Analysis of thermal degradation process of Nafion‐117 with age‐momentum correlation method

The thermal degradation of Nafion membrane was analyzed with age‐momentum correlation (AMOC) measurement and four‐electrode AC impedance measurement. In the heated sample, the decrease in proton conductivity was observed. The lifetimes and corresponding relative intensities showed fairly good agreement between heated and nonheated samples within the experimental error. In the analysis of the photopeak of annihilation γ‐ray, on the other hand, the difference between those two kinds of samples was observed, and this difference was found to be caused by the annihilation of free positrons with low energy electrons by using AMOC method. The decrease in proton conductivity was caused by the low energy electrons, namely sulfonic radicals. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1–7, 2008     

Adhesion and friction properties of molecularly thin perfluoropolyether liquid films on solid surface

The adhesion and friction properties of molecularly thin perfluoropolyether (PFPE) lubricant films dip-coated on a diamond-like carbon (DLC) overcoat of magnetic disks were studied using a pin-on-disk-type micro-tribotester that we developed. The load and friction forces were simultaneously measured on a rotating disk surface under an increasing/decreasing load cycle and slow sliding conditions. Experiments were performed using two types of PFPE lubricants: Fomblin Z-tetraol2000S with functional end-groups and Fomblin Z-03 without any end-group. The curves of the friction force as a function of the applied load agree with the curves estimated using the Johnson-Kendall-Roberts (JKR) model. The friction forces on the Z-03 films having different thicknesses were not found to decrease drastically; however, the friction forces on the Z-tetraol film were found to decrease drastically when the film thickness is more than ~1.2 nm. This drastic change in the case of the Z-tetraol film is estimated to be affected by the coverage of the lubricant film.     

Formation of trimer and dimer radical cations of methyl-substituted benzenes in gamma-irradiated low-temperature matrices

Dimer and trimer radical cations of benzene, toluene, and xylenes were produced selectively after gamma-irradiation in low-temperature 2-methylpentane matrices with electron scavengers: oxygen (O(2)) and sec-butyl chloride (sec-BuCl). The charge resonance (CR) band of the trimer radical cation (M(3)(+)) produced via the corresponding dimer radical cation (M(2)(+)) is clearly seen in the solution containing O(2) as the temperature increases over a range from 80 to 90 K. In o-xylene solution, a fairly strong and distinct M(3)(+) CR absorption is observed; this is due to the large M(3)(+)/M(2)(+) relative extinction coefficient. All benzene derivatives show an equilibrium between dimer and trimer radical cations at approximately 90 K; however, the equilibrium constants of toluene and the xylenes are considerably lower than that of benzene. Formation of the trimer radical cation is inhibited in sec-BuCl, which has commonly been used as a low-temperature optical matrix for producing cationic species. An ab initio DFT method is applied to predict the geometry of M(3)(+), giving "slipped sandwich" (for benzene, m-xylene, and p-xylene) and "slipped fan-shaped" (toluene and o-xylene) structures as the most plausible geometries. The experimentally observed spectroscopic parameters reflect well those predicted by TD-DFT calculation based on geometry, suggesting strong dependence of the geometry of M(3)(+) on substitution patterns. This is the first report not only of direct spectroscopic observation of aromatic trimer radical cations in the condensed phase but also on the quantitative analysis of their equilibria.     

Self-condensed nanoparticles of oligofluorenes with water-soluble side chains

Self-condensation of the amphiphilic fluorene trimer occurs in the solvent mixture, giving pure "green" fluorescent nanoparticles with controlled radii of 20-100 nm. The origin of the green fluorescence is attributed to the excimer emission via excitation of aggregated dimer structures in the nanoparticles rather than the keto-defects. The present study also suggests the possibility of spectral tuning of emissions from oligofluorene aggregates.     

Texture and Stability of Emulsions: Role of Oscillatory Structural Forces

A digitized optical imaging technique was used to obtain the droplet size distribution, texture, and the radial distribution function which determines the inter-droplet interactions in emulsion systems. The effects of sucrose ester and polyglycerin stearic acid ester as emulsifiers on the stability (i.e., creaming) of oil-in-water food emulsions were investigated, ft was observed that as the concentration of the emulsifier was increased, the droplet size decreased, and the emulsion became more monodispersed and the stability increased. This was confirmed by the experimentally determined radial distributions and the structure factors. It was found that the emulsion made with the fatty acid ester was more stable than that with sucrose ester, and was less polydisperse with better texture. A statistical thermodynamic model was applied which accounts for the droplet-droplet interaction forces, i.e., oscillatory structural forces, and the polydispersity effect to predict the creaming velocity of an oil-in-water emulsion. Good agreement was found between the experimentally determined creaming velocity and the model predictions.     

Removal of Particles from Substrates by Electro-Osmotic Flow

The detergent process or detergency is defined as the removal of soil, or matter out of place, from a substrate immersed in a medium through the application of a mechanical force in the presence of a detergent which lowers the adhesion of the soil to the substrate¹⁾. Regarding the mechanical force in the detergent process for porous solids such as fabrics, detergency is considered to be governed by flow behavior of the washing medium inside the porous solids. For example, the fabric can be considered as a system of capillaries; the space between fibers is a capillary and the fiber surface is the capillary wall. In the washing process, soil particles adhering to the fiber surface can be detached by the tangential flow of washing liquid in the capillaries.     

Solid-state electrochemical CO2 sensor by coupling lithium ion conductor (Li2CO3-Li3PO4-Asl2O3) with oxide ion-electron mixed conductor (La0.9Sr0.1MnO3)

A solid-state electrochemical cell of the type O₂(air), PtLa_0.9Sr_0.1MnO₃/Li₂CO₃(+5 mol% Li₃PO₄ + 6 mol% Al₂O₃)/Au, CO₂, O₂ was composed to determine CO₂ concentration, where Li₂CO₃, a lithium ion conductor, was used as an electrolyte, and the perovskite-type oxide (La_0.9Sr_0.1MnO₃)/O₂-electrode as a reference electrode. The electromotive force (EMF) of the cell was found to be proportional to the logarithm of CO/₂ partial pressure in CO₂/O₂/N₂ gas mixtures at temperatures between 300 and 400 °C. The EMF responded to changes of CO₂ partial pressure within 1 min at 400 °C. The sensitivity to CO₂ of this cell was not affected by coexistence of O₂, and the EMF remained constant after the first 15 days. The mechanism for sensing CO₂ is discussed.     

Simple and environmentally friendly preparation and size control of silver nanoparticles using an inhomogeneous system with silver-containing glass powder

A simple, environmentally friendly method for preparing highly size-controlled spherical silver nanoparticles was developed that involved heating a mixture of silver-containing glass powder and an aqueous solution of glucose. The stabilizing agent for silver nanoparticles was found to be caramel, which was generated from glucose when preparing the nanoparticles. The particle size was independent of the reaction time, but it increased proportionally with the square root of the glucose concentration in the range 0.25–8.0 wt% (corresponding to particle sizes of 3.48 ± 1.83 to 20.0 ± 2.76 nm). Difference of the generation mechanism of silver nanoparticles between this inhomogeneous system and a system in which Ag⁺ was homogeneously dispersed was discussed.     

Sugar nanowires based on cyclodextrin prepared by single particle nanofabrication technique

The direct formation of nanowires consisting of cyclodextrins by single particle nanofabrication technique (SPNT) is investigated in the present paper. Substittuted cyclodextrin (CD) derivatives and their composite with poly(4-bromostyrene) caused efficient cross-linking reaction upon irradiation, and gave nanostructures by SPNT. Successful visualization of the nanostructures by atomic force microscopy suggested drastic increase in the surface area of the materials based on CDs, leading to considerable increase in the selective adsorption efficiency of the molecules fit to the size of the hydrophobic holes of CDs.