subsystems developed so far are reasonable. The calculated phase diagram established in this study was also in good agreement with the analysis of the diffusion zone in tests on Pu-U-Zr/Fe couples. This suggests that the diffusion zone formed at the fuel-cladding interface in the reactor system can be assessed using the phase diagram in the quaternary Fe-Pu-U-Zr system.