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Luminescent oxygen sensor composed of platinum-porphyrin and a gas-permeable polymer binder was applied as an optical crack sensor paint for infrastructure. The sensor paints were designed as a three-layered structure in which the luminescent oxygen sensor layer was sandwiched between oxygen barrier layers. The sensor paints emitted intense luminescence under UV light irradiation, and the luminescence was efficiently quenched when a new crack formed on the concrete surface. Microcracks, which were

In this study, dual luminescent polymer sensors based on a pressure-sensitive palladium(II) tetraphenylporphyrin, PdTPP, and a temperature-sensitive europium(III) complex, EuDT, were newly fabricated by spray-coating or electrospinning of the solutions containing polystyrene as a matrix for the simultaneous detection of both pressure and temperature. The pressure and temperature responses were recorded as a function of the luminescence changes, and their sensitivities were carefully evaluated. The electrospun nanofibrous films exhibited a higher pressure-sensitivity than the corresponding spray-coated films, which was most likely attributed to their highly porous structures. In addition, accurate temperatures at the sample surface were determined from the luminescence intensities of the temperature-sensitive dye, which were used for the temperature correction of the surface pressure measurements. It was demonstrated that the accuracy of the pressure measurements based on the luminescence intensities of the pressure-sensitive dye was significantly improved after the temperature corrections. This is the first report of dual luminescent nanofibrous polymer sensors.

Side chain clicked polystyrene derivatives formed by the Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction showed colorimetric ion sensing behaviors when donor-acceptor chromophores, prepared by a [2+2] cylcoladdition-retroelectrocyclization between electron-rich alkynes and tetracyanoethylene (TCNE)/7,7,8,8-tetracyanoquinodimethane (TCNQ), were attached to the triazole rings. The metal ion sensing behaviors could be explained according to the theory of hard and soft acids and bases (HSAB). Hard acidic metal ions were mainly recognized by the hard basic anilino-nitrogen moieties, resulting in a decrease in the charge-transfer (CT) bands. In contrast, soft acidic metal ions led to a bathochromic shift in the CT bands due to the selective interactions with the soft basic cyano-nitrogen atoms. With the triazole spacers, more soft (and/or borderline) metal ions were recognized by the donor-acceptor chromophores probably due to more space for the various sized metal ions. The chemodocimetric anion sensing behaviors of the clicked polystyrenes were almost the same as those of the counter polystyrenes without the triazole spacers. Overall, the triazoles in this study do not serve as colorimetric sensor units towards both metal ions and anions, but they are effective spacers between the polymer main chain and ion sensing donor-acceptor side chain chromophores.

We have been developing smart photonic coating for structural materials to visualize strain mapping on steel or aluminum and to detect cracks on concrete. In the technology, strain imaging sheet made of colloidal photonic crystal film coated on a polyethylene terephthalate sheet. The strain imaging sheets change structural color by mechanical deformation. Now we have been testing smart photonic coating for real concreate bridges One of the key issues is the durability of the sheet for long-term use at the outfield site. In outdoor exposure test and in laboratory accelerated exposure test, polystyrene particles in the colloidal photonic crystal film were damaged and lost the structural color. To protect the deteriorating, top coat layer containing ultraviolet absorber was effective to reduce the damage of the colloidal photonic crystal film.

CO2 capture-reduction (CCR) is a recently developed catalytic process that combines two critical functions of the CO2 utilization path in one process, namely CO2 capture and subsequent transformation (e.g. reduction by H2) into chemical fuels or intermediates such as CO. A bifunctional catalyst material is needed and the two functions are activated by means of an isothermal unsteady-state operation (i.e. gas switching). This work employs operando space- and time-resolved DRIFTS, XAFS, and XRD to elucidate the nature and functions of Cu and the promoters. Both unpromoted and K/Ba-promoted Cu/Al2O3 catalysts were studied to illuminate the active surface species varying along the catalyst bed. The K promoter was found to uniquely facilitate efficient CO2 capture in the form of surface formates, dispersion of active metallic Cu and suppression of surface Cu oxidation. The CO2-trapping efficiency of the K-promoted catalyst is so high that CO2 capture takes place gradually along the catalyst bed towards the reactor outlet, hence creating large spatial and temporal gradients of surface chemical species. Understanding these features is of central importance to design efficient CCR catalysts. Furthermore, a completely different path for CO2 reduction was evidenced for the unpromoted and Ba-promoted Cu catalysts where CO2 can directly react with metallic Cu and oxidize its outer surface and thus releasing CO. These results also provide important new mechanistic insights into the widely investigated reverse water–gas shift reaction and the role that K and Ba promoters play.

Here we will propose the conceptual new idea of the inspection of concrete bridge using smart materials and mobile IoT system. We apply opal photonic crystal film to detect cracks on concrete infrastructures. High quality opal photonic crystal films were coated on black color PET sheet over 1000 cm2 area. The opal film sheet was cut and adhered to concrete or mortar test pieces by epoxy resin. In the tensile test, the structural color of the opal sheet was changed when the crack was formed. As a demonstration, we have installated the opal film sheet on the wall of the concrete bridge. Our final purpose is the color change will be recorded by portable CCD devices, and send to expert via IoT network.

Visualization of the oxygen partial pressures was carried out at the surface of a gas diffusion layer (GDL) for the first time together with the upper part of the gas-flow channel of the cathode of a running polymer electrolyte fuel cell (PEFC) using two different oxygen-sensitive luminescent dye films. The visualized distributions of the oxygen partial pressures at the GDL and the upper gas-flow channel during the PEFC operation were very different in a conventional test cell. The change in the distribution of the oxygen partial pressures was observed by changing the oxygen utilization, which should be connected with the reactive locations in the membrane-electrode assembly (MEA). A numerical calculation was carried out to understand the distributions of water and current density inside the MEA. The water distribution inside the MEA was confirmed to strongly affect the distributions of the current density and the oxygen /partial pressure.

The rapid growth of the click chemistry concept enables the production of a wide variety of functional polymers. Among the new generation of click chemistry reactions, the highly efficient addition reactions between electron-rich alkynes and cyano-based acceptors, referred to as alkyne-acceptor click chemistry, have found promising application possibilities as polymeric chemosensors. The donor-acceptor chromophores, formed by this click chemistry reaction, feature intense charge-transfer (CT) bands in the visible region, but they are hardly fluorescent. Importantly, the chromophores possess two different nitrogen atoms, namely the aniline nitrogen and cyano nitrogen. The recognition of some specific metal cations by different nitrogen atoms in the polymers led to different modes of changes in the absorption spectra. For example, the hard acid of Fe(3+) ion was recognized by the aniline nitrogen, resulting in a decrease in the CT bands. On the other hand, the soft acid of the Ag(+) ion was captured by the cyano nitrogen, leading to a bathochromic shift in the CT bands. Some specific anions, such as CN(-), F(-), and I(-) ions, were also recognized by a chemodocimetric detection mode, discoloring the original solutions. When the CT bands decreased upon the addition of analytes, the polymers were found to serve as turn-on fluorescent sensors. In this perspective, the detailed detection modes of the new polymeric chemosensors are fully described.

The paper reviews control of surface wetting via the production of polymer coatings sensitive to changes in external conditions. Graft polymer compositions having the adaptive properties are obtained by method of surface-initiated atom transfer radical polymerization on aluminum surface. The chemical composition of polymer coatings is confirmed by X-ray photoelectron spectroscopy. The morphology of the modified surface is investigated by scanning electron microscopy. The possibility of wetting control of modified aluminum surfaces modified in a wide range with a change in the pH value and temperature is shown.

During start-up/shut-down processes of a polymer electrolyte fuel cell, platinum particles are lost from the catalyst layer at the cathode due to corrosion of the carbon supports. We simulated the start-up/shut-down cycle by exchanging gases at the anode between hydrogen and air. During the gas exchange, the distribution of oxygen partial pressures at the anode was visualized by our real-time/space visualization system, which clearly showed the location of H2- and O2-rich areas along the gas-flow channel from the inlet to the outlet. The gas exchange rate was found to be much slower than that predicted from the simple replacement and to be correlated to the proton transfer derived from carbon corrosion of the cathode catalyst layer. By the visualization results, it was found that the shut-down process gives more serious effect than the start-up process. After the degradation, the oxygen partial pressure at the cathode was visualized during the cell operation. Oxygen was consumed mainly in the middle of the MEA because the MEA was degraded mainly near the inlet and outlet of reactant gases in the cell.

Luminescent oxygen-sensory polymer-coatings composed of platinum tetrakis(pentafluorophenyl)-porpholactone (PtPL) and -porphyrin (PtPP) with poly(trimethylsilylpropyne) (PMSP) were prepared for visualization of the oxygen partial pressure on two parallel planes or a biplanar surface. PMSP formed a smooth and tough coating as a high oxygen-permeable polymer matrix with a thickness of ca. 2 μm, which homogeneously contained the luminescent dye probe, PtPL or PtPP. Under UV light (395 nm) irradiation, the coatings displayed strong magenta and red luminescence with maximum peaks at 750 and 650 nm ascribed to the PtPL and PtPP, respectively. The luminescence of the two coatings was efficiently quenched by oxygen which allowed the development of engineering curve to analyze the oxygen partial pressure. The luminescence intensities of the two coatings were separately monitored in order to allow the simultaneous measurement of the oxygen partial pressure distribution upon two planar surfaces.

Active control of flow over object surfaces achieved by means of mechanical and/or electrical methods has recently been studied. However, there has been no report on actively switching the surface drag of an object by chemical modification of the object's surface. Poly(N-isopropylacrylamide) (PNIPA) was grafted onto the surface of an aluminium (Al) substrate via (A) surface-initiated atom transfer radical polymerization and (B) radical polymerization with an azo-group surface initiator. The grafting density was 0.19 and 0.15 chains nm−2, respectively. The water contact angle of the PNIPA-grafted Al surface reversibly changed between 55° and 82° for (A) and between 42° and 65° for (B) at temperatures of 25 and 40 °C, which was ascribed to the temperature-responsive, hydrophilic–hydrophobic switching of the grafted PNIPA surface. The PNIPA grafting was applied on the surface of an ogive-shaped Al model. The normalized dropping speed of the model in water increased 1.1 times at 42 °C in comparison to that at 22 °C. Switching of the surface drag of PNIPA-grafted Al in water was demonstrated on the basis of the hydrophilicity and hydrophobicity of the grafted Al surface, the switching occurring with a change in temperature. Copyright © 2010 Society of Chemical Industry

A triple-layered luminescent polymer coating was prepared to simultaneously detect both oxygen and temperature upon the coating. The coating was composed of an oxygen and a temperature sensory layer based on platinumporphyrin (PtTFP) and ruthenium phenanthroline (Ru(phen)) dye molecule, respectively. The temperature-sensitive Ru(phen) was dispersed in gas-barrier polyvinyl alcohol as the first layer, which was further coated with a water-proofing fluorine-containing polymer. The oxygen sensory layer composed of the oxygen-sensitive PtTFP and high oxygen-permeative poly(1-trimethylsilyl-1-propyne) was coated as the third layer. The two luminescences were separately monitored: the oxygen partial pressure and temperature in the range of 0-21 kPa and of 25-120 °C were successfully detected.

Poly[1-trimethylsilyl-1-propyne-co-1-(3-pyridyl)propyne] 1 was prepared both as a polymer-ligand of a palladium porphyrin (PdOEP) and of a platinum porphyrin (PtTFP) and as a highly gas-permeable polymer matrix of the porphyrin. The porphyrin acted as a phosphorescence probe which could be quenched with oxygen and sense the oxygen partial pressure. 1 gave a smooth and tough coating with a thickness of ca. 2 µm which homogeneously involved the porphyrin. The porphyrin-1 coatings displayed strong red-colored phosphorescences (the emission maximum at 670 and 650 nm for PdOEP and PtTFP, respectively), and their intensity significantly decreased with an increase in the oxygen partial pressure on the coating. The high oxygen-quenching efficiency or the high oxygen pressure sensitivity of the porphyrin's phosphorescence was observed even at cryogenic temperature. Aggregation of the porphyrin was suppressed in the coating by ligation of the porphyrin with the nitrogenous residue of 1 to significantly reduce spatial noise in the phosphorescence measurement or the oxygen-pressure sensing. PtTFP-1 was coated on the surface of a delta wing model. The oxygen-pressure distribution on the coated model was successfully visualized in a cryogenic wind tunnel test. Copyright © 2008 John Wiley & Sons, Ltd.

Polyphenylacetylene derivatives substituted by dialkylanilino-appended alkyne side chains were synthesized by Rh-catalyzed polymerization. Improved oxygen barrier ability was achieved by the postfu...

We will present a simple and low cost method to visualize local strain distribution in deformed aluminum plates. In this study, aluminum plates were coated with opal photonic crystal film with tunable structural color. The photonic crystal films consist of a silicone elastomer that contains an array of submicron polystyrene colloidal particles. When the aluminum sheets were stretched, the change in the spacing of the colloidal particles in the opal film alters the color of the film. This approach could be useful as a new strain gauge having a visual indicator to detect mechanical deformation.

Fuel cells are devices that produce electric power by means of the chemical reaction of oxygen and fuels more efficiently than current technologies, and they are expected to become a cleaner source of energy. Despite considerable recent advances, especially in polymer electrolyte membrane fuel cells (PEMFCs), existing technology still has drawbacks, including kinetic limitations on the oxygen reduction reaction and the instability of Pt catalysts and polymer membranes nearby, in particular during startup–shutdown cycles. The chemical reactions are uneven throughout the reaction field and not well understood. A central issue in fuel cell research is the measurement of the parameters that determine performance during cell operation, a difficult task owing to the structure of these devices. The distribution of liquid water in operating fuel cells has been measured and imaged through neutron radiography, by NMR spectroscopy, and by X-ray microtomography, and temperatures have been recorded with a thermograph. Hydrogen cross-over from the anode to cathode has been studied by mass spectrometry and magnetic resonance imaging in an operating PEMFC. Oxygen consumption and H2O2 formation, as well as the local catalytic activity of a catalyst have been investigated and visualized in solution with a scanning electrochemical microscope. However, to improve the performance and durability of PEMFCs, it is crucial to understand distributions in real time not only of liquid water but also of reactants and products (oxygen, fuel, CO2, water vapor, etc.) throughout the cell. Here we present a laboratoryuse, nondestructive system for visualizing oxygen distribution in the interior of the operating fuel cells which relies on dye films painted on the transparent gas flow field. Oxygen partial pressures were successfully visualized with spatial and time resolutions of 300 mm and 500 ms, respectively. We found that the oxygen distribution in PEMFC is not in accordance with that expected based on the current, which suggests a significant contribution from water. This imaging system is applicable to other important parameters such as water, carbon monoxide, and temperature, and should help in the design of new fuel cell separators and a reaction field called a membrane-electrode assembly (MEA). An oxygen-sensitive porphyrin, tetrakis(pentafluorophenyl)porphyrinatoplatinum (PtTFPP), was used in the visualization system. This dye complex was dispersed in an oxygenpermeable polymer matrix, poly(1-trimethylsilyl-1-propyne) (pTMSP), for making a thin, water-insoluble dye film. To understand the properties of the dye film, we placed the film in an environment with controlled oxygen partial pressure (mixtures of oxygen, nitrogen, and water vapor at 0–26 kPa of a total of approximately 101.3 kPa), temperature, and humidity, and irradiated it with a laser light at a wavelength of 407 nm. The emission from the film was filtered (> 600 nm), and the intensity was measured with a charge-coupled device (CCD) camera. Figure 1a shows a Stern–Volmer plot of the

Luminescent oxygen sensory polymer coatings composed of platinum tetrakis(pentafluorophenyl)porpholactone and -porphyrin with poly(trimethylsilylpropyne) were prepared. Two luminescence peaks at 75...

Start-up and shut-down cycling in PECFs causes severe degradation, because the carbon supports at the cathode catalyst layers are corroded due to the instantaneous reaction with H2O. We developed a new CO2 visualization system using a CO2-sensitive dye for detecting the generation of CO2 during the corrosion processes in real time and with spatial resolution. The corrosion occurring during the shut-down process continued longer near the inlet and produced a more serious effect than during the start-up process, near the outlet. This new CO2 visualization technique should help to minimize the corrosion of carbon supports in all types of PEFCs. © 2012 The Electrochemical Society. [DOI: 10.1149/2.018204esl] All rights reserved.

We describe the capsulation of colloidally templated polythiophene (P3-TAA) arrays with multi-walled carbon nanotubes (MWNTs) after colloidal template electropolymerization. The dissolution of the polystyrene (PS) particle templates, which were assembled via the Langmuir-Blodgett (LB)-like technique, allowed the formation of hollow-shell Janus type arrays.

Electrochemically oxidized patterns of stable poly(nitroxide radical)s at the nano-scale were demonstrated by controlling lithographic parameters, such as voltage, scan speed, and sweep duration.

A luminescent porphyrin dye film has been coated onto a transparent separator on the cathode side of a direct methanol fuel cell (DMFC) to visualise clearly oxygen distribution under operating conditions by analysing emission from the dye.

A dual-mode and a non-Stern–Volmer type oxygen pressure-sensitive coating was prepared by combining the cobaltporphyrin (CoP) ligated with a polymer and 1-pyrenebutyric acid (Py): the combination of the rapid and reversible oxygen (O2)-adduct formation of the CoP was accompanied by a visible absorption spectral change and luminescence quenching of Py with oxygen. The oxygen sensor composed of CoP/Py was successfully characterized by a significantly high oxygen sensitivity under the practical atmospheric oxygen pressure of 10–21 kPa. Py was adsorbed on an anodized aluminium substrate. Its luminescence decreased by quenching with oxygen which obeyed the conventional Stern–Volmer equation. Copolymers of vinylidenechloride with 1-vinylimidazole, 1-vinyl-2-methylimidazole, and 4-vinylpyridine (1, 2 and 3, respectively) were prepared to provide both an oxygen-barrier coating for the first luminescent Py layer and CoP ligation for tuning the oxygen-adduct formation equilibrium. The luminescent Py layer was further coated with a second polymer layer: The oxygen-barrier polymer coating enhanced the Stern–Volmer type luminescence intensity from the Py layer. Visible absorption of the CoP-containing polymer second layer increased in response to the oxygen-adduct formation or oxygen partial pressure, which overlapped and reduced the luminescence from the Py layer. The sum of the luminescence decreased along with an increase in the oxygen partial pressure, yielding a non-Stern–Volmer type response or high sensitivity to the oxygen partial pressure.