Organic–inorganic nanomatrix structure and properties of related naturally occurring rubbery macromolecules

The outstanding mechanical properties of soft materials i.e. natural rubber are partly due to the organic–inorganic nanomatrix structure because numerous organic microparticles are dispersed in a small amount of an inorganic nanomatrix composed of inorganic nanoparticles and organic macromolecules. Here we form an organic–inorganic nanomatrix using graft-copolymerization of a vinyl monomer with an inorganic oxide precursor onto natural rubber particles with an average diameter of 1 μm dispersed in water. The inorganic oxide precursor is converted into inorganic oxide nanoparticles through hydrolysis and condensation, forming chemical linkages between natural rubber microparticles and inorganic oxide nanoparticles. Transmission electron microscopy indicates that the organic–inorganic nanomatrix is densely filled with inorganic oxide nanoparticles and the natural rubber microparticles are dispersed in the nanomatrix. This nanomatrix composite realizes both energetic elasticity and entropic elasticity of a soft material, opening a novel field of building block chemistry with respect to a pair of organic microparticles and inorganic nanoparticles.     

Boiling heat transfer characteristics of a sulfuric-acid flow in thermochemical iodine–sulfur cycle

The Japan Atomic Energy Agency has been conducting research and development on the thermo-chemical iodine–sulfur (IS) process, which is one of the most attractive water-splitting hydrogen production methods that uses nuclear thermal energy. The sulfuric acid decomposer is one of the key components of the IS process. The boiling heat transfer coefficients of sulfuric acid solutions are required to design the sulfuric acid decomposer. These coefficients were measured in aqueous solutions where the mole fraction of H₂O ranged from 0.17 to 0.37 (heat flux range from 16.9 kW/m² to 5.6 kW/m²) and compared with the empirical correlations formulated for binary mixtures. A combination of the Stephan–Körner correlation, using the empirical constant A₀ = 2.00, and the Nishikawa–Fujita correlation was used to predict the experimental results with an accuracy of ±10%.     

Investigation of radiation-induced surface activation effect in austenitic stainless steel under ultraviolet and γ-ray irradiations

The radiation-induced surface activation (RISA) effect will be applied to the core design in supercritical light water reactor (SCWR) in order to achieve a high performance with excellent economy and safety. The purpose of the present study is to investigate the RISA effect in the candidate fuel cladding materials in SCWR such as PNC1520. The change of weldability due to RISA effect and the related microstructure analysis were performed in oxidized PNC1520 and 304 stainless steel with various oxidization periods. The phases contained in the surface oxide layer of the present specimen were identified as Fe₂CrO₄, γ-Fe₂O₃, and Fe₂O₃. The lifetime of 13.8 days for wettability improving factor was confirmed in the ultraviolet (UV) irradiation. Meanwhile, the long life of 13.8 days and short life of 0.8 days for wettability improving factors were identified in the γ-ray irradiation. Based on the fact that the band gap energies of Fe₂CrO₄, γ-Fe₂O₃, and Fe₂O₃ were, respectively, 2.1, 2.0, and 2.2 eV, and the photo energies of UV and γ-ray irradiation were 4.48 eV and 13.3 MeV, it is therefore clarified that the hydrophilization on the oxide layer is ascribed to the RISA effect.     

Accumulation and elimination profiles of paralytic shellfish poison in the short-necked clam Tapes japonica fed with the toxic dinoflagellate Gymnodinium catenatum

The paralytic shellfish poison (PSP)-producing dinoflagellate Gymnodinium catenatum (Gc) was fed to the short-necked clam Tapes japonica, and the accumulation, transformation and elimination profiles of PSP were investigated by means of high-performance liquid chromatography with postcolumn fluorescence derivatization (HPLC-FLD). The short-necked clams ingested most of the Gc cells (4 x 10(6) cells) supplied as a bolus at the beginning of the experiment, and accumulated a maximal amount of toxin (181 nmol/10 clams) after 12 hr. The rate of toxin accumulation at that time was 16%, which rapidly decreased thereafter. During the rearing period, a variation in toxin composition, derived presumably from the transformation of toxin analogues in the clams, was observed, including a reversal of the ratio of C2 to C1, and the appearance of carbamate (gonyautoxin (GTX) 2, 3) and decarbamoyl (dc) derivatives (decarbamoylsaxitoxin (dcSTX) and dcGTX2, 3), which were undetectable in Gc cells. The total amount of toxin contained in clams and residue (remaining Gc cells and/or excrement in the rearing tank) gradually declined, and only about 1% of the supplied toxin was detected at the end of the experiment.     

SFG study on potential-dependent structure of water at Pt electrode/electrolyte solution interface

Structure of water at Pt/electrolyte solution interface was investigated by sum frequency generation (SFG) spectroscopy. Two broad peaks were observed in OH stretching region at ca. 3200 cm⁻¹ and ca. 3400 cm⁻¹, which are known to be due to the symmetric OH stretching (υ₁) of tetrahedrally coordinated, i.e., strongly hydrogen bonded “ice-like” water, and the asymmetric OH stretching (υ₃) of water molecules in a more random arrangement, i.e., weakly hydrogen bonded “liquid-like” water, respectively. The SFG intensity strongly depended on electrode potential. Several possibilities are suggested for the potential dependence of the SFG intensity.     

Synthesis and electrochemistry of cubic rocksalt Li–Ni–Ti–O compounds in the phase diagram of LiNiO2–LiTiO2–Li[Li1/3Ti2/3]O2

On the basis of extreme similarity between the triangle phase diagrams of LiNiO₂–LiTiO₂–Li[Li_1/3Ti_2/3]O₂ and LiNiO₂–LiMnO₂–Li[Li_1/3Mn_2/3]O₂, new Li–Ni–Ti–O series with a nominal composition of Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ (0 ≤ z ≤ 0.5) was designed and attempted to prepare via a spray-drying method. XRD identified that new Li–Ni–Ti–O compounds had cubic rocksalt structure, in which Li, Ni and Ti were evenly distributed on the octahedral sites in cubic closely packed lattice of oxygen ions. They can be considered as the solid solution between cubic LiNi_1/2Ti_1/2O₂ and Li[Li_1/3Ti_2/3]O₂ (high temperature form). Charge–discharge tests showed that Li–Ni–Ti–O compounds with appropriate compositions could display a considerable capacity (more than 80 mAh g⁻¹ for 0.2 ≤ z ≤ 0.27) at room temperature in the voltage range of 4.5–2.5 V and good electrochemical properties within respect to capacity (more than 150 mAh g⁻¹ for 0 ≤ z ≤ 0.27), cycleability and rate capability at an elevated temperature of 50 °C. These suggest that the disordered cubic structure in some cases may function as a good host structure for intercalation/deintercalation of Li⁺. A preliminary electrochemical comparison between Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ (0 ≤ z ≤ 0.5) and Li_6/5Ni_2/5Ti_2/5O₂ indicated that charge–discharge mechanism based on Ni redox at the voltage of >3.0 V behaved somewhat differently, that is, Ni could be reduced to +2 in Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ while +3 in Li_6/5Ni_2/5Ti_2/5O₂. Reduction of Ti⁴⁺ at a plateau of around 2.3 V could be clearly detected in Li_1+z/3Ni_1/2−z/2Ti_1/2+z/6O₂ with 0.27 ≤ z ≤ 0.5 at 50 °C after a deep charge associated with charge compensation from oxygen ion during initial cycle.     

Electrical Properties of Superlattice-Structured Bi4Ti3O12–PbBi4Ti4O15 Single Crystals

Single crystals of superlattice-structured ferroelectrics composed of Bi₄Ti₃O₁₂ and PbBi₄Ti₄O₁₅ were grown and the properties of polarization hysteresis and leakage current along the a -axis were investigated. Oxidation treatment led to a marked increase in leakage current at room temperature, showing that electron hole acts as a detrimental carrier for electrical conduction. A well-developed polarization hysteresis with a remanent polarization of 41 μC/cm² was observed, which is suggested to originate from the peculiar ferroelectric displacement of Bi in the Bi₂O₂ layers.     

The development of pivot bearing with multiple degrees of freedom: 1st report: Prototype of pivot bearing with two degrees of freedom

This paper deals with the prototype of a new pivot bearing having two degrees of freedom. The idea of the pivot bearing is based on a continuous velocity joint (CVJ). The experimental axial stiffness and contact pressure are compared with those determined by theoretical analysis. Then, it is confirmed that the pivot bearing swings smoothly with a range of ±25°. Furthermore, the stiffness of the bearing increases as the swinging angle becomes larger. Therefore, this newly developed pivot bearing may be applied to a parallel mechanism, a joint of robot and so on.     

Quantum Effects on Hydrogen Isotopes Adsorption in Nanopores

We have investigated the applicability of simulations and theoretical techniques for exploring the selectivities of hydrogen isotopes. We have simulated the adsorption isotherms of H₂ in an idealized carbon slit pore at 77 K by using the grand canonical Monte Carlo simulations with the Feynman-Hibbs effective potential (FH-GCMC) and the rigorous path integral method (PI-GCMC), and we obtained good agreement between the isotherms from both simulations. This suggests that FH-GCMC, which uses the approximative Feynman-Hibbs treatment, is as useful as PI-GCMC for exploring H₂ adsorption at 77 K. Moreover, we show that the ideal adsorption solution theory (IAST) can predict the selectivity of D₂ over H₂ in the interstices of single-wall carbon nanotube (SWNT) bundles at 77 K (below 0.1 MPa) very well by comparing the obtained results with the mixture adsorption FH-GCMC simulations. This indicates that IAST is also applicable to the estimation of the selectivity of D₂ over H₂ at moderate pressures and at 77 K from experimental single-component adsorption isotherms. We also demonstrate that the FH-GCMC simulation can reproduce the experimental adsorption isotherms of H₂ and D₂ in aluminophosphate AlPO₄-5 at 77 K. Finally, we analyze the selectivity of D₂ over H₂ by IAST with the experimental single-component adsorption isotherms of H₂ and D₂ at 77 K for a variety of adsorbents: AlPO₄-5, activated carbon fibers (ACFs), HiPco SWNT, and SWNHs. The selectivities predicted by the experimental adsorption data based on the results from the FH-GCMC simulations are presented and discussed.