Electrical conduction in UO2+x

The temperature dependence of electrical conductivity in UO_2+x has been measured in the temperature range 800–1340 K. It is suggested that an electrical current is carried by positive holes in the 2p band of oxygen, produced by the transfer of electrons to the vacant 5f band in U⁺⁵ ions associated with defect complexes.     

Electrical conductivity and thermoelectric power in irradiated UO2 + x

Two kinds of UO_{2 + x}, the O/U ratios of which were 2.002 and 2.004, respectively, were irradiated to a dose range between 1.14 × 10¹⁴ and 1.90 × 10¹⁸ fissions/cm³, and electrical conductivity changes were measured. A steep decrease in conductivity was observed with increasing dose up to 1 × 10¹⁵ fissions/cm³, a gradual increase followed between 1 × 10¹⁵ and 1 × 10¹⁸ fissions/cm³ and above this dose the conductivity abruptly increased. Thermoelectric power measurements were also carried out for the specimens irradiated in the dose range up to 1.90 × 10¹⁸ fissions/cm³. It might be suggested that p-type conduction contributes to the electrical conductivity in irradiated specimens up to 1.90 × 10¹⁸ fissions/cm³.     

Electrical conductivity of UO2-ThO2 solid solutions

The electrical conductivities of UO_2+x. ThO₂ and their solid solutions, in thermodynamic equilibrium with the gas phase, were measured as a function of temperature, and of oxygen partial pressure in the temperatnre range 800 to 1200°C. The slope of the plot log α versus 1/$\text{T}$ for UO_2+x and UO₂-rich solid solutions exhibits a single region, whereas in the ThO₂-rich solid solutions it exhibits two regions. The pressure dependence of the conductivity (σ) in the UO₂-rich solid solutions can be represented by σ ∝ [O_i] ∝ in the range of $\text{0.01 < x < 0.1}$. Here, O_i is an interstitial oxygen and the partial pressure of oxygen, and it varies with the ThO₂ content. At greater deviation from stoichiometry ($\text{x ? 0.1}$) the presence of U₄O₉ or (Th U)₄O₉ phases influences the conductivity data. In ThO$\text{2}$ or ThO₂-rich solid solutions. P-type conduction at high oxygen pressures is interpreted as arising from the incorporation of excess oxygen into oxygen vacancies.     

Phasengleichgewichte in den systemen UO2-UO2,67-ThO2 und UO2 + x-NPO2

Solid-state chemical investigations have established that in the compositional range UO₂-UO_2.67-ThO₃ of the U-Th-O ternary system, the following single-phase domains exist: U₃O₈, which does not dissolve any ThO₂ in the solid state; an ordered M₄O₉ phase on the section between U₄O₉ and U₂Th₂O₉, below ≈ 1150 °C; and a phase with fluorite structure which occupies a large part of the system and which at 1250 °C is bounded by the compositions UO₂-UO_2.25 (U_0.43, ThO_0.57)O_0.25-ThO₃. The maximum O/M ratio of the “fluorite” phase is O:(U + Th) = 2.25. The highest oxidation valency of uranium is 5.30; this value falls as more thorium oxide is incorporated in the (U.Th)O_{2 + x} “fluorite” phase.     

Shell model calculation of enthalpy of solution of MgO in UO2+x

A computer program to evaluate the formation energies of defects in fluorite crystals is developed on the basis of the shell model Intrinsic defects of UO₂ are calculated with this program using the potential parameters reported by Catlow. The results are in agreement with those of Catlow. The present computer program is applied to a study of nonstoichiometry of the solid solutions of MgO and UO_2+x The calculation of the enthalpy of solution of MgO in UO_2+xis carried out on the basis of several defect models for charge compensation in the solid solution Mg_yU_1?yO_2±xThe calculated results are discussed in the light of our recent experimental work. It is proved that the present theoretical calculation predicts reasonably well the nonstoichiometric properties of the solid solution.     

The thermal conductivity of UO2 vapor

The thermal conductivity, λ of a saturated vapor over UO_1.96 is calculated in the temperature range 3000–6000 K. The calculation shows that the contribution to λ from the transport of reaction enthalpy dominates all other contributions. All possible reactions of the gaseous species UO₃, UO₂, UO, U, O, and O₂ are included in the calculation. We fit the total thermal conductivity to the empirical equation λ = exp(a+ b/T+cT+dT² + eT³), with λ in cal/(cm s K), T in kelvins, a = 268.90, B = − 3.1919 × 10⁵, C = −8.9673 × 10⁻², d = 1.2861 × 10⁻⁵, and E = −6.7917 × 10⁻¹⁰.     

Vaporization study on UO2 and (U1−yNby)O2+x by mass-spectrometric method

The vapor pressures over UO_2.000 and (U_1?yNb_y)O_2+x (y = 0.01, 0.05, x = 0.000–0.022) were measured by the mass-spectrometric method in the temperature range 2025–2343 K. The main gas species over UO_2.000 were observed to be UO₃(g) and UO₂(g) and those over (U_1?yNb_y)O_2+x were NbO₂(g), NbO(g), UO₃(g) and UO₂(g). The partial vapor pressures of almost all gas species over (U_1?yNb_y)O_2+x increased with increasing O/M (M = U + Nb) ratio. With increasing Nb content in (U_1?yNb_y)O_2.000, the partial vapor pressures of UO₂(g) and UO₃(g) decreased and those of NbO(g) and NbO₂(g) increased. The congruently vaporizing composition in the (U_1?yNb_y)O_2+x phase was estimated to be ($\text{U}{}_{\mathrm{0.985\pm 0.005}}\text{Nb}{}_{\mathrm{0.015\pm 0.005}}\text{)O}{}_{2.000}$ from the compositional dependence of the total vapor pressures. The partial molar enthalpy and entropy of oxygen of (U_1?yNb_y)O_2+x calculated from the partial pressures of gaseous species NbO₂(g) and NbO(g) were in fairly good agreement with those previously obtained by the present authors with a thermobalance.     

Frequency dependence of electrical conductivity and dielectric constant of UO2

The dielectric constant and electrical conductivity of single crystal and polycrystalline UO₂ are found to be frequency dependent. The dielectric constant measured at low frequencies is anomalously large at room temperature but decreases to a limiting value (~25) below about 130 K. A knee observed in the temperature dependence of the conductivity of polycrystalline UO₂ corresponds to a process having an activation energy of 0.15 eV.     

Reduction of UO2 by H2

The reactivity of H₂ towards UO₂²⁺ has been studied experimentally using a PEEK coated autoclave where the UO₂²⁺ concentration in aqueous solution containing 2 mM carbonate was measured as a function of time at p_H2∼40 bar. The experiments were performed in the temperature interval 74-100 °C. In addition, the suggested catalytic activity of UO₂ on the reduction of UO₂²⁺ by H₂ was investigated. The results clearly show that H₂ is capable of reducing UO₂²⁺ to UO₂ without the presence of a catalyst. The reaction is of first order with respect to UO₂²⁺. The activation energy for the process is 130 ± 24 kJ mol⁻¹ and the rate constant is k_298K=3.6×10⁻⁹ l mol⁻¹ s⁻¹. The activation enthalpy and entropy for the process was determined to 126 kJ mol⁻¹ and 16.5 J mol⁻¹ K⁻¹, respectively. Traces of oxygen were shown to inhibit the reduction process. Hence, the suggested catalytic activity of freshly precipitated UO₂ on the reduction of UO₂²⁺ by H₂ could not be confirmed.     

Sintering diagrams of UO2

Ashby's method of constructing sintering diagrams has been modified to obtain relative contribution diagrams directly from the computer. It is endeavoured here to study the interplay of sintering variables and mechanisms and determine the factors that affect the participation of mechanisms in UO₂. By studying the physical properties, it emerges that the order of inaccuracies is small in most cases and do not affect the diagrams. On the other hand, even a 10% error in activation energies, which is quite plausible, would make a significant difference to the diagram. The main criticism of Ashby's approach is that the numerous properties and equations used, communicate their inaccuracies to the diagrams and make them unreliable. Our study has considerably reduced the number of factors that need to be refined to make the sintering diagrams more meaningful.     

Fission-induced densification of UO2

A new technique has been developed to study fission-induced densification and hot-pressing of UO₂ at very low temperatures without complications from fracturing or other concurrent thermal effects. Thin disks of UO₂ of 0.22 to 20% enrichment and differing microstructural stability, were irradiated in the core of the CP — reactor at temperatures below 200°C and at pressures from 1 atm to 20.7 MPa. Results indicate that the pressurizing medium, NaK, had penetrated the open porosity at high pressure and impeded densification. To rationalize this effect, the previously proposed models for radiationinduced densification are critically reviewed. Modifications to models involving thermal sintering and hot-pressing, and pore resolution appear the most tenable. The former mechanism leads to predictions that fission-induced hot-pressing can occur, and ex-reactor sintering and hot-pressing should correlate with in-reactor densification. The proximity of pores and grain boundaries is also stressed. The effect of NaK logging is rationalized by changes in pore surface energy and by stabilization of small pores aginst complete resolution.     

Optical properties of UO2 and PuO2

We perform first-principles calculations of electronic structure and optical properties for UO₂ and PuO₂ based on the density functional theory using the generalized gradient approximation (GGA) + U scheme. The main features in orbital-resolved partial density of states for occupied f and p orbitals, unoccupied d orbitals, and related gaps are well reproduced compared to experimental observations. Based on the satisfactory ground-state electronic structure calculations, the dynamical dielectric function and related optical spectra, i.e., the reflectivity, adsorption coefficient, energy-loss, and refractive index spectrum, are obtained. These results are consistent with the available experiments.     

A mechanism for the ease of slip in UO2+x

The microstructure of plastically deformed hyperstoichiometric uranium dioxide crystals has been reexamined by transmission electron microscopy. Although the U₄O₉ phase is present with its usual superlattice structure, dislocations which thread interfaces between it and the adjacent UO₂ phase exhibit uniform contrast, (i.e., no separation into superdislocations is resolved). Dislocations lying totally within the UO₂ phase are decorated by “shadows” of gray contrast, which can be removed by heating in the microscope atmosphere. These have been identified as “atmospheres” of U₄O₉. A geometrical argument, based on the coordinates of anion interstitials published by Willis, is used to explain how these “atmospheres” might account for the observed incidence of extensive cross-slip in plastically deforming UO_2+x.     

Kinetics of initial stage of sintering of UO2 and UO2 with Nd2O3 addition

The kinetics of initial stage sintering of UO₂ powder were reinvestigated, using Ar-10% H₂ atmosphere. The effect of the addition of neodynium oxide was studied. The results revealed that surface and grain boundary diffusion mechanisms act simultaneously. The values of activation energies were found to be $\text{48.48 ± 3.51 kcal/mole}$ in the temperature range 870–942°C and $\text{89.88 ± 9.87 kcal/mole}$ in the temperature range of 942–1030°C for UO₂, and $\text{115.61 ± 7.77 kcal/mole}$ in the temperature range 1030–1150°C for UO₂ + Nd₂O₃. An important decrease in the calculated diffusion coefficient occurs by the addition of Nd₂O₃.     

Phase diagram of the UO2-FeO1+x system

Phase-relation studies of the UO₂-FeO_1+x system in an inert atmosphere are presented. The eutectic point has been determined, which corresponds to a temperature of (1335 ± 5) °C and a UO₂ concentration of (4.0 ± 0.1) mol.%. The maximum solubility of FeO in UO₂ at the eutectic temperature has been estimated as (17.0 ± 1.0) mol.%. Liquidus temperatures for a wide concentration range have been determined and a phase diagram of the system has been constructed.