Synthesis & fabrication of lithium-titanate pebbles for ITER breeding blanket by solid state reaction & spherodization

⁶Li produces tritium by (n, α) nuclear reaction, ⁶Li + ¹n → ⁴He + ³H. Lithium titanate (Li₂TiO₃) enriched with ⁶Li, is the most promising candidate for solid test blanket module (TBM) material for fusion reactors. Various processes are reported in literature for the fabrication of Li₂TiO₃ pebbles for its use as TBM material. A process has been developed based on the solid state reaction of lithium-carbonate and titanium-dioxide for the synthesis of lithium titanate and pebble fabrication by extrusion, spherodization and sintering. This paper discusses the sequence of steps followed in this process and the properties obtained. Analytical grade titanium-dioxide and lithium-carbonate were taken in stoichiometric ratio and were milled to ensure thorough intimate mixing and obtain fine particles less than 45 μm before its calcination at 900 °C. Following calcination, the agglomerated product was again milled to fine particles of size less than 45 μm. Aqueous solution of ploy-vinyl-alcohol was added as binder prior to its feeding in the extruder. The extruded strips were spherodized and spherical pebbles were dried and sintered at 900 °C for different duration. Pebbles of desired density and porosity were obtained by suitable combination of sintering temperature and duration of sintering. Properties of the prepared pebbles were also characterized for sphericity, pore size distribution, grain size, crushing load strength, etc. The values were found to be conforming to the desired properties for use as solid breeder. The attractive feature of this process is almost no waste generation.     

Activation analysis and waste management for blanket materials of multi-functional experimental fusion–fission hybrid reactor (FDS-MFX)

The preliminary studies of the activation analysis and waste management for blanket materials of the multi-functional experimental fusion–fission hybrid reactor, i.e. Multi-Functional eXperimental Fusion Driven Subcritical system named FDS-MFX, were performed. The neutron flux of the FDS-MFX blanket was calculated using VisualBUS code and Hybrid Evaluated Nuclear Data Library (HENDL) developed by FDS Team. Based on these calculated neutron fluxes, the activation properties of blanket materials were analyzed by the induced radioactivity, the decay heat and the contact dose rate for different regions of the FDS-MFX blanket. The safety and environment assessment of fusion power (SEAFP) strategy, which was developed in Europe, was applied to FDS-MFX blanket for the management of activated materials. Accordingly, the classification and management strategy of activated materials after different cooling time were proposed for FDS-MFX blanket.     

A New Model for Exchange of Deuterium in Oxide Ceramics for Protium in Light Water Molecule at Room Temperature

For exchange of deuterium (D) in oxide ceramics for protium (H) in light water molecule at room temperature is proposed the one way diffusion model: absorption of proton and adsorption of OH^- due to dissociation of H₂O at the surface, diffusion of proton, release of deuteron in trapping site due to local molecular recombination with proton and the subsequent trapping of another proton into the vacant trapping site. The one way diffusion model has been formulated in form of the mass balance equations for free proton and both proton and deuteron trapped in trapping sites which include the rate constants of chemical reactions for proton described above. The solutions of the concentrations of deuterons retained and protons uptaken in the specimen have been fitted to the experimental data and the rate constants of the chemical reactions relevant to the D-H exchange have been determined. The rate constants of the chemical reactions are discussed. Moreover, potential applications of the one way diffusion model are discussed.     

Preliminary spectrum shifter design for intermediate energy nuclear data benchmark experiments with DT neutrons

Integral benchmark experiments with DT neutrons are not always sufficient for nuclear data benchmarking in the MeV region, below 10 MeV. A neutron spectrum shifter, which will be placed between a sample and a DT neutron source, is effective to moderate DT neutrons incident to the sample. In order to estimate effects of the spectrum shifter, the ratio of the contribution of 14 MeV neutrons in the leakage neutron and gamma-ray spectra was calculated with MCNP-4C for an experimental configuration at FNS of JAEA, Japan. The calculations were carried out for a Li₂TiO₃ sample with a Be, D₂O, or ⁷LiD spectrum shifter. It was found out that the Be shifter was superior to others and the Be shifter was effective to decrease the contribution of 14 MeV neutrons especially for secondary gamma-ray spectrum measurements.     

N-TiO2 nanoparticles embedded in silica prepared by Ti ion implantation and annealing in nitrogen

Room-temperature Ti ion implantation and subsequent thermal annealing in N₂ ambience have been used to fabricate the anatase and rutile structured N-doped TiO₂ particles embedded in the surface region of fused silica. The Stopping and Range of Ions in Matter (SRIM) code simulation indicates a Gaussian distribution of implanted Ti, peaked at ∼75 nm with a full width at half maximum of ∼80 nm. However, the transmission electron microscopy image shows a much shallower distribution to depth of ∼70 nm. Significant sputtering loss of silica substrates has occurred during implantation. Nanoparticles with size of 10-20 nm in diameter have formed after implantation. X-ray photoelectron spectroscopy indicates the coexistence of TiO₂ and metallic Ti in the as-implanted samples. Metallic Ti is oxidized to anatase TiO₂ after annealing at 600 °C, while rutile TiO₂ forms by phase transformation after annealing at 900 °C. At the same time, N-Ti-O, Ti-O-N and/or Ti-N-O linkages have formed in the lattice of TiO₂. A red shift of 0.34 eV in the absorption edge is obtained for N-doped anatase TiO₂ after annealing at 600 °C for 6 h. The absorbance increases in the ultraviolet and visible waveband.     

Depth profiling of Al2O3 + TiO2 nanolaminates by means of a time-of-flight energy spectrometer

Atomic layer deposition (ALD) is currently a widespread method to grow conformal thin films with a sub-nm thickness control. By using ALD for nanolaminate oxides, it is possible to fine tune the electrical, optical and mechanical properties of thin films. In this study the elemental depth profiles and surface roughnesses were determined for Al₂O₃ + TiO₂ nanolaminates with nominal single-layer thicknesses of 1, 2, 5, 10 and 20 nm and total thickness between 40 nm and 60 nm. The depth profiles were measured by means of a time-of-flight elastic recoil detection analysis (ToF-ERDA) spectrometer recently installed at the University of Jyväskylä. In TOF-E measurements ⁶³Cu, ³⁵Cl, ¹²C and ⁴He ions with energies ranging from 0.5 to 10 MeV, were used and depth profiles of the whole nanolaminate film could be analyzed down to 5 nm individual layer thickness.     

Neutronics Experimental Study on Tritium Production in Solid Breeder Blanket Mockup with Neutron Reflector

Neutronics experiments have been performed for the solid breeder blanket using a DT neutron source at the FNS facility in JAEA. We have applied the blanket mockup composed of two enriched Li₂TiO₃ and three beryllium layers, and measured the detailed spatial distribution of the tritium production rate (TPR) using enriched Li₂CO₃ pellets. TPRs in the pellets have been measured by a liquid scintillation counter. Experiments have been done under a condition with a neutron reflector surrounding the DT neutron source. Numerical simulations have been performed using the MCNP-4C with the FENDL-2.0 and JENDL-3.3. The ranges of ratios of calculation results to experimental ones (C/Es) are 0.97–1.17 concerning with local TPR, and 1.04–1.09 for the integrated tritium production. It is found that the total integrated tritium production, which corresponds to tritium breeding ratio, can be predicted within uncertainty of 10% using the Monte Carlo calculation code and latest nuclear data libraries.     

Analysis of fuel temperature effects on reactivity of light water reactor fuel assemblies by using MVP-2 adopting an exact resonance elastic scattering model

Using the continuous-energy Monte Carlo code MVP-2 adopting a resonance elastic scattering model considering the thermal motion of a target nucleus (the exact model) for major heavy nuclides, analysis of fuel temperature effects on reactivity of mockup UO₂ and MOX fuel assemblies for light water reactors was performed, and the results were compared with those of the conventional asymptotic model. A base condition was a hot operating condition with an in-channel void fraction of 40% and fuel temperature of 520 ℃ for the BWR fuel assemblies and a hot zero-power condition with fuel temperature of 284 ℃ for the PWR fuel assemblies. The fuel temperature of a high-temperature condition was 1500 ℃ for both types of assemblies. The calculated results showed that the exact model made the neutron multiplication factors at the high-temperature condition lower by ?220 to ?440 pcm (10^?5 Δk) and the Doppler reactivity between the base- and high-temperature conditions more negative by 7% to 10% compared with those obtained by the asymptotic model. The energy-dependent reaction rates of capture and ν-fission were also analyzed to study the detail mechanism in the effect of the exact model on the assembly reactivity.     

Treatment of UO2 pellets used for preparing fuel elements of HTR-10 followed by supercritical fluid extraction

International interest in high temperature gas-cooled reactor (HTGR) has been increasing in recent years. It is important to study on reprocessing of spent nuclear fuel from HTGR for recovery of nuclear resource and reduction of nuclear waste. Treatment of UO₂ pellets used for preparing fuel elements of the 10 MW high temperature gas-cooled reactor (HTR-10) followed by supercritical fluid extraction was investigated. When UO₂ pellets were dissolved and extracted with tri-n-butyl phosphate (TBP)–HNO₃ complex in supercritical CO₂ (SC-CO₂), the extraction efficiency was less than 7% under experimental conditions. After UO₂ pellets were ground into UO₂ fine powders, the extraction efficiency of the UO₂ fine powders with TBP–HNO₃ complex in SC-CO₂ could reach 92%. After UO₂ pellets broke spontaneously into U₃O₈ powders under O₂ flow and 600 °C, the extraction efficiency of the U₃O₈ powder with TBP–HNO₃ complex in SC-CO₂ could reach more than 98%.     

Recovery of neutron-irradiation-induced defects of Al2O3, Y2O3, and yttrium-aluminum garnet

SiC fiber-reinforced SiC matrix composites (SiC_f/SiC) are considered as one of the candidates for blanket materials in future fusion reactors and as an advanced fuel cladding material for next-generation fission reactors. Generally, the densification of SiC needs sintering additives and oxides such as Al₂O₃, Y₂O₃, and yttrium-aluminum garnet (YAG, Y₃Al₅O₁₂), which are frequently added to SiC. However, the effects of neutron irradiation on sintering additives are still unclear. In this study, we performed the neutron irradiation of Al₂O₃, Y₂O₃, and YAG at fluences up to 2.0–2.5 × 10²⁴ n/m² (E > 0.1 MeV) at 60–90 °C. The isochronal recovery of the macroscopic volume of Al₂O₃ against annealing temperature showed smooth and continuous shrinkage at a temperature of up to 1200 °C, and the volume slightly increased above that temperature. In contrast, the volume of Y₂O₃ showed quick shrinkage at the low temperature range, and slower and smooth recovery was observed up to ～1100 °C. In the case of YAG, the recovery of volume occurred in a step-wise manner at 600–750 °C, and continuous shrinkage occurred at temperatures lower and higher than that temperature range. The activation energies for the macroscopic volume recoveries of three oxides were obtained from the Arrhenius plots of the rate coefficients. Two-stage recovery was observed for Al₂O₃, whereas more complicated recovery processes were suggested for Y₂O₃ and YAG.     

Vacuum plasma etching of 1 wt% La2O3 dispersed tungsten

Vacuum plasma etching of 1 wt% La₂O₃ doped tungsten alloy surfaces were carried out to refine the surface morphology for enhancing its bonding characteristics with copper for fusion reactor components. Three different gas compositions containing argon with zero, 14.3 and 25 vol% hydrogen were used to carry out the plasma etching from 30 to 120 s on the given samples. Mitutoyo surface roughness (R_a) measurement, FORM TALYSURF and scanning electron microscopy (SEM) were employed to measure the changes in the surface roughness. Plasma etching with 14.3 vol% hydrogen mixture was found to be the best in micro-roughening the alloy surface. The maximum increase of 44% in R_a value was obtained with this gas mixture, when etched for 90 s.     

Synthesis and characterization of SnO2 nanoparticles embedded in silica by ion implantation

Tin dioxide nanoparticles embedded in silica matrix were fabricated by ion implantation combined with thermal oxidation. Silica substrate was implanted with a 150 keV Sn⁺ ions beam with a fluence of 1.0 × 10¹⁷ ions/cm². The sample was annealed for 1 h in a conventional furnace at a temperature of 800 °C under flowing O₂ gas. According to the structural characterization performed by X-ray diffraction and transmission electron microscopy techniques, metallic tetragonal tin nanoparticles with a volume average size of 12.8 nm were formed in the as-implanted sample. The annealing in oxidizing atmosphere promotes the total oxidation of the tin nanoparticles into tin dioxide nanoparticles with a preferential migration toward the surface of the matrix, where large and coalesced nanoparticles were observed, and a small diffusion toward the bulk, where smaller nanoparticles were found.     

Alkali Metal Ion and Lithium Isotope Selectivity of HZr2(PO4)3

HZr₂(PO₄)₃ has been synthesized by the heat treatment of NH₄Zr₂(PO₄)₃ and its properties as an ion exchanger have been examined with the main focus on its alkali metal ion and lithium isotope selectivity. The distribution coefficients for alkali metal ions revealed that HZr₂(PO₄)₃ was lithium ion-specific and showed little affinity toward potassium, rubidium or cesium ion. The lithium and sodium ion uptakes from aqueous solutions were monotonously increasing functions of pH. Isotopically, HZr₂(PO₄)₃ was ⁶Li-specific. Contrary to ion uptake, the lithium isotope effect was a monotonously decreasing function of pH; a larger separation factor was observed at a lower pH. This result was consistent with the existence of two different ion exchange sites formed in lithium ion-inserted HZr₂(PO₄)₃.     

Surface nanostructuring of SrTiO3 single crystals by slow highly charged ions and swift heavy ions

Single crystals of strontium titanate have been irradiated with both slow highly charged Xe ions extracted from an Electron Beam Ion Trap and swift heavy Xe ions. After irradiation, the crystals were investigated by scanning force microscopy in air. In both cases nanohillocks due to impact of individual projectiles were observed. This similarity originates from the fact that both swift heavy ions and slow highly charged ions initially transfer their energy to the electronic system of the target, leading to a localized region of high electronic excitation. This electronic excitation is subsequently transferred to the lattice atoms by electron-phonon coupling, leading to pronounced lattice heating. The formation of surface hillocks can then be ascribed to a melting process. We also present first evidence for the existence of a potential energy threshold for nanohillock formation on strontium titanate surfaces by slow highly charged ions.     

Wettability of liquid caesium iodine and boron oxide on yttria-stabilized zirconia

During the Fukushima Daiichi Nuclear Power Plant accident occurred in 2011, volatile fission products (FPs) such as Cs and I had released and caused environmental contamination and public exposure, respectively. However, the release mechanism of these FPs from fuels under the accident is still not completely understood. In recent years, we have focused on the wettability of liquid FPs against solid fuels, because the interface between the fuel surface and the FPs becomes the migration pathway, which might have large influences on the release behaviour of the FPs. Here, we studied the wettability of liquid CsI and B₂O₃ on yttria-stabilized zirconia (YSZ) solid surface by the sessile drop test, where YSZ is a simulated material of the fuel. It was revealed that liquid CsI exhibited extremely high wettability against the YSZ surface with the contact angle of nearly zero. This high wettability may act to suppress the FPs release. Furthermore, it was confirmed that the crystal orientation and surface roughness of the YSZ solids have large influences on the wettability of liquid B₂O₃. The present results contribute for deep understanding of the release behaviour of the volatile FPs from fuels.     

Investigation of thermal neutron scattering data for BeF2 and LiF crystals

The influences of thermal neutron scattering data for BeF₂ and LiF crystals on molten salt reactor physics are investigated in this work. Based on the structure parameters of BeF₂ and LiF, the coherent scattering for both crystals is added to NJOY source code. The ENDF6 format thermal neutron scattering sub-libraries for both crystals are evaluated with their phonon spectra using LEAPR; the ACE format data are produced by NJOY subsequently. Finally, the effect of thermal neutron scattering of BeF₂ and LiF crystals on k _eff and spectrum are investigated. The result shows that thermal neutron scattering for bound state of BeF₂ and LiF influence k _eff and spectrum obviously. The elastic scattering cross section for bound state of crystals is smaller than free atom; it makes k _eff decrease (1%–2%) and spectra be hardened. The higher temperature the bound state has, the smaller coherent elastic scattering cross section it gets; therefore, k _eff decreases with temperature. It is suggested that the thermal neutron data of LiF and BeF₂ should be taken into account for molten salt reactor.     

Concentrations of CsCl and SrCl2 from a Simulated LiCl Salt Waste Generated by Pyroprocessing by Using Czochralski Method

Separation of CsCl and SrCl₂ from LiCl was carried out by using a separation technology, the Czochralski crystallization method. It was experimentally confirmed that Cs as well as Sr could be separated simultaneously from a LiCl molten salt by the suggested crystallization process without any additive or adsorption medium. The concentrations of Cs and Sr in LiCl decreased from 1.81 and 4.18 wt% in the initial salt to minimum values of 114 and 36 ppm in the grown LiCl crystal, respectively. The separation mechanism of Cs and Sr is described by the solubility difference of the solutes between the molten and solid states. It is expected that the total amount of salt waste will decrease drastically, because most of LiCl could be recovered by recycling with an electroreduction process.     

Development and characterization of the control assembly system for the large 2400 MWth Generation IV gas-cooled fast reactor

The present paper is related to the design and neutronic characterization of the principal control assembly system for the reference large (2400 MWth) Generation IV gas-cooled fast reactor (GFR), which makes use of ceramic–ceramic (CERCER) plate-type fuel-elements with (U–Pu) carbide fuel contained within a SiC inert matrix. For the neutronic calculations, the deterministic code system ERANOS-2.0 has been used, in association with a full core model including a European fast reactor (EFR)-type pattern for the control assemblies as a starting point. More specifically, the core contains a total of 33 control (control system device: CSD) and safety (diverse safety device: DSD) assemblies implemented in three banks. In the design of the new control assembly system, particular attention was given to the heat generation within the assemblies, so that both neutronic and thermal–hydraulic constraints could be appropriately accounted for. The thermal–hydraulic calculations have been performed with the code COPERNIC, significant coolant mass flow rates being found necessary to maintain acceptable cladding temperatures of the absorber pins.     

Relative Reactivities of Radioiodine Released from U3O8 in Oxygen and Helium Atmospheres toward Propane

Chemical form of radioiodine released from U₃O₈ will be UI_x in helium and I₂ in oxygen atmospheres. Relative reactivities of these iodines toward organic compounds have been studied at a temperature range of 250~500°C, by choosing propane as a reactant. The UI_x has a higher reactivity than I₂, particularly at a temperature range of 300~400°C. Above that temperature, both iodine species show a similar reactivity. In the reactions, CH₃I, C₂H₅I, i, and n-C₃H₇I are formed: relative yields depend on both temperature and atmosphere. Two reaction processes participate in the formation of organic iodides. One is an iodine-initiation reaction and is relatively important at a lower temperature. The other is a radical-initiation reaction and become predominant as the temperature rises.