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 crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Molecular species of 1-O-alk-1′-enyl-2-acyl-, 1-O-alkyl-2-acyl- and 1,2-diacyl glycerophospholipids in Japanese oysterCrassostrea gigas (Thunberg)

Molecular species of 1-O-alk-1′-enyl-2-acyl-, 1-O-alkyl-2-acyl-, and 1,2-diacyl-sn-glycero-3-phosphoethanolamine (EPL) andsn-glycero-3-phosphocholine (CPL) of Japanese oysterCrassostrea gigas were analyzed by selectedion monitoring gas chromatography/mass spectrometry using electron impact ionization. The characteristic fragment ions, [RCH=CH+56]⁺ due to the alkenyl residue in thesn-1 position and [RCO+74]⁺ due to the acyl residue in thesn-2 position of alkenylacylglycerols, [R+130]⁺ due to the alkyl residue in thesn-1 position and [RCO+74]⁺ due to the acyl residue in thesn-2 position of alkylacylglycerols, [RCO+74]⁺ due to the acyl residues in thesn-1 and/orsn-2 positions of diacylglycerols, and [M−57]⁺ being indicative of the corresponding molecular weight, were used for structural assignments. For alkenylacyl EPL and CPL, 19 and 16 molecular species were determined, respectively. Two molecular species, 18∶0alkenyl-22∶6n−3 and 18∶0-alkenyl-22∶2-non-methylene interrupted diene (NMID), amounted to 53.2% and 47.9%, respectively. The alkylacyl EPL and CPL consisted of 16 and 20 molecular species, respectively, and the prominent components were 18∶0alkyl-22∶2NMID, 20∶1alkyl-20∶1n−11 (27.4%) and 20∶1alkyl-20∶2NMID (16.3%) in the former, and 16∶0alkyl-20∶5n−3 (23.0%) and 16∶0alkyl-22∶6n−3 (21.6%) in the latter. For the diacyl EPL and CPL, 14 and 51 molecular species were determined, respectively. The major molecular species were 18∶0–20∶5n−3 (37.4%), 16∶0–20∶5n−3 (14.2%) and 18∶1n−7–22∶2NMID (13.2%) in the former, and 16∶0–20∶5n−3 (33.4%) and 16∶0–22∶6n−3 (22.3%) in the latter. It was found that there were significant differences in the molecular species between the alkylacyl and diacyl EPL and the alkylacyl and diacyl CPL; the number of molecular species was larger in CPL than in EPL, while the number of total carbons and double bonds of the major molecular species were larger in the EPL than in the CPL. Alkenylacyl EPL were similar to alkenylacyl CPL in molecular species composition.     

Properties of aqueous solutions for two binary mixed systems between two kinds of bile salts and nonionic surfactants

The micellar properties of aqueous binary mixed solutions for two systems consisting of sodium cholate (NaC)-octaoxyethylene glycol mono n-decyl ether (C₁₀E₈) and sodium glycocholate (NaGC)-C₁₀E₈ have been studied on the basis of surface tensions, polarity of the micelle interior and the mean aggregation number. Application of two theoretical treatments, based on regular solution and excess thermodynamic quantities for critical micellar concentration (CMC) data from surface tension curves of two mixed systems showed that the mole fraction of each bile salt in the mixed micelles near the CMC is lower than that of the corresponding prepared mole fraction in the mixed solution. The polarity of the interior suggested that the hydrophobicity of intramicelles increased with the increase of the mole fraction of bile salt in the mixed solution and that the mixed micelles become dramatically more hydrophobic at a mole fraction of 0.68 for NaGC−C₁₀E₈ system and 0.75 for NaC−C₁₀E₈ system, respectively. This implies that the micelles become richer in the bile salt molecules and the tendency appears strongly for NaGC−C₁₀E₈ system due to the strong cohesion between the conjugated glycines in the NaGC molecules. The decrease of aggregation number with the increase of the mole fraction of bile salts shows that the micelles approach those of the single system of each bile salt. This supports the previously mentioned facts.     

Synthesis of thermosetting poly(phenylene ether) containing allyl groups

New thermosetting poly(2-allyl-6-methylphenol-co-2,6-dimethylphenol)s (3) have been developed by oxidative coupling copolymerization of 2-allyl-6-methylphenol (1) with 2,6-dimethylphenol (2), followed by thermal curing. Copolymerization was conducted in nitrobenzene in the presence of copper(I) chloride and pyridine as the catalyst under a stream of oxygen, producing high molecular weight copolymers (M_n∼50,000) with broad molecular weight distributions (M_w/M_n∼35). The structure of resulting copolymers 3 was characterized by IR, ¹H, and ¹³C NMR spectroscopy. Cross-linking reactions of copolymers were carried out by thermal treatment in the absence or presence of a peroxide (3 wt%, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-butane). The 10% weight loss and glass transition temperatures of the cured copolymers were 436 °C in nitrogen and 235 °C, respectively after curing at 70 °C for 1 h and 300 °C for 1 h. The average refractive index of the cured copolymer (3b) film was 1.5407, from which the dielectric constant (ε) at 1 MHz was estimated as 2.6. The ε and dissipation factor of copolymer-films at 1 MHz were directly measured from their capacitances as 2.5-2.6 and 0.0015-0.0019, respectively.     

Quantitative determination of corrosion products and adsorbed water on copper in humid air containing SO2 by IR-RAS measurements

The time dependency of the amounts of corrosion products and co-existing adsorbed water on copper in humid air containing SO₂ was estimated from a series of in situ time-resolved IR-RAS spectra on the basis of the relations between the band intensities and the mass changes of the corrosion products, which were determined by simultaneous measurement of IR-RAS and QCM. The amounts of both corrosion products increased slowly at the initial stage and later increased rapidly. Although the relative humidity was kept constant, the amount of adsorbed water increased nearly the same behavior as that of corrosion products in the stage of relatively small amounts of corrosion products and later increased rapidly when the amounts of corrosion products increased. In humid air without SO₂, sulfite gradually decomposed and some of it changed into sulfate.     

An Advanced Oscillation Mixing Method for Improving the Cooling Uniformity in Quenching

In quenching, the cooling uniformity is most important to diminish distortion occurring on work pieces. As a trial to accomplish uniform cooling, therefore, there exist various mixing methods of a quenchant and the quenchant circulation with an external pump has so far been the well accepted mixing method. However, this study proposes an advanced oscillation mixing method that can improve more the cooling uniformity in quenching. The proposed method includes a stirrer in oscillating motion, so that the simultaneous oscillating and mixing movements of the stirrer are considered to provide efecfively the uniform cooling characteristics for the quenchant. In comparison with the case of the circulation pump mixing, the investigation using the oscillation mixing method has demonstrated the following two experimental facts:(1) the short vapor blanket stage caused by the quick breakage of the oil vapor blanket and (2) the reduced variation of the quenching distortion.     

A novel gait generation method independent of target settling-time adjustment for underactuated limit cycle walking

This paper proposes a novel gait generation method for surely achieving constraint on impact posture in limit cycle walking. First, we introduce an underactuated rimless wheel model without ankle-joint actuation and formulate a state-space realization of the control output using the stance-leg angle as a time parameter through an input–output linearization. Second, we determine a control input that moves the control output to a terminal value at a target stance-leg angle during the single-support phase. Third, we conduct numerical simulations to observe the fundamental gait properties and discuss the relationship between the gait symmetry and mechanical energy restoration. Furthermore, we mathematically prove the asymptotic stability of the generated walking gait by analytically deriving the restored mechanical energy.     

A content search system considering the activity and context of a mobile user

People routinely carry mobile devices in their daily lives and obtain a variety of information from the Internet in many different situations. In searching for information (content) with a mobile device, a user’s activity (e.g., moving or stationary) and context (e.g., commuting in the morning or going downtown in the evening) often change, and such changes can affect the user’s degree of concentration on his or her mobile device’s display and information needs. Therefore, a search system should provide the user with an amount of information suitable for the current activity and a type of information suitable for the current context. In this study, we present the design and implementation of a content search system that considers a mobile user’s activity and context, with the goal of reducing the user’s operation load for content search. The proposed system switches between two kinds of content search systems according to the user’s activity: the location-based content search system is activated when the user is stationary (e.g., standing and sitting), while a menu-based content search system is activated when the user is moving (e.g., walking). Both systems present information according to user context. The location-based system presents detailed information via menus and a map according to location-based categories. The menu-based system presents only a few options to enable users to get content easily. Through user experiments, we confirmed that participants could get desired information more easily with this system than with a commercial search system.     

Enzyme-linked immunosorvent assay using vertical microreactor stack with microbeads

The advantages of vertical microreactor stack with three-dimensional (3D) structure for immunoassay are discussed. The vertical microreactor stack uses vertical fluid flow operation with multifunctional fluid filters. The multi function of fluid filter is very effective for micromixing and passive valve operation. The mechanism of micromixing is discussed by using computational fluid dynamics (CFD), and we know that the mixing mechanism based on Coanda effect. To evaluate the micromixing performance of fluid filter, we demonstrated enzyme reaction with unique repeat mixing operation. As the results, we proved that the fluid filter has very effective mixing performance. The detection limit, which demonstrated by competition enzyme-linked immunosorvent assay (ELISA), is comparable with recommended detection limit, which suggested by Japanese ministry for the environment.