The α–β Transformation in Silicon Nitride Single Crystals

Single crystals of α-Si₃N₄ were annealed at 2000°–2150°C. The β phase was detected after annealing at 2150°C only when the crystals were surrounded by MgO·3Al₂O₃ or Y₂O₃ powders. On the other hand, no evidence of the α–β transformation was found when the crystals were annealed without additives. The solution–precipitation mechanism was concluded to be the dominant factor in the α–β transformation of Si₃N₄.     

Fabrication and Mechanical Properties of Continuously Graded MoSi2–ZrO2(2Y) Materials Using Wet-Molding

Continuously graded MoSi₂-ZrO₂(2Y) materials with high density (97.5% of theoretical) have been fabricated by uniaxial wet-molding, followed by hot pressing (1000°C/1 h/30 MPa) and hot isostatic pressing (1400°C/2 h/196 MPa). Their composition profiles are greatly influenced by the viscosity of mixed solutions of glycerin and ethanol used as a dispersion medium; a linear compositional gradient from MoSi₂/ZrO₂(2Y) 70/30 to 20/80 mol% is obtained from the solution (50/50 vol%) with a viscosity of 20 mPa s. Vickers hardness (Hv) and fracture toughness (KIC) increase from 9.7 to 12.4 GPa and from 5.1 to 12.5 MPa m1/2, respectively, with increasing ZrO₂(2Y) composition.     

Replication of Microstructures by Roll-to-Roll UV-Curing Embossing

The characteristics of pattern replication and releasing in a roll-to-roll ultraviolet- (UV) curing embossing process were investigated. The roll embossing system was designed for large-area continuous embossing, with employment of a fast curing resin, a heat damage protector, and a surface energy reducing coating. A 60° V-groove pattern with a groove period of 30 µm was embossed. It was found that the replication quality was profoundly influenced by the pattern geometry, the pattern direction, and the mold surface energy. In particular, the pattern direction significantly affected the edge sharpness and the surface topography of replicated features. In the parallel groove mode, a significant amount of tearing and sliding occurred, whereas in the transverse groove mode, biting marks were observed on the side wall of the V-groove. A simple mechanical model was used to explain the difference in pattern releasing with different pattern layouts. The replication quality was found to be significantly improved with the application of a fluorinated coating on the roll mold.     

THE EXTRACTION OF NEPTUNIUM(V) BY METHYLTRIOCTYLAMMONIUM CHLORIDE AND 1-PHENYL-3-METHYL-4-BENZOYL-5-PYRAZOLONE

The synergistic effect of methyltrioctylammonium chloride (QCI) on the extraction of Np(V) by 1-phenyl-3-methyl-4-benzoyl-pyrazolone(HP) in benzene is studied over the pH range 2-6. This system extracts Np(V) better than any previously reported. The interaction of the extractants and monomer-dimer equilibria affect the distribution behavior of Np(V) in a complicated manner. Analysis of the results suggests that NpO₂ ⁺ (M⁺) is extracted as mixed dimers, (QMP₂QCl)_o and (QMP₂QP)_o.     

Gas diffusion electrodes for polymer electrolyte fuel cells using novel organic/inorganic hybrid electrolytes: effect of carbon black addition in the catalyst layer

We have prepared novel gas diffusion electrodes for polymer electrolyte fuel cells (PEFC) using new organic/inorganic hybrid electrolytes. The catalyst layers were prepared by mixing 3-(trihydroxysilyl)-1-propanesulfonic acid [(THS)Pro-SO₃H], 1,8-bis(triethoxysilyl) octane (TES-Oct), Pt loaded carbon black (Pt-CB) and water, followed by a sol-gel reaction. It was found that addition of uncatalyzed carbon black (u-CB) into the cathode catalyst layer enhanced the performance at high current density region, due to an increase in the gas diffusion rate. The optimum volume ratio of u-CB/Pt-CB was found to be 0.1, at which the gas diffusivity and the catalyst utilization are well balanced.     

Investigation of the effect of surface phosphate ester dispersant on viscosity by coarse-grain modeling of BaTiO slurry

To understand the role of phosphate ester dispersant, we investigated the rheology of a BaTiO slurry. For the model case, a coarse-grain molecular dynamics (CGMD) simulation was performed with the butyral polymer didodecyl hydrogen phosphate (DHP) in the toluene/ethanol solvent. By systematically analyzing the effect of DHP from an atomic-scale first principle and from all-atom MD to microscale CGMD simulation, we investigated how the adsorption of a DHP dispersant on a BaTiO surface affects the microstructure rheology of a BaTiO slurry. The first-principle and all-atom MD simulation suggests that DHP molecules prefer to locate near the BaTiO surface. CGMD simulation shows a reduction in viscosity with an increase in dispersants, suggesting that the dispersant population near the BaTiO surface plays a key role in controlling the rheology of the BaTiO slurry. In this study, we propose an approach for understanding the BaTiO slurry with molecular-level simulations, which would be a useful tool for efficient optimization of slurry preparation.     

The metabolism and distribution of docosapentaenoic acid (n−6) in rats and rat hepatocytes

In this study, a new marine oil that contains 45% docosahexaenoic acid (DHA, 22∶6n−3) and 13% docosapentaenoic acid (DPA, 22∶5n−6) was administered to rats. The metabolism and distribution of DPA in rats was investigated. In experiment 1, the effects of DHA and n−6 fatty acids (linoleic acid, I A; arachidonic acid, AA; and DPA) on AA contents were investigated in vivo. LA group: LA 25%, DHA 30%; LA-DPA group: LA 15%, DPA 10%, DHA 35%; LA-AA-DPA group: LA 10%, AA 5%, DPA 10%, DHA 35% were administered to rats for 4 wk. In the liver, the AA content in the LA-DPA and LA-AA-DPA groups was significantly higher than in the LA group. The decreased AA contents in the LA group might be caused by DHA administration. Although DHA also was administered in the LA-DPA and LA-AA-DPA groups, the AA contents in these two groups did not decrease. These results suggested that DPA retroconverted to AA, blunting the decrease in AA content caused by DHA administration. To conduct a detailed investigation on DPA metabolism and its relation with AA and DHA, rat hepatocytes were cultured with pruified DPA and DHA for 24 h. We discovered the retroconversion of DPA to AA occurred only when AA content was decreased by a high DHA administration; it did not occur when AA content was maintained at a normal level.     

Role of Acetic Acid Added to the Reaction Media for the Enantio-differentiating Hydrogenation of Methyl Acetoacetate Over a Tartaric Acid-modified Nickel Catalyst

The role of acetic acid added to the reaction media for the enantio-differentiating hydrogenation of methyl acetoacetate over a (R,R)-tartaric acid-in-situ-modified nickel catalyst was studied from the viewpoint of the hydrogenation rate during repeated runs. The hydrogenation of methyl acetoacetate on the “enantio-differentiating sites” of a tartaric acid-modified nickel catalyst was specifically accelerated by the acetic acid added to the reaction media to increase the enantio-differentiating ability of the catalyst. In order to increase the enantio-differentiating ability, the addition of acetic acid to the reaction media was required in each run during the repeated use of the catalyst.     

Study of the properties of nickel oxide and nickel as precursors for the tartaric acid-NaBr-modified nickel catalyst

Nickel oxide was prepared by the decomposition of nickel hydroxide and then the nickel oxide was reduced to form the nickel catalyst. The properties of the nickel oxide and the reduced nickel were studied in relation to the enantio-differentiating ability (e.d.a.) of a tartaric acid-NaBr-modified reduced nickel catalyst. The modified nickel catalyst prepared from nickel oxide with less non-stoichiometric oxygen produced a high e.d.a. for the hydrogenation of methyl acetoacetate. The high crystallinity of the nickel oxide and the resultant nickel would be required to attain a high e.d.a.     

Structural color films with lotus effects, superhydrophilicity, and tunable stop-bands

The structural blue color of a Morpho butterfly originates from the diffraction of light and interference effects due to the presence of the microstructures on the wing of the butterfly. Structural color on the surface of a damselfish reversibly changes between green and blue. Inspired by these creatures, we have been trying to prepare high-quality and functional structural color films. We describe our efforts in this Account. A useful technique to prepare such structural color films in colloidal solution is a "lifting" method, which allows us to quickly fabricate brilliant colloidal crystal films. The thicknesses of the films can be controlled by precisely adjusting the particle concentration and the lifting speed. Moreover, in order to prepare a complicated structure, we have used template methods. Indeed, we have successfully prepared the inverse structure of the wing of a Morpho butterfly with this technique. Initially, however, our structural color films had a whitish appearance due to the scattering of light by defects in the colloidal crystal film. Later, we were able to prepare a non-whitish structural color film by doping an appropriate dye in the colloidal particles to absorb the scattering light. In addition to the structural blue color, the wing of the Morpho butterfly has superhydrophobic properties. According to Wenzel's equation, the hydrophobic and hydrophilic properties are enhanced when the roughness of the hydrophobic and hydrophilic surface is increased, respectively. Based on this mechanism, we have successfully prepared structural color films with superhydrophobic properties, as well as with superhydrophilic properties. Another important property that can be seen in nature is tunable structural color, such as the color change that can be seen on the surface of a damselfish. In order to mimic such color change, we have developed several tunable structural color films. In particular, we have successfully prepared phototunable photonic crystals using photoresponsive azobenzene derivatives. In order to apply these structural color films, we developed a technique for patterning them by taking advantage of the wettability of the substrate surface. These materials can be used in the future for self-cleaning pigments and tunable photonic crystals.