Melting behaviour of oxide systems for heterogeneous transmutation of actinides. II. The system MgO–Al2O3–PuO2

Isothermal sections of the phase diagram of the system MgO–Al₂O₃–PuO₂ at various temperatures were calculated using sublattice models. The results show that below 2133 K no liquid occurs in the system. Above 2133 K liquid starts to form at the Al₂O₃–PuO₂ side. The phase diagram of the pseudo-binary system PuO₂–MgAl₂O₄ was also obtained from an isopleth T–x calculation.     

Ductile–brittle transition of polycrystalline iron and iron–chromium alloys

Fracture toughness of polycrystalline Fe, Fe–3%Cr and Fe–9%Cr was measured by four-point bending of pre-cracked specimens at temperatures between 77 K and 150 K and strain rates between 4.46 × 10⁻⁴ and 2.23 × 10⁻² s⁻¹. For all materials, fracture behaviour changed with increasing temperature from brittle to ductile at a distinct brittle–ductile transition temperature (T_c), which increased with increasing strain rate. At low strain rates, an Arrhenius relation was found between T_c and strain rate in each material. At high strain rates, T_c was at slightly higher values than those expected from extrapolation of the Arrhenius relation from lower strain rates. This shift of T_c was associated with twinning near the crack tip. For each material, use of an Arrhenius relation for tests at strain rates at which specimens showed twinning gave the same activation energy as for the low strain rate tests. The values of activation energy for the brittle–ductile transition of polycrystalline Fe, Fe–3%Cr and Fe–9%Cr were found to be 0.21, 0.15 and 0.10 eV, respectively, indicating that the activation energy for dislocation glide decreases with increasing chromium concentration in iron.     

Thermodynamic studies on Cs4U5O17(s) and Cs2U2O7(s) by emf and calorimetric measurements

The oxygen potentials over the phase field: Cs₄U₅O₁₇(s)+Cs₂U₂O₇(s)+Cs₂U₄O₁₂(s) was determined by measuring the emf values between 1048 and 1206 K using a solid oxide electrolyte galvanic cell. The oxygen potential existing over the phase field for a given temperature can be represented by: Δμ(O₂) (kJ/mol) (±0.5)=−272.0+0.207T (K). The differential thermal analysis showed that Cs₄U₅O₁₇(s) is stable in air up to 1273 K. The molar Gibbs energy formation of Cs₄U₅O₁₇(s) was calculated from the above oxygen potentials and can be given by, Δ_fG⁰ (kJ/mol)±6=−7729+1.681T (K). The enthalpy measurements on Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) were carried out from 368.3 to 905 K and 430 to 852 K respectively, using a high temperature Calvet calorimeter. The enthalpy increments, (H⁰_T−H⁰₂₉₈), in J/mol for Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) can be represented by, H⁰_T−H⁰_298.15 (Cs₄U₅O₁₇) kJ/mol±0.9=−188.221+0.518T (K)+0.433×10⁻³T² (K)−2.052×10⁻⁵T³ (K) (368 to 905 K) and H⁰_T−H⁰_298.15 (Cs₂U₂O₇) kJ/mol±0.5=−164.210+0.390T (K)+0.104×10⁻⁴T² (K)+0.140×10⁵(1/T (K)) (411 to 860 K). The thermal properties of Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) were derived from the experimental values. The enthalpy of formation of (Cs₄U₅O₁₇, s) at 298.15 K was calculated by the second law method and is: Δ_fH⁰_298.15=−7645.0±4.2 kJ/mol.     

Structural characterization of amorphous Fe–Si and its recrystallized layers

We have synthesized amorphous Fe–Si thin layers and investigated their microstructure using transmission electron microscopy (TEM). Si single crystals with (1 1 1) orientation were irradiated with 120 keV Fe⁺ ions to a fluence of 4.0 × 10¹⁷ cm⁻² at cryogenic temperature (120 K), followed by thermal annealing at 1073 K for 2 h. A continuous amorphous layer with a bilayered structure was formed on the topmost layer of the Si substrate in the as-implanted specimen: the upper layer was an amorphous Fe–Si, while the lower one was an amorphous Si. After annealing, the amorphous bilayer crystallized into a continuous β-FeSi₂ thin layer.     

Radiation effects on MgAl2O4–yttria stabilized ZrO2 composite material irradiated with Ne ions at high temperatures

Spinel (MgAl₂O₄) and yttria stabilized ZrO₂ (YSZ) are candidates for fuel materials for use in nuclear reactors and the optical and insulating materials for fusion reactors. In our previous studies, the amorphization of spinel under 60 keV Xe ion irradiation at RT was observed. On the other hand, amorphization could not be confirmed in YSZ single crystals under the same irradiation conditions. In the present study, the damage evolution process of polycrystalline spinel–YSZ composite materials has been studied by in situ TEM observation during ion irradiation. The irradiation was performed with 30 keV Ne⁺ ions at a flux of 5 × 10¹³ ions cm⁻² s⁻¹ at 923 K and 1473 K, respectively. The observed results revealed a clear difference in morphology of damage depending on irradiation temperature and crystal grains. In the irradiation at 923 K, defect clusters and bubbles were formed homogeneously in YSZ grains. On the other hand, at 1473 K, only bubble formation was observed. The bubbles grew remarkably with increasing ion fluence in both grains. Even though the growth of the bubbles was observed in both grains, the average diameter of grown bubbles in spinel grains was larger than those in YSZ ones. The bubbles tended to form along the grain boundary at both temperatures.     

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.     

The effect of temperature and oxygen content on the flowing liquid metal corrosion of structural steels in the Pb–Bi eutectic

We performed corrosion tests of 1000 h each on approximately 20 types of structural steels (austenitic, ferritic and martensitic) in convection loops with flowing Pb–Bi at 500, 450 and 400 °C and a temperature gradient of 100 °C. These experiments were performed in liquid Pb–Bi with different oxygen concentrations (from approximately 1 × 10⁻⁶ to 2 × 10⁻⁵ wt.%) to ascertain at what oxygen concentration and up to what temperature the oxygen technology can create protective oxide or spinel layers to reduce or prevent corrosion. The results showed that the structural materials contemplated for building an ADS system, including 9% Cr–1% Mo (W) martensitic steels and similar steels with a higher Si content (2–3%), can be used with their surface unpassivated at up to 450 °C and suffer only minimal corrosion (up to 5 μm/year). At higher temperatures, their surface must be passivated prior to and regularly during the operation; however, no technology to perform such passivation in the presence of Pb–Bi is known that this time. In addition, we measured the impact of various alloying elements, such as Fe, Cr, Ni, Mn, Si, Al and Mo, on the corrosion of such steels and searched for potential ways to passivate their surface or create protective oxide or spinel layers during operation by varying the amount of oxygen in liquid Pb–Bi.     

A rail transportable lead–bismuth cooled reactor

A conceptual design of a small reactor cooled by lead–bismuth is developed. The main constraint on this reactor design is its transportability. The whole reactor module should be transportable on a rail cart. This imposes a volume envelope of approximately 4.5 × 4.5 × 24 m and the maximum weight of about 300 tons. Therefore, the reactor vessel is 3 m in diameter and 3.85 m tall. In order to satisfy the proliferation resistance requirements the reactor is sealed after the fuel is loaded and shall not be opened until it is shipped back after it reaches its end of lifetime after 15years. The reactor fuel is 11% and 13% enriched plutonium nitride. Reactor power is 50 MW_th which translates into 15 MW_e. Reactor pool is at nearly atmospheric pressure. Core inlet and outlet temperature are 350 and 365 °C, respectively. The reactor uses electromagnetic pumps to drive the primary coolant circulation. Secondary system consists of saturated steam cycle operating at 7 MPa and 290 °C. This reactor is well suited for secluded areas with the demand for electricity such as small islands.     

Calculation of thermodynamic parameters of U–Pu–N system with carbon and oxygen impurities

Mixed nitride fuels are being considered for advanced FBR, but very little is known about the thermodynamic properties of these fuels. For an overall composition of the nitride fuel with small amounts of oxygen and carbon impurities, thermodynamic properties, e.g. carbon activity and partial pressures of nitrogen, carbon-monoxide, plutonium and uranium, were calculated in present work. These calculations were based on standard Gibbs free energies of the binary compounds, present in this multi-component system (U,Pu)–C–N–O. For an over all composition of the fuel, stable phase-field was determined by minimization of the Gibbs free energy of the system. The fabrication experiences of various workers, reported in literature, have shown that depending on the impurity content, nitride fuel can exist in two phase fields, mono-nitride phase in equilibrium with sesquinitride phase or mono-nitride phase in equilibrium with dioxide phase. Therefore, in present calculations special attention was given to the thermodynamic behavior of these two phase-fields. A comparison of calculated thermodynamic properties indicated that nitride fuel with dioxide as second phase will be superior to the one with sesquinitride.     

Effect of tin on the irradiation growth of polycrystalline zirconium

Measurements of irradiation growth of polycrystalline Zr-1.5% Sn and Zr-0.1% Sn alloys at 353 K and 553 K have been made following fast neutron irradiation with fluences up to 3.1 × 10²⁵ n/m². At 353 K, growth of Zr-1.5% Sn virtually saturated at a strain of 4.5 × 10⁻⁴ after a fluence of ˜10²⁴ n/m². At this temperature, Zr-0.1% Sn continued to grów until ˜ 2 × 10²⁵ n/m², when the strain levelled off at ˜ 1.2×10⁻³. At 553 K, Zr-1.5% Sn initially grew about twice as fast as the 0.1% Sn alloy, but both eventually reached the same steady state rate of ˜ 2.4 × 10⁻²⁹ m²/n. Comparison of the data for the 1.5% Sn material with those for Zircaloy-2 from earlier work reveals that at 353 K, growth is suppressed by the presence of Sn atoms, which may serve as vacancy traps. However, at 553 K, minor additions and impurities in Zircaloy-2 (such as Fe, Ni, Cr and O) play an important role and cannot be neglected. The growth behaviour of Zr-0.1% Sn is similar to that of pure polycrystalline zirconium, especially at 353 K, indicating that the addition of Sn at this concentration does not strongly influence the growth of zirconium.     

Thermodynamic properties of nonstoichiometric urania-gadolinia solid solutions in the temperature range 700–1100° C

Partial molar thermodynamic quantities for urania-gadolinia solid solutions of compositions U_1−yGd_yO_2+x, with y values of 0.04 to 0.27, have been obtained using a solid electrolyte galvanic cell technique. The measurements were made for O/M ratios ranging from near stoichiometry to 2.20, and for temperatures ranging from 700 to 1100°C. The results for pure UO_2+x are in accordance with data reported earlier. The oxygen potentials for U_1−yGd_yO_2+x are higher than for pure UO_2+x and increase positively with increasing Gd content or excess oxygen. They can be represented as a function of the mean U valence, except at the stoichiometric composition. Both the partial molar entropy and enthalpy increase negatively with increasing Gd content or excess oxygen.     

Reactions between U–Zr alloys and Fe at 923 K

Interdiffusion experiments were carried out at 923 K with the diffusion couples consisting of U–23 at.% Zr/Fe and U–23 at.% Zr–1 at.% Ce/Fe. The reaction layer adjacent to the Fe was a single Zr-depleted UFe₂ phase. The phases in the reaction layers were estimated consistently with the calculated U–Zr–Fe ternary isotherm. The diffusion path obtained in this study was similar to that reported for the U–Pu–Zr/HT9-steel couple at 923 K, when those paths were expressed on the (U+Pu)–Zr–(Fe+Cr) composition triangle. The reaction layers grew in proportion to the square root of the annealing time. The addition of approximately 1 at.% of Ce to the U–23 at.% Zr alloy has little effect on the reaction between U–23 at.% Zr and Fe.     

Determination of boron in Zr–Nb alloys by glow discharge quadrupole mass spectrometry

Direct determination of boron in Zr–2.5%Nb, Zr–1%Nb alloys and zirconium metals which are extensively used as structural materials in nuclear reactors has been carried out by glow discharge quadrupole mass spectrometer (GD-QMS). Relative sensitive factor (RSF) values for boron were determined using different solid standard reference materials (Zircaloy and steel). A comparison of the GD-QMS results obtained using these RSF values, with DC–Arc-AES (direct current arc atomic emission spectrometry)/certified values showed reasonably good agreement in all the Zr-based materials analysed for boron in the range of 0.1–7 mg kg⁻¹. Quantitation of boron in Zr matrix is possible even with a steel standard when certified for Zr and B. Internal precision (intra-sample precision) was found to be typically ±4% RSD (relative standard deviation) and the inter-sample precision was ±10% RSD for boron at 0.1 mg kg⁻¹ levels. The overall accuracy of the procedure was found to be ±8% at 0.5 mg kg⁻¹ levels of boron using Zircaloy and steel standards. Under optimised experimental conditions the detection limit for boron was found to be ±13 μg kg⁻¹.     

Photoluminescence of Au formed in 12CaO · 7Al2O3 single crystal by Au-implantation

Au⁺ ion implantation with fluences from 1 × 10¹⁴ to 3 × 10¹⁶ cm⁻² into 12CaO · 7Al₂O₃ (C12A7) single crystals was carried out at a sample temperature of 600 °C. The implanted sample with the fluence of 1 × 10¹⁵ cm⁻² exhibited photoluminescence (PL) bands peaking at 3.1 and 2.3 eV at 150 K when excited by He–Cd laser (325 nm). This was the first observation of PL from C12A7. These two PL bands are possibly due to intra-ionic transitions of an Au⁻ ion having the electronic configuration of 6s², judged from their similarities to those reported on Au⁻ ions in alkali halides. However, when the concentration of the implanted Au ions exceeded the theoretical maximum value of anions encaged in C12A7 (2.3 × 10²¹ cm⁻³), surface plasmon absorption appeared in the optical absorption spectrum, suggesting Au colloids were formed at such high fluences. These observations indicate that negative gold ions are formed in the cages of C12A7 by the Au⁺ implantation if an appropriate fluence is chosen.     

Surface excitation parameter for semiconducting III–V compounds

In the rapid development of mesoscopic science, the study of surface excitations in solids and overlayer systems plays a crucial role. The surface excitation parameter which describes the total probability of surface plasmon excitations by an electron traveling in vacuum before impinging on or after escaping from a semiconducting III–V compound has been calculated for 200–2000 eV electrons crossing the compound surface. These calculations were performed using the dielectric response theory with sum-rule-constrained extended Drude dielectric functions established by the fits of these functions to optical data. Surface excitation parameters calculated for InSb, InAs, GaP, GaSb or GaAs III–V compounds were found to follow to a simple formula, i.e. P_s = aE^−b, where P_s is the surface excitation parameter and E is the electron energy. These surface excitation parameters were then applied to determine the elastic reflection coefficient for electrons elastically backscattered from III–V compounds using the Monte Carlo simulations. Good agreement was found for the electron elastic reflection coefficient between calculated results and experimental data.     

Electrical conductivity and non-stoichiometry in the (U,Gd)O2±x system

The isothermal electrical conductivity and oxygen potential of the (U,Gd)O_2±x solid solution were measured in various oxygen partial pressure regions at 1200 °C and 1300 °C. The electrical conductivity gradually decreased with decreasing oxygen partial pressure even in the hypo-stoichiometric region. These findings were in contrast to the implication of a hypo-stoichiometry where the electrical conductivity is increased through the formation of oxygen vacancies. The (U_1−yGd_y)O_2−y/2 was defined as a new stoichiometric composition to determine the relationship between the deviation of the oxygen composition from stoichiometry and oxygen partial pressure. The dependence of the new oxygen deviation, z in (U_1−yGd_y)O_2−y/2+z, on the oxygen partial pressure corresponds to the dependence of the electrical conductivity, and thus a consistent defect structure model can be deduced from both the dependence curves. It suggests that the defect type is oxygen interstitial even below the oxygen composition of 2.     

A Raman study of the nanocrystallite size effect on the pressure–temperature phase diagram of zirconia grown by zirconium-based alloys oxidation

The pressure–temperature phase diagrams of different zirconia samples prepared by oxidation of Zircaloy-4 and Zr–1%Nb–0.12O alloys were monitored by Raman spectrometry from 0.1 MPa to 12 GPa and from 300 to 640 K. These new diagrams show that the monoclinic–tetragonal equilibrium line is strongly downshifted in temperature compared to literature measurements performed on usual polycrystalline zirconia. In addition, the monoclinic–orthorhombic equilibrium line is slightly shifted to higher pressure (i.e. 6 GPa). The crystallite sizes smaller than 30 nm, are thought to be responsible for these equilibrium line displacements. The tetragonal phase obtained in temperature under high pressure can be quenched at room temperature, if the pressure is maintained, and it is destabilised and transforms completely into monoclinic phase if the pressure is released. These results confirm that coupled effects of stress, temperature and nanosized grain are responsible for the formation of the tetragonal phase near the metal/oxide interface during the oxidation of zirconium-based alloys.     

Thoria doped with cations of group VB–synthesis and sintering

The cations M⁵⁺ (M=V, Nb and Ta) were doped in thoria through gel-combustion synthesis using citric acid as fuel. Thorium dioxide feed powders thus prepared were cold compacted without binder or lubricant and sintered to a high density (9.5 Mg m⁻³) at relatively low temperatures (1623 K). The powders were characterised for the residual carbon, crystallite size, specific surface area, particle size distribution and bulk density. The distribution of the dopant in the thoria matrix was analyzed by electron probe microanalysis. The reactivity of the calcined powders was determined by measuring the density of the sintered compacts prepared from them. For the first time it is demonstrated that apart from niobia, even tantala and vanadia can bring about accelerated sintering in thoria if they are doped through a wet chemical route viz., the gel-combustion procedure. The maximum densities obtained by doping with vanadia (0.02 mol%), niobia (0.50 mol%) and tantala (0.50 mol%) were 9.8 Mg m⁻³ (1573 K), 9.68 Mg m⁻³ (1423 K) and 9.69 Mg m⁻³ (1623 K), respectively.     

Boiling heat transfer behavior of lead–bismuth–steam–water direct contact two-phase flow

The boiling heat transfer behavior of lead–bismuth (Pb–Bi)–steam–water direct contact two-phase flow was experimentally investigated. Experimental study was performed using Pb–Bi–steam–water direct contact boiling two-phase flow loop. The heat transfer rate was estimated from data of one-dimensional flow direct contact boiling of water in Pb–Bi. It is assumed in the analysis that film boiling occurs at the surfaces of a small water droplet after water is injected into hot Pb–Bi flow, because of the large temperature difference between water and Pb–Bi (i.e. 493 K and 733 K for injection water and Pb–Bi temperature, respectively). The heat transfer occurs between Pb–Bi and steam without phase change after all water completely evaporates. The overall heat transfer coefficient decreased with the superheat at low injection flow rate and was nearly constant for high injection flow rate. The local heat transfer coefficient was higher than average one in the whole tube, which means that the direct contact boiling heat transfer coefficient was high and it decreased in the downstream direction. Almost all the water vaporized in the test tube at high pressure according to the local and total heat transfer rate.