Pyrochlore type compound Nd2(Zr,Ce)2O7 is considered to precipitate in ThO2-based fuel, that is not observed in irradiated UO2. In order to evaluate the influences on fuel properties, thermomechanical properties of the pyrochlore type compounds, Ln2Zr2O7 (Ln=La, Pr, Nd, Eu, Gd, Dy) and Nd2Ce2O7 were investigated. We synthesized the samples by solid-state reaction and pelletized by spark plasma sintering to make high density (≥ 90 %T.D.) pellets. The phase states and lattice parameters were examined by using X-ray diffraction and SEM/EDX analysis. The lattice parameters of Ln2Zr2O7 depended on the ionic radii of lanthanide ions. The heat capacity, thermal conductivity, linear thermal expansion coefficient, and elastic constants were also measured. It was confirmed that the thermal conductivities for Ln2Zr2O7 were lower than that for ThO2 and depended on Ln ionic radii. The values of elastic constants tended to increase with increasing the Ln ionic radii, corresponding to the thermal conductivity.

Mo3Ru5MPd (M = Ru, Rh, Pd) as the simulated materials for the undissolved residue in the nuclear fuel reprocessing were prepared by arc melting method. The physical properties and oxidation behavior of the alloys were evaluated from viewpoint of the safety and economy in the reprocessing. The electrical resistivity, ρ, of Mo3Ru5RhPd was shown to be 0.8 μΩm at room temperature. On the other hand, the ρ values of samples without Rh were marked at 0.4 μΩm. The thermal properties of the each sample had the different thermal transfer characteristics. In particular, although the thermal conductivities of Mo3Ru5RhPd and Mo3Ru5Pd2 samples show almost the same value, the lattice thermal conductivities of both samples showed different values. Oxidation behavior was analyzed using the thermogravity(TG) and differential thermal analyses(DTA). The TG curve of each sample by oxidation showed different results. These results indicate that the simulated materials of the alloys without Rh: Mo-Ru-Pd were not appropriate to simulate the thermophysical characteristics of the typical simulated materials with undissolved residue Mo-Ru-Rh-Pd alloys. Therefore, in the spent nuclear fuel reprocessing, the mock test of reprocessing without to use Rh is difficult to carry out.

In the Zn-Sn-Sb ternary system, Zn4Sb3, ZnSnSb2, and ZnSb have attracted attentions as advanced thermoelectric materials. Zn-Sn-Sb based alloys with various compositions were fabricated and the thermoelectric properties were investigated. That system is composed by orthorhombic ZnSb phase, tetragonal ZnSnSb2 phase with chalcopyrite structure, and rhombohedral SnSb phase. Large Sn content increases volume fraction of the metallic SnSb phase, which degenerate the powar factor. The ZnSb based alloy shows relatively large Seebeck coefficient. Sn substitution for ZnMxSb1-x significantly enhances the power factor, which indicates that Sn is effective dopant for ZnSb.

Although AgSbTe2 exhibits excellent thermoelectric properties, the single phase is unstable and second phases such as Ag2Te and Sb2Te3 are easy to precipitate. In the present study, we tried to stabilize the AgSbTe2 phase by adding a small amount of another phase. Here we chose Pb0.16Ge0.84Te as the adding phase because the crystal structure and the lattice parameter were completely the same as those of AgSbTe2. The samples of (Ag0.5Sb0.5Te1-x(Pb0.16Ge0.84Te)x (x = 0, 0.01, 0.02, 0.05, and 0.1) were prepared and the phase stability and the thermoelectric properties were examined. The AgSbTe2 phase was stabilized in the samples of x = 0.01 and 0.02. All the samples exhibited large thermoelectric figure of merit.

CoSb3 is known as a skutterudite compound that could exhibit high thermoelectric figure of merit. However, the thermal conductivity of CoSb3 is relatively high. In order to enhance the thermoelectric performance of this compound, we tried to reduce the thermal conductivity of CoSb3 by substitution of Rh for Co and by Tl-filling into the voids. The polycrystalline samples of (Co,Rh)Sb3 and Tl-filled CoSb3 were prepared and the thermoelectric properties such as the Seebeck coefficient, electrical resistivity, and thermal conductivity were measured in the temperature range from room temperature to 750 K. The Rh substitution for Co reduced the lattice thermal conductivity, due to the alloy scattering effect. The minimum value of the lattice thermal conductivity was 4 Wm-1K-1 at 750 K obtained for (Co0.7Rh0.3)Sb3. Also the lattice thermal conductivity rapidly decreased with increasing the Tl-filling ratio. T10.25Co4Sb12 exhibited the best ZT values; the maximum ZT was 0.9 obtained at 600 K.

Oxygen potentials of (Th0.7Ce0.3)O2-x were experimentally determined by means of thermogravimetric analysis as a function of non-stoichiometry at 1173 and 1273 K. Oxygen potentials of (Th0.7Ce0.3)O2-x at each temperature increased with increase of oxygen to metal (O/M) ratio (=2-x) and steep increases of the oxygen potentials when approaching O/M ratio = 2 were observed. These characteristics are typical for non-stoichiometric fluorite-type actinide dioxides. The oxygen potentials of (Th0.7Ce0.3)O2-x were similar to those of CeOO2-x when they were plotted as a function of average Ce valence.

The oxygen potentials at 1273 K of mixed oxide (MOX) fuels with Am and 26 kinds of fission product elements (FPs), simulating low-decontaminated MOX fuel and high burn-up of up to 250 GWd/t, have been measured by using thermogravimetric analysis (TGA). The oxygen potentials for simulated low-decontaminated MOX fuels were higher than the fuels without FPs and increased with increasing simulated burn-up.

Fine bulk samples of delta-phase Hf hydride with various hydrogen contents (CH) ranging from 1.62 to 1.72 in the atomic ratio (H/Hf) were prepared, and their thermal and mechanical properties were characterized. In the temperature range from room temperature to around 650 K, the heat capacity and thermal diffusivity of the samples were measured and the thermal conductivity was evacuated. The elastic modulus was calculated from the measured sound velocity. The Vickers hardness was measured at room temperature. Effects of CH and/or temperature on the properties of Hf hydrides were discussed. At room temperature, the thermal conductivity values of the Hf hydrides were 23 Wm−1K−1. The Young's and shear moduli and the Vickers hardness of Hf hydride decreased with increasing CH.

Thermal conductivities of Cs-M-O (M = Mo or U) ternary compounds, observed in the pellet-cladding gap region and in the pellet periphery in irradiated oxide fuels with high oxygen potentials, were investigated. Bulk samples of Cs2MoO4 and Cs2UO4 were prepared by hot pressing or spark plasma sintering, and their thermal diffusivities were measured by the laser flash method from room temperature to 823 K for Cs2MoO4 and to 900 K for Cs2UO4. The thermal conductivities were evaluated from the thermal diffusivity and bulk density, and the specific heat capacity values available in the literature. The thermal conductivities of Cs2MoO4 and Cs2UO4 were quite low compared with UO2 (e.g. 0.5 Wm−1K−1 at 800 K for Cs2MoO4).

Mechanical properties of titanium, zirconium, and hafnium hydrides were evaluated by indentation tests in the present study. Single-phase bulk specimens of titanium, zirconium, and hafnium hydrides with a fluorite type structure were produced using a Sieverts' apparatus. The indentation hardness values of titanium and hafnium hydrides were lower than those of the pure metals and drastically decreased with increasing hydrogen content. The hardness of zirconium hydride was higher than that of pure zirconium and slightly depended on hydrogen content. The hardness of the hydrides decreased with increasing maximum indentation load, which has been referred to as indentation size effect. The dependences of hardness on the indentation depth for the hydrides were found to obey the Nix–Gao model. The indentation size effects for the hydrides were significantly smaller than those for the pure metals.

Young's moduli of hydrogenated Zr-Nb alloys were evaluated by using a multiple elastometer in the temperature range from room temperature to 773 K, based on the cantilever characteristic vibration technique. The decreasing rate of Young's modulus against the temperature was independent on the additive amount of Nb. The Young's modulus for the hydrogen solid solution of Zr-Nb alloys decreased and that those for the alloys with partially precipitated hydride slightly changed with increasing hydrogen content in both of Zr-1.0Nb and Zr-2.5Nb. The decreasing rates with hydrogen content of hydrogen solid solution of Zr-Nb alloys were almost same as that of Zr hydrogen solid solution. This result was considered because all specimens largely consisted of α-zirconium in which the solute hydrogen was found to decrease the Young's modulus.

PuO2 and AmO2 solid solutions: (Pu, Am)O2 are one of the candidates of fuels in a sub-critical accelerator-driven system (ADS). To understand the fuel performance, the thermophysical properties such as thermal conductivity and heat capacity are quite important. However, it is very hard to experimentally determine the physical properties of plutonium as well as americium compounds due to their handling-difficulties. Molecular dynamics (MD) would be a specific method to describe the physical properties of such materials. In the present study, we have investigated thermophysical properties of PuO2, AmO2, and their solid solutions in the temperature range from 300 to 2,500 K. The lattice parameter, compressibility, heat capacity, linear thermal expansion coefficient, and thermal conductivity were evaluated. A Morse-type potential function added to the Busing-Ida type potential was employed as the potential for interatomic interactions. The calculated lattice parameters of (Pu, Am)O2 obeyed Vegard's law, and the values increased with temperature. The heat capacities of (Pu, Am)O2 were similar in any compositions. The thermal conductivities of (Pu, Am)O2 were lower than those of PuO2 and AmO2, indicating that a point-defect scattering effect of phonons could be realized in the MD calculations.

Thermodynamic modeling has been performed for O-Am binary system and O-Pu-Am ternary system on the basis of thermodynamic data available in the literature. The interaction parameters of the excess Gibbs energies of the fluorite structure FCCC1 phase in the O-Am and the O-Pu-Am systems were evaluated with respect to the deviation from the ideal solution in oxygen potential, respectively. The thermodynamic modeling used in this study is based on the CALculation of PHAse Diagram (CALPHAD) technique.

SPS technique was applied for fabrication of UN pellets. The dense sample was obtained with relatively low sintering temperature without any milling process and sintering additive, indicating that the SPS technique is suitable for fabrication of nitride fuel. The thermal conductivity and Young's modulus in axial direction were higher than those of reported values. EBSP analysis and electronic calculation supposed that weak grain orientation in [100] direction of the sample lead to these higher values.

The molecular dynamics (MD) calculation was performed for minor actinide (MA: Np and Am)-containing mixed oxide (MOX) fuels, U0.7-xPu0.3MAxO2, in the temperature range from 300 to around 2500 K to evaluate the thermal expansion, heat capacity, and thermal conductivity. The MD results showed that the calculated heat capacity and thermal conductivity were similar in all the composition ranges, indicating that MA scarcely affected the thermal properties of the MOX fuel in the perfect crystal system.

We studied the thermoelectric properties of BaSi2 and SrSi2. The polycrystalline samples were prepared by spark plasma sintering (SPS). The electrical resistivity (ρ), Seebeck coefficient (S), and thermal conductivity (κ) were measured above room temperature. The maximum values of the dimensionless figure of merit (ZT) were 0.01 at 954 K for BaSi2 and 0.09 at 417 K for SrSi2. We tried to enhance the ZT values of BaSi2 and SrSi2 by prepareing and characterizing La-doped BaSi2 and (Ba,Sr)Si2 solid solution.

With the goal of developing high-performance bulk thermoelectric materials, we have characterized ternary silver thallium tellurides. The ternary silver thallium tellurides exhibit extremely low thermal conductivity (<0.5 Wm−1K−1) and consequently their thermoelectric performance is excellent. Although the extremely low thermal conductivity materials, as typified by the ternary silver thallium tellurides, would be a new class of next-generation thermoelectric materials, thallium compounds are unsuitable for practical application because of their toxicity. Against such a background, we are currently exploring thallium-free thermoelectric materials with extremely low thermal conductivity. In this paper, we will briefly summarize the thermoelectric properties of ternary thallium tellurides obtained in our group. Further experiments aimed at improving the ZT of these materials will be presented. Finally, we will propose two candidates: Ag8GeTe6 and Ga2Te3 as thallium-free low thermal conductivity materials.

We made various nitride fuels containing simulated FP elements and evaluated the effect of these FP elements on the properties of the nitrides. For Uranium Neodymium nitride solid solution the lattice parameter increased with Nd content, thermal expansion coefficient did not change and thermal conductivity decreased with Nd content. The thermal expansion for Pd containing UN, where Pd precipitated as UPd3 in the grain boundaries of UN, was nearly the same as that of UN and the thermal conductivity for Pd containing in the UN matrix decreased with Pd content. For Mo containing UN Mo precipitated as Mo metal isotropically. Both the thermal expansion and thermal conductivity did not vary with Mo content This might result from the low Mo contents at these simulated burnups.

Polycrystalline ingots of the lanthanide based ternary intermetallics: LaNiSb, GdNiSb, ErNiSb and ErPdSb were prepared and characterized. The thermoelectric properties of ErNiSb and ErPdSb were measured at high temperatures. We succeeded in preparing the single phase ingots of ErNiSb and ErPdSb, while the ingots of LaNiSb and GdNiSb contain appreciable quantities of the impurity phases. ErNiSb and ErPdSb crystallize the MgAgAs-type structure (half-Heusler structure). ErNiSb and ErPdSb indicate positive values of the Seebeck coefficient. The values at room temperature are 36 and 240 micro VK-1 for ErNiSb and ErPdSb, respectively. The electrical resistivity of ErNiSb and ErPdSb decreases with temperature, indicating semiconductor-like behavior. ErPdSb exhibits a relatively large power factor 1.5x10-3 Wm-1K-2 at around 700 K, which is approximately two times larger than that of ErNiSb.

Solidification of molten ceramics during molten state processing of High-Level Waste (HLW) was studied to investigate a possibility of a simpler and flexible process for immobilisation of HLW. Simulated HLW was heated together with different reducing agents (TiN with AlN or TiO2) either at 1673 K or 1873K for 1 to 3 hours under Ar atmosphere. Cooling rates of 5 K/min and 10 K/min did not result in any obvious differences in the products obtained under the standard condition used in the present study. The composition and quantity of the reducing agent had a significant effect on the melting and solidifying behaviour of the simulated HLW. The results suggest the possible further studies to improve the solidification process and the final product.