Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Effect of metallic ions in photo-induced graft copolymerization onto cellulose

In photo-induced graft copolymerization of methyl methacrylate onto cellulose, the effect of metallic ions as sensitizer was investigated. Some metallic ions were effective in their adsorbed states and accelerated the formation of grafts in the order Fe²⁺ > Ag⁺ > Fe³⁺. However, Cu²⁺ acted negatively, and little effect was observed for Co²⁺, Ni²⁺, Mn²⁺, Zn²⁺, and Cr³⁺. In the systems in which aqueous metallic salt solutions were added, the formation of grafts was generally depressed, but Fe³⁺ was an exception. The effect of metallic ions on the scission reaction of cellulose main chains did not necessarily agree with the effect on the formation of grafts. This is attributed to the varied interaction between cellulose and the different active species produced by irradiation, depending on the type of metallic ions used.     

Antioxidizing component,musizin, inrumex japonicus houtt

A substance with antioxidant properties was obtained from the hexane extract of roots ofRumex japonicus Houtt. The active component of the hexane extract was isolated and characterized as 2-acetyl-1,8-dihydroxy-3-methyl naphthalene, trivially named musizin (MUS). The antioxidant activities of MUS in six types of fats and oils were higher than that of butyl hydroxyanisole (BHA) and δ-tocopherol (δ-TOC). Together, TOC and MUS have a synergistic effect, because comparable amounts of either had lower antioxidant activity than various combinations of the two antioxidants. When we studied the antioxidant properties of a mixture of MUS and δ-TOC with methyl linoleate (MeLH), we found that the rates of destruction of the two antioxidants were comparable, but that their destruction occurred sequentially, with MUS first followed by δ-TOC, after which the oxidation of MeLH quickly occurred. Comparison of the antioxidant activity of MUS and its analogs suggests that only one of the two hydroxyl groups in MUS is involved in its antioxidant activit. Intermolecular hydrogen bonding may be involved.     

Graft copolymerization to cellulose. Effect of sodium thiosulfate on hydrogen peroxide initiator system

The effect of sodium thiosulfate on the graft copolymerization of methyl methacrylate to cellulose in the hydrogen peroxide initiator system was investigated. The addition of sodium thiosulfate in general was effective for decreasing the per cent grafting and the average molecular weight of grafts and increasing the formation of homopolymer, and the effects became pronounced with increasing hydrogen peroxide concentration. Moreover, the addition of sodium thiosulfate slightly suppressed the formation of grafts at a hydrogen peroxide concentration of 3 mmole/l., but greatly promoted it at 20 mmole/l. Traces of metallic ions present in cellulose could not be eliminated sufficiently by treatment with 3N hydrochloric acid. Such ions were found to interact with hydrogen peroxide and thus participate directly in the initiation and termination of the polymerization reaction. EDTA, the chelating agent, was highly effective for suppressing such participation of metallic ions. In the hydrogen peroxide initiator system applied to the EDTA-treated samples, sodium thiosulfate caused an effective initiation of graft formation.     

Pervaporation via silicon-based membranes: Correlation and prediction of performance in pervaporation and gas permeation

Pervaporation (PV) is a membrane technology that holds great promise for industrial applications. To better understand the PV mechanism, PV dehydrations of various types of organic solvents (methanol, ethanol, iso-propanol, tert-butanol, and acetone) were performed on five types of organosilica and two types of silicon carbide-based membranes, all with different pore sizes. Water permeance was dependent on the types of organic aqueous solutions, which suggested that organic solvents penetrated the pores and hindered the permeation of water. In addition, water permeance of various types of membranes in PV was well correlated with hydrogen permeance in single-gas permeation. Furthermore, a clear correlation was obtained between the permeance ratio in PV and that in single-gas permeation, which was confirmed via the modified-gas translation model. These correlations make it possible to use single-gas permeation properties to predict PV performance.     

Reinforcement of polypropylene by cellulose microfibers modified with polydopamine and octadecylamine

Cellulose microfibers (CMFs) having surfaces modified with polydopamine (PDPA) and octadecylamine (ODA) were prepared, and their reinforcing abilities for polypropylene (PP) were investigated. The PDPA coating was made via self-polymerization of dopamine (P-CMF), and subsequent alkylation was conducted by the reaction with ODA (OP-CMF). The modified CMFs exhibited improved dispersibility in the PP matrix due to the reduced hydrophilicity. The OP-CMF/PP composite prepared by batch mixing had a higher tensile modulus compared to that for the pure PP and composites with unmodified CMFs. However, excess alkylation lowered the tensile modulus, and the presence of an optimal degree of alkylation was demonstrated. The CMF/PP-IM composites fabricated by injection molding exhibited improved tensile properties compared to those prepared by batch mixing. Both the tensile modulus and yield stress were increased by increasing the CMF content and improved by the surface modification of the CMFs.     

Texture of primary recrystallization on nonoriented electrical steel sheet with phase transformation

The magnetic properties of nonoriented (NO) electrical steel sheet are commonly improved if the texture of their products possesses “cube texture” (e.g., {100 〈0vw〉, “goss texture”) (i.e., 110〈011〉, and less 222 texture). Industrially “cube type” has not been obtained, but “goss texture” has been. In a greater or lesser degree, {222} texture exists. To improve “goss texture” and reduce 222 texture, the grain size of the material prior to cold rolling should be larger. When the grain size before cold rolling is larger, during primary recrystallization, “goss texture” is enriched, 222 texture is decreased, and the grain grows so easily that higher induction and lower core loss can be obtained. This does not depend on the presence of phase transformation. In case of NO steel with phase transformation, heat treatment before cold rolling has been done below the austenite transition temperature (Acin1) in order to prevent the fine grain size caused by α → γ(+α) → α transformation. By using material that was heated over Acin1 and cooled with changing cooling rates, this study describes (a) the relationship between textures before cold rolling and the texture of the final product, and (b) the development of the magnetic properties.     

Infiltrating the zebrafish swarm: design,implementation and experimental tests of a miniature robotic fish lure for fish–robot interaction studies

Robotic fish are nowadays developed for various types of research, such as bio-inspiredrobotics, biomimetics and animal behavior studies. In the context of our research on the social interactions of the zebrafish Danio Rerio, we developed a miniature robotic fish lure for direct underwater interaction with the living fish. This remotely controlled and waterproof device has a total length of 7.5 cm with the same size ratio as zebrafish and is able to beat its tail with different frequencies and amplitudes, while following the group of living animals using a mobile robot moving outside water that is coupled with the robotic lure using magnets. The robotic lure is also equipped with a rechargeable battery and can be used autonomously underwater for experiments of up to 1 h. We performed experiments with the robot moving inside an aquarium with living fish to analyze its impact on the zebrafish behavior. We found that the beating rate of the tail increased the attractiveness of the lure among the zebrafish shoal. We also demonstrated that the lure could influence a collective decision of the zebrafish shoal, the swimming direction, when moving with a constant linear speed inside a circular corridor. This new robotic fish design and the experimental results are promising for the field of fish–robot interaction.     

Anaerobic degradation of palm oil mill effluent (POME)

The biodegradation characteristics of palm oil mill effluent (POME) and the related microbial community were studied in both actual sequential anaerobic ponds in Malaysia and enrichment cultures. The significant degradation of the POME was observed in the second pond, in which the temperature was 35-37 °C. In this pond, biodegradation of major long chain fatty acids (LCFA), such as palmitic acid (C16:0) and oleic acid (C18:1), was also confirmed. The enrichment culture experiment was conducted with different feeding substrates, i.e. POME, C16:0 and C18:1, at 35 °C. Good recovery of methane indicated biodegradation of feeds in the POME and C16:0 enrichments. The methane production rate of the C18:1 enrichment was slower than other substrates and inhibition of methanogenesis was frequently observed. Denaturing gradient gel electrophoresis (DGGE) analyses indicated the existence of LCFA-degrading bacteria, such as the genus Syntrophus and Syntorophomonas, in all enrichment cultures operated at 35 °C. Anaerobic degradation of the POME under mesophilic conditions was stably processed as compared with thermophilic conditions.     

Micromachining of electroformed nickel mold using thick photoresist microstructure for imprint technology

In order to fabricate polymer-based microstructures with feature sizes on the order of micrometers, we have been developing a microimprint technology with a fine nickel (Ni) mold instead of a conventional photolithography technique. The Ni mold was successfully fabricated by electroforming using a positive thick photoresist microstructure patterned on a silicon substrate as a replication master. The photoresist microstructure with excellent edge quality can be obtained under irradiation with single wavelength (g line) selected from a high-pressure mercury lamp. In addition, its sidewall angle in the range of 65° to 84° can be controlled precisely by varying the distance between a photomask and a photoresist surface. On the structured photoresist master, Ni was electroplated up to a thickness of about 110 μm, and then removed from the master. In this process, two-step electroplating at different current densities was carried out in order to prevent deformation of the photoresist master due to stress generated in a Ni electrodeposit. With the Ni mold, fine patterns with a width of 10 or 30 μm and a depth of 24 μm were almost completely transferred to polymetric materials (PMMA). The geometrical dimensions of the fabricated PMMA microstructures were found to be only about 10% reduction against the Ni mold.