Co-continuous monolithic titania prepared by organic polymer monolith as pore template

We achieved preparation of co-continuous titania based monolithic materials using several organic polymer monoliths as pore templates. Firstly, the organic polymer monoliths that had well controlled structures were prepared, and filled the pores of polymer monolith with tetra-n-butyl titanate (titan monomer). The following hydrolysis of the titan monomer resulted in titanium dioxide. The polymer monolith was removed by calcination at elevated temperature. We carefully studied the utility of polymer monolithic template, filling method of the titan monomer, and calcination conditions to realize co-continuous titania monolith. In addition, by the change of domain size (size of a skeleton + size of through a pore) of template, we were able to control domain size of the resulting titania monoliths.     

Preparation of SrBi 2 Ta 2 O 9 Thin Films by Liquid-Delivery MOCVD Without Additional Solvents

SrBi 2 Ta 2 O 9 thin films were prepared by ECR plasma enhanced metalorganic chemical vapor deposition (ECR-MOCVD) with a liquid-delivery system using one cocktail source without an additional solvent. The strontium-tantalum double alkoxide, Sr{Ta[OC 2 H 4 H(CH 3 ) 2 ](OC 2 H 5 ) 5 } 2 , was dissolved in stabilized trimethyl bismuth, Bi(CH 3 ) 3 / dioxane. This source system has been used in a conventional bubbling system. Deposition rate and the composition of the films were strictly controlled by the concentration and the composition of the cocktail source. Therefore, high reproducibility was realized by using this system. The constituent phase of the stoichiometric SBT film as-deposited at 500 C on a (111)Pt/TiO 2 /SiO 2 /Si substrate was a fluorite phase and transformed to the single phase of SBT by the post annealing at 800 C. It showed almost the same ferroelectricity as the stoichiometric composition film.     

Mixed powder coating film using thermoplastic polyester and its alkaline resistance

To improve alkaline resistance, a newly mixed powder coating film using thermoplastic polyethylene terephthalate (PET) was investigated. Two kinds of polyvinyl butyral (PVB) and two kinds of polyamide (PA) were chosen as the secondary polymer. The melting temperatures (T _ms) of these materials were lower than that of primary PET polymer so the mixed powder coating was able to form a dual phase film through a fluidized bed coating process. Microscope and Fourier transform infrared spectroscopy (FTIR) observations revealed that the dual phase structure was indeed successfully formed and there was a secondary layer over the entire surface area of the film. This mixed powder coating film significantly enhanced the alkaline resistance to an environment filled with NaOH solution at 40°C in which a secondary material would be effective in protecting the film. With regard to both alkaline resistance and film formability, PET/PVB was superior to the PET/PA mixture.     

Research on some basic deformations in free forging with robot and servo-press

Due to the disadvantages in casting or hot forging of Ti alloy artificial bones, such as low strength and high energy cost, this paper prompted an alternative method to manufacture individuated artificial bones. Free forging with a 6-axis freedom robot and servo-press could be very economical in the forming of complex shape parts because of its high flexibility and simple die-setting. Based on this system, the authors studied deformations of some basic elements, which could be assembled to artificial bones with complex shape. Firstly, the compression limit and effect of compression parameters on the roundness during reducing diameter process were declared for Al alloy and pure Ti. Secondly, an approximate theoretical equation of bending angle or curvature radius was proposed, and it matches experimental results well. Finally, a dimension prediction equation was presented by considering effect of material anisotropy, and then the ladder part without width spread was manufactured accordingly.     

Microelectrode-based hydrogen peroxide detection during oxygen reduction at Pt disk electrode

We investigated the diffusion process of H₂O₂ generated during O₂ reduction at a Pt microdisk electrode used as a generator for scanning electrochemical microscopy (SECM). First, the amount of O₂ consumption and generated H₂O₂ at the Pt generator electrode are estimated using a detector electrode installed in the SECM. Based on the results, a large amount of O₂ consumption and generated H₂O₂ are detected at the center of each generator electrode. According to the measurement, the O₂ starvation and H₂O₂ detection currents can be defined. Subsequently, the O₂ starvation and H₂O₂ detection currents are measured by varying the generator size. As a result, these currents decrease with a decrease in the generator electrode size, however, the H₂O₂ diffusion process is changed for the generator diameter of less than 50 μm. Finally, the O₂ starvation and H₂O₂ detection measurements were conducted using a Nafion-coated Pt microdisk electrode. The amount of O₂ consumption is not suppressed, while the amount of generated H₂O₂ decreases with the Nafion layer prepared on the Pt electrode. This result indicates that the thickness of the H₂O₂ diffusion layer in the H₂SO₄ solution is dramatically diminished by coating the Nafion layer on the Pt generator.     

Single molecule fluorescence autocorrelation measurement on anisotropic molecular diffusion in nematic liquid crystal

Diffusion kinetics of three dyes in nematic liquid crystals are studied with single-molecule fluorescence autocorrelation spectroscopy. Markedly large anisotropy was observed in the diffusion coefficient and structure of diffusion molecules showed no marked effect on the anisotropy.     

Synthesis and thermal cure of high molecular weight polybenzoxazine precursors and the properties of the thermosets

High molecular weight polybenzoxazine precursors have been synthesized from aromatic or aliphatic diamine and bisphenol-A with paraformaldehyde. The precursors were obtained as soluble white powder. Molecular weight was estimated from the size exclusion chromatography to be several thousands. The structure of the precursors was confirmed by IR, ¹H NMR and elemental analysis, indicating the presence of cyclic benzoxazine structure. The ratio of the ring-closed benzoxazine structure and the ring-opened structure in the high molecular weight precursor was estimated from ¹H NMR spectrum and also from the exotherm of DSC, showing that the ratio of the ring-closed benzoxazine structure was 77–98%. The precursor solution was cast on glass plate, giving transparent and self-standing precursor films, which was thermally cured up to 240 °C to give brown transparent polybenzoxazine films. The toughness of the crosslinked polybenzoxazine films from the high molecular weight precursors was greatly enhanced compared with the cured film from the typical low molecular weight monomer. Tensile measurement of the polybenzoxazine films revealed that polybenzoxazine from aromatic diamine exhibited the highest strength and modulus. While, polybenzoxazine from longer aliphatic diamine had higher elongation at break. The viscoelastic analyses showed that the glass transition temperature of the polybenzoxazines derived from the high molecular weight precursors were as high as 238–260 °C. Additionally, these novel polybenzoxazine thermosets showed excellent thermal stability.     

Water vapor solubility of poly(lactic acid) films modified the surface by vacuum ultraviolet irradiation

Surface modification of poly(lactic acid) (PLA) film is performed via 172 nm excimer lamp irradiation. Effects on water vapor solubility and physical properties via vacuum ultraviolet (VUV) irradiation are studied systematically. After VUV irradiation, water vapor solubility increases approximately 11–43% in the low‐pressure region and approximately 20–38% in the high‐pressure region as surface hydrophilicity increased. The increase is attributed to hydrogen bonding with the carboxyl groups because of VUV radiation. The modified layer is significantly swelling after water vapor sorption. The hydrophilic layer forms a thickness of 2–3 μm from the irradiated surface via VUV radiation, but no changes are observed inside the irradiated film. Therefore, PLA film solubility after irradiation is enhanced by hydrophilicity and the swelling effect of the surface. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42200.     

Absolute Configuration of β- and α-Asymmetric Carbons within β-O-4-Structures in Hardwood Lignin

In this study, we investigated the proportion of erythro- and threo-forms of β-O-4-ether structures and their enantiomeric compositions in hardwood lignin by applying the ozonation method to birch wood meal. Optical activity was not substantially observed in either the erythronic or threonic acids obtained as the ozonation products of β-O-4-structures in birch wood meal. The proportions of the four stereoisomeric forms {(αS,βR)-erythro, (αR,βR)-threo, (αS,βS)-threo, and (αR,βS)-erythro forms} were estimated to be 37-38%, 13-14%, 12-13%, and 36-37% based on the yields of erythronic and threonic acids, and on their optical activities. The proportions suggest that the entire components of β-O-4-ether structures in birch wood lignin have R- and S-configurations at the β-carbon in approximately the same quantities {(βR)-β-O-4-structure: (βS)-β-O-4-structure = 50–52:48–50}; i.e., that the β-ether structures are essentially racemic. This estimation implies that, during lignin biosynthesis, an equal number of enantiomeric forms of β-O-4-bonded quinone methides were formed by radical coupling reactions.