Phase equilibrium of PuO2−x − Pu2O3 based on first-principles calculations and configurational entropy change

Combination of an oxygen vacancy formation energy calculated using first-principles approach and the configurational entropy change treated within the framework of statistical mechanics gives an expression of the Gibbs free energy at large deviation from stoichiometry of plutonium oxide PuO₂. An oxygen vacancy formation energy 4.20 eV derived from our previously first-principles calculation was used to evaluate the Gibbs free energy change due to oxygen vacancies in the crystal. The oxygen partial pressures then can be evaluated from the change of the free energy with two fitting parameters (a vacancy-vacancy interaction energy and vibration entropy change due to induced vacancies). Derived thermodynamic expression for the free energy based on the SGTE thermodynamic data for the stoichiometric PuO₂ and the Pu₂O₃ compounds was further incorporated into the CALPHAD modeling, then phase equilibrium between the stoichiometric Pu₂O₃ and non-stoichiometric PuO_2−x were reproduced.     

RBS investigations of buffer layers between YBa2Cu3O7−x and silicon

The deposition of high-quality high-T_c superconducting films on silicon wafers for future hybrid electronic devices is strongly hampered by the interdiffusion between films and substrate. This effect degrades the superconducting properties seriously and is a strong function of temperature. Since high processing temperatures are inevitable for good films, suitable buffer layers are needed to reduce the interdiffusion. We have investigated the combinations ZrO₂/Si(100), BaF₂/Si(100), and noble-metal/TiN/Si(100) at temperatures up to 780°C in oxidizing ambient. YBa₂Cu₃O_7−x films have been deposited onto the buffer layers by laser ablation. Thereafter the interfaces have been analyzed by Rutherford backscattering. So far only ZrO₂ has demonstrated sufficient stability to serve as a buffer layer for the laser-ablated YBa₂Cu₃O_7−x films. All other combinations suffer from interdiffusion or oxidation.     

Analysis of structural modifications in γ-irradiated PbO–B2O3–SiO2 glasses by FTIR spectroscopy

The effect of γ-irradiation on the structure of lead borosilicate glasses of varying composition has been probed by FTIR spectroscopy, before and immediately after γ-irradiation. The glasses were irradiated at Calliope ⁶⁰Co plant (RC ENEA Casaccia, Rome), and the spectra were recorded after absorbed doses of 50 Gy, 500 Gy, and 4 kGy. The structural analysis have been made considering both the effect of composition and of irradiation. The experimental results clearly indicate that after irradiation a significant change in structure of borosilicate glass network is observed.     

Magnetic ordering in superconducting YBa2(Cu1−xFex)3Oy oxide

Magnetic susceptibility measurement and the zero-field muon-spin-relaxation experiment have been made for the YBa₂(Cu_1−xFe_x)₃O_y system. The susceptibility has been measured in the field strong enough for the magnetic flux to penetrate the superconductor and the resultant temperature dependence has demonstrated the field cooled effect and a cusp at low temperatures below T_c. The cusp has been observed when the high field has been applied. The dynamical depolarization rate of the muon obtained by the muon-spin-relaxation experiment has shown the maximum at the same temperature as the cusp. The results suggest that the spin glass freezing of localized magnetic moment takes place at the temperature of the cusp, which is consistent with the previous Mössbauer effect experiments. The magnetic phase diagram for the system has been obtained.     

Comparative study of silicate glasses containing Bi2O3, PbO and BaO: Radiation shielding and optical properties

The radiation shielding and optical properties of xBi₂O₃:(100-x)SiO₂, xPbO:(100-x)SiO₂ and xBaO:(100-x)SiO₂ glass systems (where 30 ? x ? 70 is the composition by weight%) have been investigated. Total mass attenuation coefficients (μ_m) of glasses at 662 keV were improved by increasing their Bi₂O₃ and PbO content, which raised the photoelectric absorption in glass matrices. Raising the BaO content to the same fraction range, however, brought no significant change to μ_m. These results indicate that photon is strongly attenuated in Bi₂O₃ and PbO containing glasses, and but not in BaO containing glass. The results from the optical absorption spectra show an edge that was not sharply defined; clearly indicating the amorphous nature of glass samples. It is observed that the cutoff wavelength for Bi₂O₃ containing glass was longer than PbO and BaO containing glasses.     

Gamma-ray shielding and structural properties of PbO-SiO2 glasses

Gamma-ray attenuation coefficients have been determined experimentally using a narrow beam transmission method for the xPbO(1−x)SiO₂ (x = 0.45-0.70) glass system at 662, 1173 and 1332 keV photon energies. These values have also been obtained theoretically using the ‘mixture rule’ and the ‘XCOM’ computer software. The results have been used to calculate half value layer parameters. Gamma-ray shielding properties of PbO-SiO₂ glass samples have been compared with standard radiation shielding concretes. The molar volume, FTIR and acoustic investigations have been used to study the structural properties of the prepared glass system.     

Ion-beam induced effects in α-Al2O3 at 15 K

In order to study the primary effects of ion-beam induced damage formation in sapphire, implantation and subsequent damage analysis by Rutherford backscattering spectrometry (RBS) in channelling configuration were performed at 15 K without change of the sample temperature. We used 80 keV Na, 150 keV K and 150 keV Ar to investigate the damage accumulation with increasing ion fluence. During the RBS measurement with 1.4 MeV He ions at 15 K, defect annealing was observed. From the measured channelling spectra, defect profiles were calculated using the computer code DICADA. These profiles are narrower and distinctly lower than those calculated by SRIM2003, especially below the surface. This suggests an enhanced recombination of defects within this area. The damage concentration at the peak maximum is analysed as a function of ion fluence or rather displacements per atom. The model that was applied contains two different types of defects, namely point defects and clusters and takes into account the defect annealing under the He beam. For both defect profiles and damage accumulation, no significant influence of the implanted ion species was observed.     

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.     

Micro-PIXE and channeling PIXE analysis of Ag-doped YBa2Cu3O7−δ thin films

Nuclear Microscopy, utilizing a 2 MeV He⁺ beam for channeling Rutherford Backscattering (RBS) and PIXE analysis, was used to characterise Ag-doped YBa₂Cu₃O_7−δ thin films and measure the lateral distribution of the Ag. The samples were prepared by in situ two-beam pulsed laser deposition in order to investigate the effects of such dopings on critical current densities [1 and 2]. Films deposited at temperatures above 650°C form needle-like surface structures with a length of up to 100 μm; these tend to align with in-plane a–b axis. Results for a sample prepared at a substrate temperature of 730°C and a maximum Ag concentration of 5 at.% are discussed. The needle-like structures were found to be rich in Ag and Cu, and the YBa₂Cu₃O_7−δ film contained 0.02 at.% Ag. Broad beam PIXE-channeling results indicate that 19% of the Ag is substitutional.     

Radiation effects on PbO-Al2O3-B2O3-SiO2 glasses by FTIR spectroscopy

The infrared absorption spectra of PbO-Al₂O₃-B₂O₃-SiO₂ glasses have been measured in the spectral range 600-4000 cm⁻¹ before and after absorbed dose of 50 Gy, 4 kGy and 50 kGy to investigate the structural change due to irradiation. The structural change due to composition has also been discussed. The experimental results clearly indicate that after irradiation, a significant change in structure of lead alumino borosilicate glass network is observed. It was shown that BO₄ groups decreases and BO₃ groups increases with the increase of Al₂O_3.     

Transformation of Al2O3 to LiAlO2 in Pb–17Li at 800 °C

A FeCrAl substrate was pre-oxidized for 2 h at 1000 °C to thermally grow an external Al₂O₃ scale and then isothermally exposed to Pb–17 at.% Li for 1000 h at 800 °C to determine if this layer would protect the underlying alloy from dissolution. After exposure, a small mass gain was measured, indicating that the layer did inhibit dissolution. However, characterization of the external layer determined that it had transformed to LiAlO₂ with an increased thickness and a much larger grain size than the original layer. This observation has implications for the use of Al₂O₃ as a permeation barrier in Pb–Li cooled fusion blanket systems.     

An experimental study on linear differential scattering coefficients of the radioactive compounds UO2(C2H3O2)2 · 2H2O and Th(NO3)4 · 5H2O at 60 keV

The linear differential scattering coefficients at 60 keV have been measured for UO₂(C₂H₃O₂)₂ · 2H₂O (uranyl-acetate) and Th(NO₃)₄ · 5H₂O (thorium-nitrate) radioactive compounds at seven angles ranging from 60° to 120° at intervals 10°. The obtained results have been compared with relativistic and non-relativistic theoretical values.     

A comparative EPR study of ion implantation induced damage in Si, Si1−xGex (x ≠ 0) and SiC

Electron Paramagnetic Resonance (EPR) measurements have been made to investigate the build up of damage in silicon in relaxed crystalline Si_1−xGe_x (x = 0.04, 0.13, 0.24, 0.36) and in 6H-SiC as a result of increasing the ion dose from low levels (10¹² cm⁻²) up to values (10¹⁵ cm⁻²) sufficient to produce an amorphous layer. Si, Si_1−xGe_x (x ≠ 0) and SiC were implanted at room temperature with 1.5 MeV Si, 2 MeV Si and 0.2 MeV Ge ions respectively. A comparison is made between the ways in which the type and population of paramagnetic defects depend on ion dose for each material.     

Decomposition and multiphase reactions in the system UO2(NO3)2·6H2O-Ni(NO3)2·6H2O at elevated temperatures

Solid state reactions between uranyl nitrate hexahydrate and nickel nitrate hexahydrate in mixtures of various ratios have been studied at elevated temperatures. The binary system of uranyl nitrate hexahydrate and nickel nitrate hexahydrate was found to form a eutectic of composition 53 mol% uranyl nitrate hexahydrate and 47 mol% nickel nitrate hexahydrate at 40 °C. The overlap of evolution of nitric oxide (NO) and water vapour above 230 °C confirmed the presence of hydroxynitrates of uranium and nickel as intermediate products. These hydroxynitrates began to react above 280 °C to form nickel uranate, NiU₃O₁₀, in the case of mixtures containing 75 mol% uranyl nitrate hexahydrate. When the proportion of uranyl nitrate hexahydrate in the mixture was higher than 75 mol%, U₃O₈ formed along with nickel uranate. For the mixtures containing uranyl nitrate hexahydrate lower than 75 mol%, NiO was observed to form along with NiU₃O₁₀.     

Phase studies in the UO2-Gd2O3 system

The incorporation of gadolinium directly into nuclear fuel is important regarding reactivity compensation, which enables longer fuel cycles. The incorporation of Gd₂O₃ powder directly into the UO₂ powder by dry mechanical blending is the most attractive process, because of its simplicity. Nevertheless, processing by this method leads to difficulties while obtaining sintered pellets with the minimum required density. This is due to the bad sintering behavior of the UO₂-Gd₂O₃ mixed fuel, which shows a blockage in the sintering process that hinder the densification process. Minimal information exists regarding the possible mechanisms for this blockage and this is restricted to the hypothesis based on the formation of a low diffusivity Gd rich (U,Gd)O₂ phase. The objective of this investigation was to study the phase formation in this system, thus contributing to clarifying the causes of the blockage. Experimental evidence indicated the existence of phases in the (U,Gd)O₂ system that revealed structures different from the fluorite-type UO₂ structure. These phases appear to be isostructural to the phases observed in the rare earth-oxygen system.     

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.     

Carbon deposition from a γ-irradiated CO2/CO/CH4/C2H6 gas mixture on the manganese oxides MnO, Mn3O4 and Mn2O3

The composition of oxides formed on steel surfaces within power reactors may influence heat transfer efficiency. Previous studies have indicated that carbon is deposited on spinal-type oxides containing manganese, iron, cobalt, nickel and chromium. In this investigation, characterised manganese oxides have been subjected to γ-irradiation under conditions similar to those experienced in reactors in an effort to understand the catalytic processes involved in deposit initiation and growth. Mn₃O₄ and Mn₂O₃, under the conditions present in the γ-cell, were reduced to MnO during the time of exposure. Relative carbon deposition rates were observed to follow the trend MnO>Mn₃O₄≈Mn₂O₃.     

Variation of optical band gap with radiation dose in PbO-B2O3 glasses

The effect of dose variation of γ-irradiation on optical band gap of PbO-B₂O₃ glasses have been studied in the wavelength region from 200 to 1200 nm. Absorption of glasses in near ultraviolet/visible have been used to calculate the optical mobility gap and width of tail before and after irradiation. The decrease in transmission due to irradiation indicates the formation of colour centers and structural changes in glass matrix. The optical spectrum has been measured before irradiation and in 50 Gy-50 kGy absorbed dose range.     

Study on borate glass system containing with Bi2O3 and BaO for gamma-rays shielding materials: Comparison with PbO

In this work, the mass attenuation coefficients and shielding parameters of borate glass matrices containing with Bi₂O₃ and BaO have been investigated at 662 keV, and compare with PbO in same glass structure. The theoretical values were calculated by WinXCom software and compare with experiential data. The results found that the mass attenuation coefficients were increased with increasing of Bi₂O₃, BaO and PbO concentration, due to increase photoelectric absorption of all glass samples. However, Compton scattering gives dominant contribution to the total mass attenuation coefficients for studied glass samples. Moreover the half value layers (HVL) of glass samples were also better than ordinary concretes and commercial window glass. These results reflecting that the Bi-based glass can use replace Pb in radiation shielding glass. In the case of Ba, may be can use at appropriate energy such as X-rays or lower.     

Phase transitions in U3O8−z: I, heat capacity measurements

The heat capacity of U₃O_8−z with various O/U ratios was measured in the range from 250 to 750 K, and λ-type heat capacity anomalies were found in each sample. The transition temperatures were 487 and 573 K for UO_2.663, 490 and 576 K for UO_2.656 and 508, 562 and 618 K for UO_2.640. The entropy changes of the transitions were 0.44 and 0.39 J K⁻¹mol⁻¹ for UO_2.663, 0.58 and 0.47 J K⁻¹mol⁻¹ for UO_2.656 and 0.62, 0.51 and 0.25 J K⁻¹mol⁻¹ for UO_2.640, increasing as O/U decreases. The enthalpy change due to the transition varied linearly with the transition temperature except for UO_2.640, showing the presence of the same mechanism of phase transition among the samples with various O/U ratios. The mechanism of the phase transition was discussed on the assumption that the transition is originated from the order-disorder rearrangement of U⁵⁺ and U⁶⁺ with a consequent displacement of atoms, similarly to the case of U₄O_9−y.