Sawtooth-shaped stringiness with front frame formation for polyacrylic pressure-sensitive adhesives with two different molecular structures

The formation of sawtooth-shaped stringiness during 90° peeling was investigated using crosslinked poly(n-butyl acrylate–acrylic acid) and poly(2-ethylhexyl acrylate–acrylic acid) random copolymers with an acrylic acid content of 5 wt.% and different crosslinking degrees as pressure-sensitive adhesives (PSAs). The gel fraction was measured by toluene extraction of PSA, and it increased with crosslinker content for both systems. The observed stringiness was sawtooth-shaped, but there were three different types; both the typical sawtooth shape and the frame formed at the front tip with interfacial failure, and the sawtooth shape formed with cohesive failure. The change in the stringiness shape was affected strongly by the gel fraction of PSA. The peel rate under constant peel load was measured and revealed that the peel rate was lowest upon formation of the front frame type. A good relation was found between peel rate and peel strength, with a greater peel strength upon formation of the front frame type. The concentrated stress at the peeling tip is released by progress of peeling and deformation of the adhesive layer (stringiness) for no frame type. On the other hand, the sufficient interfacial adhesion delays the progress of peeling, and the applied larger stress causes cavitation in the PSA layer for front frame type. The formed cavity grows and the front frame type formed as a result. That is, internal deformation occurred preferentially over peeling. In order to improve the peel strength, the front frame type is the most useful stringiness shape.     

Influences of debonding rate and temperature on tack properties and peel behavior of polyacrylic block copolymer/tackifier system

The influences of debonding rate and temperature on the peel behavior of polyacrylic block copolymer/tackifier system were investigated. Poly(methyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(methyl methacrylate) triblock copolymer (MAM) with hard block contents of 23 (MAM-23) and 16 wt.% (MAM-16) and a 1/1 blend with a diblock copolymer (MA) consisting of the same components (MAM-23/MA, total hard block content of 15 wt.%) were used as the base polymer. A special rosin ester was used as a tackifier at various contents in the block copolymer/tackifier system. The peeling process at the probe/adhesive interface during probe tack testing was observed using a high-speed microscope at 23 °C with debonding rate of 10 mm/s. Three different peeling mechanisms were observed. Type A, where peeling progressed linearly from the edge to the center of the probe without cavitation (MAM-23). Type B, where peeling progressed linearly from the edge to the center of the probe with cavitation (MAM-16). Type C, where cavitation occurred over the entire adhesive layer, and peeling initiation was delayed (MAM-23/MA). The peel behavior of MAM-23 changed from Type A to Type B with a decrease of the debonding rate (1 mm/s) or increase of the temperature (40 °C). In contrast, there was no change for MAM-16 and MAM-23/MA. Cavity formation in an adhesive layer restrains peeling; therefore, it is desirable for improvement of the adhesion strength. The tack properties increased with the tackifier content, and the formation of cavitation was less than that for the systems without the tackifier.     

deNOx Performance and Reaction Mechanism of the Di-Air System

The detailed reaction mechanism of Di-Air, which showed the unprecedented high deNO_x performance at high temperature conditions, was studied in this work. Since the Di-Air phenomenon occurs with continuous short pulse injections of hydrocarbons over NSR (NO_x storage and reduction) catalyst, this study focused on the specific function of HC as an effective reductant for NO_x reduction reaction. As a first step, the deNO_x performance was compared with three different reductant gases including CO, H₂ and C₃H₆ in a modified synthetic gas bench equipped with a gas injector which enables continuous small amount of injections. At inlet gas temperature of 450 °C C₃H₆ showed the best deNO_x performance whereas H₂ was the best at 150 °C. Moreover the result of temperature programmed desorption showed that intermediate species represented by –NCO (isocyanates) produced from C₃H₆ was thermally more stable than that produced from CO. These results confirmed that the injected HC reacts with adsorbed NO_x on NSR catalyst generating thermally stable intermediates, which could contribute the high deNO_x performance at high temperature conditions.     

PCE-based fast path control in multi-domain photonic networks

We discuss issues for controlling an optical path in large-scale photonic networks, and introduce an inter-domain path control system based on Path Computation Elements (PCEs). In the system, maximum flow information enables the load balancing of traffic, and Path Key scheme preserve the confidentiality of internal topology information among carrier networks. Based on the experimental results, we show the path setup in the introduced system is significantly faster than the manual path setup among domains in current carriers' networks. For the additional reduction of the path setup time, we propose the domain-wise paralleled signaling method. We also show that decreasing the number of nodes per domain makes path setup faster in the introduced system with deployment of the proposed signaling method.     

PVDF actuator for high‐frequency fatigue test of thin‐film metals

This paper suggests a poly(vinylidene fluoride) (PVDF) piezoelectric diaphragm actuator used in a novel fatigue test method for thin metal films. A thin‐film metal specimen is stamped on top of the actuator using a stamping epoxy. As the actuator vibrates, the stress in the specimen increases until it fails under fatigue. A finite element model of the actuator is built, and its vibration amplitude is confirmed to be in a good agreement with experiment. Then, a model of the specimen is added to this model to simulate the vibration of the specimen for fatigue test. Stress analysis of the specimen at a driving voltage of 200 V_0−p confirms that this actuator can increase the stress in the specimen to near 1 GPa, which is high enough for the fatigue test of metals such as titanium. In the experiment, a thin‐film titanium specimen is stamped on top of the actuator which is then vibrated. The stress in the fatigue gauge on thin‐film specimen increased until the specimen failed under fatigue. This shows that the proposed PVDF actuator is suitable for the fatigue test of thin‐film metals such as titanium. © 2012 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Perovskite-type oxides La1−xSrxMnO3 for cathode catalysts in direct ethylene glycol alkaline fuel cells

Carbon-supported La_1−xSr_xMnO₃ (LSM/C) was prepared by reversible homogeneous precipitation method, and its catalytic activities for oxygen reduction under the existence of ethylene glycol (EG) were investigated by using rotating disk electrode. LSM/C exhibited the high activity for oxygen reduction irrespective with the presence of EG, indicating that EG is not oxidized by LSM/C at the cathode side in the present system. Consequently, LSM/C can serve as a cathode catalyst in alkaline direct alcohol fuel cells with no crossover problem. Performance test for fuel cells operation also supported these results and showed cathodic polarization curves were not affected by the concentration of EG supplied to anode even at 5 mol dm⁻³.     

Photoswitching of electron transfer property of diarylethene–viologen linked molecular layer constructed on a hydrogen-terminated Si(111) Surface

An organic monolayer with diarylethene and viologen moieties as a photochromic and an electroactive group, respectively, was constructed on a hydrogen-terminated Si(111) surface by sequential surface reactions. Photoswitching behaviour of electron transfer from the Si electrode to viologen moiety, larger and smaller current after UV and visible irradiation, respectively, was observed. This photoswitching behaviour can be explained by a change in molecular conductivity of diarylethene moiety, which separates Si surface and viologen moiety, as a result of ring closing and opening induced by UV and visible irradiation, respectively.     

Performance decay of proton-exchange membrane fuel cells under open circuit conditions induced by membrane decomposition

The degradation in performance of proton-exchange membrane fuel cells (PEMFCs) under open circuit conditions was investigated. The oxygen reduction reaction (ORR) kinetic current density at 0.9 V was found to decrease from 36 to 4 mA cm⁻² (geometric) without significant crossover increase or loss in the electrochemically active surface area. Cyclic voltammograms for the electrodes show characteristic changes, e.g. appearance of peaks at ∼0.2 V and shift of the onset of platinum oxide formation to higher potentials. It was identified that the large ORR kinetic decay has its origins in the reduction of available Pt sites due to adsorption of anions, which are postulated to be membrane decomposition products such as sulfate ions. Procedures carried out to condense water in the fuel cell led to the expulsion of anions out of the membrane electrode assembly (MEA) resulting in the partial recovery of ORR kinetic current density to 15 mA cm⁻². In order to attain complete performance recovery of the catalyst, a more effective and practical method to flush out the anions is desirable.     

Three-dimensional expression of adhesion molecules on the superficial synovial intima of LPS-induced arthritis of the mouse knee analyzed by immuno-SEM

Three-dimensional microlocalization of adhesion molecules, i.e. ICAM-1 (intercellular adhesion molecule), VCAM-1 (vascular adhesion molecule), LFA-1 (lymphocyte function-associated antigen), Mac-1 (macrophage differentiation antigen) and VLA-4 (very late activation antigen), expressed on type-A synoviocyte (macrophage-like cell) and type-B synoviocyte (fibroblast-like cell), were detected by immuno-scanning electron microscopy (SEM) to investigate the immunoreactive microenvironment of the superficial synovial intima in lipopolysaccharide (LPS)-induced arthritis of the mouse knee. Type-B synoviocytes extended rich slender processes from the periphery and constructed a cytoplasmic network, to which ICAM-1 was restricted. VCAM-1 was expressed only in the LPS-stimulated group and was relatively limited to the microvilli of type-B synoviocytes. Type-A synoviocytes were located randomly among the network with a smoother surface and expressed Mac-1 and LFA-1, which were counter-receptors for ICAM-1, and VLA-4 for VCAM-1 on the microvilli or lamellipodia. Three-dimensional microlocalization of adhesion molecules suggests that the network constructed by cytoplasmic processes and microvilli of type-B synoviocytes forms the pathway for the migration or the foothold for the fixation of type-A synoviocytes and takes part in forming an immunoreactive environment in the articular cavity.