Phase relations and linear thermal expansion of cubic solid solutions in the Th1−xMxO2−x/2 (M = Eu, Gd, Dy) systems

Cell parameters and linear thermal expansion studies of the Th-M oxide systems with general compositions Th_1−xM_xO_2−x/2 (M = Eu³⁺, Gd³⁺ and Dy³⁺, 0.0 ? x ? 1.0) are reported. The XRD patterns of each product were refined to specify the solid solubility limits of MO_1.5 in the ThO₂ lattice. The upper solid solubility limits of EuO_1.5, GdO_1.5 and DyO_1.5 in the ThO₂ lattice under conditions of slow cooling from 1673 K are represented as Th_0.50Eu_0.50O_1.75, Th_0.60Gd_0.40O_1.80 and Th_0.85Dy_0.15O_1.925, respectively. The linear thermal expansion (293-1123 K) of MO_1.5 and their single-phase solid solutions with thoria were investigated by dilatometery. The average linear thermal expansion coefficients () of the compounds decrease on going from EuO_1.5 to DyO_1.5. The values of for EuO_1.5, GdO_1.5 and DyO_1.5 containing solid solutions showed a downward trend as a function of the dopant concentration. The linear thermal expansion (293-1473 K) of the solid solutions investigated by high-temperature XRD also showed a similar trend.     

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.     

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:

     

Analysis of oxygen potential of (U0.7Pu0.3)O2±x and (U0.8Pu0.2)O2±x based on point defect chemistry

Stoichiometries in (U_0.7Pu_0.3)O_2±x and (U_0.8Pu_0.2)O_2±x were analyzed with the experimental data of oxygen potential based on point defect chemistry. The relationship between the deviation x of stoichiometric composition and the oxygen partial pressure P_O2 was evaluated using a Kröger-Vink diagram. The concentrations of the point defects in uranium and plutonium mixed oxide (MOX) were estimated from the measurement data of oxygen potentials as functions of temperature and P_O2. The analysis results showed that x was proportional to near the stoichiometric region of both (U_0.7Pu_0.3)O_2±x and (U_0.8Pu_0.2)O_2±x, which suggested that intrinsic ionization was the dominant defect. A model to calculate oxygen potential was derived and it represented the experimental data accurately. Further, the model estimated the thermodynamic data, and , of stoichiometric (U_0.7Pu_0.3)O_2.00 and (U_0.8Pu_0.2)O_2.00 as −552.5 kJ·mol⁻¹ and −149.7 J·mol⁻¹, and −674.0 kJ · mol^-1 and −219.4 J · mol⁻¹, respectively.     

Absorption and photoluminescence study of Al2O3 single crystal irradiated with fast neutrons

Colour centers formation in Al₂O₃ by reactor neutrons were investigated by optical measurements (absorption and photoluminescence). The irradiation’s were performed at 40 °C, up to fast neutron (E_n > 1.2 MeV) fluence of 1.4 × 10¹⁸ n cm⁻². After irradiation the coloration of the sample increases with the neutron fluence and absorption band at about 203, 255, 300, 357 and 450 nm appear in the UV-visible spectrum. The evolution of each absorption bands as a function of fluence and annealing temperature is presented and discussed. The results indicate that at higher fluence and above 350 °C the F⁺ center starts to aggregate to F center clusters (F₂, F₂⁺ and ). These aggregates disappear completely above 650 °C whereas the F and F⁺ centers persist even after annealing at 900 °C. It is clear also from the results that the absorption band at 300 nm is due to the contribution of both F₂ center and interstitial ions.     

Standard enthalpy of formation of compounds of the Cd-Zr system

Thermodynamic properties of two intermetallic phases CdZr₂(s) and Cd₃Zr(s) in the binary Cd-Zr system have been investigated. The standard molar enthalpy of formation of CdZr₂(s) and Cd₃Zr(s) was obtained by measuring the reaction enthalpy of CdZr₂(s), Cd₃Zr(s) and Zr(s), respectively, using Cd(l) in a Calvet calorimeter. The values of of CdZr₂(s) and Cd₃Zr(s) at 298 K were found to be −(61.7 ± 1.2) kJ mol⁻¹ and −(72.3 ± 0.9) kJ mol⁻¹, respectively.     

H2 inhibition of radiation induced dissolution of spent nuclear fuel

In order to elucidate the effect of noble metal clusters in spent nuclear fuel on the kinetics of radiation induced spent fuel dissolution we have used Pd particle doped UO₂ pellets. The catalytic effect of Pd particles on the kinetics of radiation induced dissolution of UO₂ during γ-irradiation in containing solutions purged with N₂ and H₂ was studied in this work. Four pellets with Pd concentrations of 0%, 0.1%, 1% and 3% were produced to mimic spent nuclear fuel. The pellets were placed in 10 mM aqueous solutions and γ-irradiated, and the dissolution of was measured spectrophotometrically as a function of time. Under N₂ atmosphere, 3% Pd prevent the dissolution of uranium by reduction with the radiolytically produced H₂, while the other pellets show a rate of dissolution of around 1.6 × 10⁻⁹ mol m⁻² s⁻¹. Under H₂ atmosphere already 0.1% Pd effectively prevents the dissolution of uranium, while the rate of dissolution for the pellet without Pd is 1.4 × 10⁻⁹ mol m⁻² s⁻¹. It is also shown in experiments without radiation in aqueous solutions containing H₂O₂ and O₂ that ?-particles catalyze the oxidation of the UO₂ matrix by these molecular oxidants, and that the kinetics of the catalyzed reactions is close to diffusion controlled.     

Linear free energy relationship applied to trivalent cations with lanthanum and actinium oxide and hydroxide structure

Linear free energy relationships for trivalent cations with crystalline M₂O₃ and, M(OH)₃ phases of lanthanides and actinides were developed from known thermodynamic properties of the aqueous trivalent cations, modifying the Sverjensky and Molling equation. The linear free energy relationship for trivalent cations is as , where the coefficients a_MvX, b_MvX, and β_MvX characterize a particular structural family of MvX, r_M³⁺ is the ionic radius of M³⁺ cation, is the standard Gibbs free energy of formation of MvX and is the standard non-solvation free energy of the cation. The coefficients for the oxide family are: a_MvX = 0.2705, b_MvX = −1984.75 (kJ/mol), and β_MvX = 197.24 (kJ/mol nm). The coefficients for the hydroxide family are: a_MvX = 0.1587, b_MvX = −1474.09 (kJ/mol), and β_MvX = 791.70 (kJ/mol nm).     

Oxygen potential of (U0.88Pu0.12)O2±x and (U0.7Pu0.3)O2±x at high temperatures of 1673-1873 K

The oxygen potential of (U_0.88Pu_0.12)O_2±x (−0.0119 < x < 0.0408) and (U_0.7Pu_0.3)O_2±x (−0.0363 < x < 0.0288) was measured at high temperatures of 1673-1873 K using gas equilibrium method with thermo gravimeter. The measured data were analyzed by a defect chemistry model. Expressions were derived to represent the oxygen potential based on defect chemistry as functions of temperature and oxygen-to-metal ratio. The thermodynamic data, and , at stoichiometric composition were obtained. The expressions can be used for in situ determination of the oxygen-to-metal ratio by the gas-equilibration method. The calculation results were consistent with measured data. It was estimated that addition of 1 wt.% Pu content increased oxygen potential of uranium and plutonium mixed oxide by 2-5 kJ/mol.     

Radiation induced defects in BaBPO5:Ce and their role in thermally stimulated luminescence reactions: EPR and TSL investigations

Defect centers induced by gamma irradiation in Ce doped BaBPO₅ were investigated using EPR spectroscopy. From EPR studies, three phosphorous centered radicals were characterized on the basis of observed ³¹P hyperfine splitting and g values as , and radicals. In addition to this, two types of boron oxygen hole centers (BOHC) and O⁻ were also formed at room temperature. An intense broad signal in sample annealed in argon (g_⊥ = 1.9258 and g_‖ = 1.8839) was assigned to Ce³⁺ ions associated with the electron trapped at anion vacancy or nearby lattice defect. TSL studies showed two glow peaks, a relatively weaker one at 425 K and an intense one at 575 K. Spectral studies of the TSL glow peaks have shown that Ce³⁺ ion acts as emission center. From the temperature dependence of the EPR spectra of gamma irradiated samples, the glow peaks at 425 K and 575 K were attributed to thermal destruction of /O⁻ and BOHC, respectively, by trapping of electrons from elsewhere. The energy released in electron hole recombination process is used for the excitation of Ce³⁺ ions resulting in these glow peaks at 425 K and 575 K. The spectral studies of the TSL glow peaks have shown emission at 330 nm indicating Ce³⁺ acts as the luminescent centre. The trap depth and the frequency factor for the 425 K and 575 K peaks were determined using different heating rates method.     

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.     

Measurement of radiation-enhanced diffusion of La in single crystal thin film CeO2

The diffusion of La, a trivalent cation dopant, actinide surrogate, and high-yield fission product, in CeO₂, a UO₂ nuclear fuel surrogate, during 1.8 MeV Kr⁺ ion bombardment over a temperature range from 673 K to 1206 K has been measured with secondary ion mass spectroscopy. The diffusivity under these irradiation conditions has been analyzed with a model based on a combination of sink-limited and recombination-limited kinetics. This analysis yielded a cation vacancy migration energy of  ∼ 0.4 eV below ∼800 K, were recombination-limited kinetics dominated the behavior. The thermal diffusivity of La in the same system was measured over a range of 873-1073 K and was characterized by an activation enthalpy of . The measurement of both the migration enthalpy and total activation enthalpy separately allows the vacancy formation enthalpy on the cation sublattice to be determined;  ∼ 1 eV. The mixing parameter under energetic heavy-ion bombardment at room temperature was measured as well and found to be ∼4 × 10⁻⁵ nm⁵/eV.     

Existence states of deuterium irradiated into LiAlO2

The existence states of deuterium in LiAlO₂ were analyzed by in situ IR absorption spectroscopy during irradiation with 3 keV at room temperature. Multiple IR absorption peaks that were related to O-D stretching vibrations were observed, mainly at 2650 cm⁻¹ (O-D_α), 2600 cm⁻¹ (O-D_β), and 2500 cm⁻¹ (O-D_γ). The O-D_α was assigned to the surface O-D. The O-D_β and O-D_γ were interpreted as two distinct O-D states for three candidates: O-D of substitutional D⁺ for Li⁺; O-D of substitutional D⁺ for Al³⁺; and O-D of interstitial D⁺. O-D_β was the dominant O-D state for deuterium irradiated into LiAlO₂, and had higher stability than O-D_γ. Heating after ion irradiation led to the desorption of D₂ and an increase in the intensity of O-D_β, which implies that some of the deuterium irradiated into LiAlO₂ exists in non-O-D states, such as D⁻ captured by F centers.     

First principle studies on the electronic structures and absorption spectra in KMgF3 crystal with fluorine vacancy

The experiments indicate that the perfect KMgF₃ crystal has no absorption in the visible range, however the electron irradiation induces a complex absorption spectrum. The absorption spectra can be decomposed by five Gaussian bands peaking at 2.5 eV (488 nm), 3.4 eV (359 nm), 4.2 eV (295 nm), 4.6 eV (270 nm) and 5.2 eV (239 nm), respectively. The purpose of this paper is to seek the origins of the absorption bands. The electronic structures and absorption spectra either for the perfect KMgF₃ or for KMgF₃: with electrical neutrality have been studied by using density functional theory code CASTEP with the lattice structure optimized. The calculation results predicate that KMgF₃: also exhibits five absorption bands caused by the existence of the fluorine ion vacancy and the five absorption bands well coincide with the experimental results. It is believable that the five absorption bands are related to in KMgF₃ crystal produced by the electron irradiation.     

Study of the electronic structures of oxygen doped in LiBaF3 crystal

The most likely substituting positions of impurity oxygen ions in LiBaF₃ crystals are studied using the general utility lattice program (GULP). The calculated results indicate that the main defect model is [] in the O:LiBaF₃ crystal. The electronic structures of the LiBaF₃ crystal with the defect [] are calculated using the DV-Xα method. It can be concluded from the electronic structures that the LiBaF₃ crystal with the defect [] will exhibit a 217-280 nm absorption band and the impurity oxygen will decrease core-valence luminescence yield.     

Transport properties of I, Te and Xe in thoria-urania SIMFUEL

Diffusion properties for volatile fission products iodine and tellurium, and gaseous product xenon in a solid solution of thoria-2 mol% urania doped with fission products for simulating 2 at.% burnup were obtained by studying the release kinetics of the species from trace-irradiated fuel samples at different temperatures using post-irradiation annealing technique. Bulk diffusion coefficients for Xe, I and Te were evaluated in a well-defined powder sample of particle size in the range of 37-45 μm (25 m² kg⁻¹ BET surface area) with 97% of theoretical density. Temperature dependences of the apparent diffusion coefficients of Xe, I and Te derived from this study could be expressed in the form of Arrhenius equations for the respective cases as ln (s⁻¹) = −(19,480 ± 3300)/T − 9.3 ± 2.2 and ln (s⁻¹) = −(31,234 ± 3000)/T − 3.7 ± 2.0, (1273 ? T/K ? 1773) and ln (s⁻¹) = −(22,755 ± 1364)/T − 0.003 ± 0.775, 1700 ? T/K ? 1800. For Xe diffusion the activation energy and frequency factor are 189 kJ mol⁻¹ and 0.997 s⁻¹, respectively. For I and Te the activation energy values are 162 and 260 kJ mol⁻¹, respectively. The respective frequency factors for I and Te are 9.1 × 10⁻⁵ and 2.5 × 10⁻² s⁻¹. On comparison with the reported data in pure urania and thoria matrices a lowering of activation energy for all three species was observed in case of the fission product doped matrix. On the other hand the frequency factor has increased only in the case for diffusion of Xe. This suggests different mechanisms of transport for Xe and volatile fission products I and Te in the fuel matrix.     

Structural and gasochromic properties of epitaxial WO3 films prepared by pulsed laser deposition

The structural and gasochromic properties of epitaxial tungsten trioxide (WO₃) thin films, prepared by ArF excimer pulsed laser deposition under the controlled oxygen atmosphere, have been investigated. The WO₃ films were grown on the α-Al₂O₃ substrates, as the oxygen pressure ranged from 0.57 to 1.20 Pa and the substrate temperature ranged from 432 to 538 °C. The deposited films were characterized by Rutherford backscattering spectroscopy (RBS)/channeling, X-ray diffraction, X-ray pole figures and Raman spectroscopy. RBS and XRD results demonstrated that monoclinic WO₃ (0 0 1) films were successfully grown on the α-Al₂O₃ substrates. The crystal quality was improved by increasing both the oxygen pressure and the substrate temperature. Gasochromic coloration in the WO₃ films by exposure to diluted hydrogen gas was found to correlate with the crystal quality of the films. The gasochromic coloration was suppressed by the epitaxial growth of the films.