Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm⁻¹. This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.     

Sintering of Ceria-Doped Tetragonal Zirconia Crystallized in Organic Solvents, Water, and Air

Amorphous CeO₂–ZrO₂ gels were prepared by coprecipitation in ammonia solutions. The onset of crystallization of the gels, from calcining in air, was 420°C, while 200° to 250°C in the presence of water and organic solvents such as methanol and ethanol. The sintering behaviors of CeO₂–ZrO₂ powders were sensitive to the crystallizing conditions, since hard agglomerates formed when the precipitated gels were crystallized by normal calcination in air, whereas soft agglomerates formed when they were crystallized in water or organic solvents. CeO₂–ZrO₂ powders crystallized in methanol and water at 250°C were sintered to full theoretical density at 1150° and 1400°C, respectively, whereas that crystallized by calcination in air at 450°C was sintered to only 95.2% of theoretical density, even at 1500°C.     

Development of flexible organic light‐emitting diode on barrier film and roll‐to‐roll manufacturing

To come out with a successful organic light‐emitting diode (OLED) lighting business, it is very important to have clear differentiation of OLED from LEDs. Flexible OLED has merits, such as capability to be mounted on the curved wall, which is not easy for LEDs to achieve the feature. There are several approaches to make flexible OLEDs especially among those plastic barrier films that can bring high level of flexibility, which could not be achieved by any conventional lighting method. In this paper, barrier films with various water vapor transmission rate values, including 10^{? 6} order, are applied, and the conditions to have almost no dark spot growth under 85 °C and 85% high temperature/humidity test are shown. Flexible OLED panels are manufactured with the world's first roll‐to‐roll equipment using plastic barrier film.     

Transition of the flow in a symmetric channel with periodically expanded grooves

Transition of the flow in a periodically grooved channel is numerically investigated for periodicity indices m=1 up to 6 by assuming the two-dimensional and fully developed flow field, where m is defined as a number of grooves in which the flow repeats periodically. Critical Reynolds numbers for the onset of a self-sustained oscillatory flow from a steady-state flow are evaluated by numerical simulations. It is found that the bifurcations occur at the critical Reynolds numbers as a result of Hopf bifurcation, and a period in the streamwise direction of the oscillatory flow is twice as long as the groove pitch of the channel. In addition, flow visualization with the aluminum dust method is carried out to confirm the results obtained from the numerical simulations. The experimental results are in good agreement with the numerical ones.     

Liquefaction of wood in the presence of phenol using phosphoric acid as a catalyst and the flow properties of the liquefied wood

The liquefaction of wood in the presence of phenol using phosphoric acid as a catalyst and the flow properties of the obtained liquefied wood were investigated. It was found that phosphoric acid is a satisfactory catalyst for liquefying wood. The amount of phenol that reacts with the liquefied wood components (i.e., combined phenol) increases with an increase in liquefaction temperature, liquefaction time, catalyst content, or liquid ratio. By removing the free phenol, the resulting liquefied woods become novolaclike resins. The measurements of the flow properties of these liquefied woods reveal that the melts of liquefied woods behave as pseudoplastics and their flows obey the Ostwald de Waele power law equation. The amount of combined phenol within the liquefied wood and the presence of filler in the liquefied wood have great influence on their flow properties. The flowing temperature, activation energy, and zero shear viscosity of the liquefied woods show tendencies to increase with an increase in combined phenol. © 1994 John Wiley & Sons, Inc.     

Morphological study by TEM on uniaxially oriented thin films of PET, PEN and their blends

Uniaxially oriented thin films of poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) and their blends were prepared by applying shear strain to their respective melts, and the resulting morphologies were studied by transmission electron microscopy. Selected-area electron diffraction of each film revealed well-defined uniaxial orientation of polymer chains in the shearing direction. In the uniaxially oriented thin film of PEN, stacked-lamellar structure with the average long period of 27 nm consisting of a crystalline region about 15 nm thick and an amorphous one about 12 nm thick was found here and there in the dark-field image: PEN-type. On the other hand, stacked-lamellar structure was rarely observed in the case of PET: PET-type. In PET/PEN blends, the morphologies changed from the PET-type to the PEN-type with increasing content of PEN.     

Preparation of porous carbons from thermoplastic precursors and their performance for electric double layer capacitors

Porous carbons with high surface area were successfully prepared from thermoplastic precursors, such as poly(vinyl alcohol) (PVA), hydroxyl propyl cellulose and poly(ethylene terephthalate), by the carbonization of a mixture with MgO at 900 °C in an inert atmosphere. After carbonization the MgO was dissolved out using a diluted sulfuric acid and the carbons formed were isolated. The mixing of the PVA carbon precursor with the MgO precursors (reagent grade MgO, magnesium acetate or citrate) was done either in powder form or in an aqueous solution. The BET surface area of the carbons obtained via solution mixing could reach a very high value, such as 2000 m²/g, without any activation process. The pore structure of the resultant carbons was found to depend strongly on the mixing method; the carbons prepared via solution mixing were rich in mesopores, but those produced via powder mixing were rich in micropores. The size of mesopores was found to be almost the same as that of the MgO particles, suggesting a way of controlling the mesopore size in the resultant carbons. Measurement of capacitance was carried out in 1 mol/L H₂SO₄ electrolyte. The porous carbon with a BET surface area of 1900 m²/g prepared at 900 °C through solution mixing of Mg acetate with PVA showed a fairly high EDLC capacitance, about 250 F/g with a current density of 20 mA/g and 210 F/g with 1000 mA/g. The rate performance was closely related to the mesoporous surface area.     

Conformational disorder in the Brill transition of uniaxially-oriented nylon 10/10 sample investigated through the temperature-dependent measurement of X-ray fiber diagram

X-ray fiber diagram of uniaxially-oriented nylon 10/10 sample has been measured at the various temperatures. The 11th layer line originating from the methylene zigzag sequences became diffuse above the Brill transition region (140-170 °C), while the layer reflections corresponding mainly to the original repeating period of the parent nylon chains were kept almost unchanged. This observation makes us confirm that in the Brill transition region, the conformational disordering occurs in the methylene sequential parts with keeping the repeating period of the whole skeletal chain by still forming the intermolecular hydrogen bonds between the amide groups of the neighboring chains. This conclusion is consistent with the already-reported infrared spectral data. The characteristic X-ray diffraction patterns observed at the various temperatures were reproduced well by a computer simulation technique utilizing the previously-reported molecular dynamics calculation results.     

Prediction model of surface residual stress within a machined surface by combining two orthogonal plane models

The variation of surface residual stress within a machined surface layer caused by face turning was studied. The size of the tool’s corner radius and the feed rate affect residual stress. A process model using the finite element method is proposed and the mechanical effects of the corner radius and feed rate on a machined surface were discussed. When a tool with a small corner radius is used, surface residual stress perpendicular to the cutting direction becomes compression stress. As well, surface residual stress changes from tension to compression as the feed rate decreases. The process model consists of an orthogonal cutting simulation and an indentation-like simulation of a corner radius into a work piece surface. The simulated results show quantitative agreement with the residual stress measured experimentally. The integrity of the machined surface will be controlled more efficiently if the cutting conditions during finishing are determined with the proper consideration of the surface generating process.