Penetration Routes of Oxygen and Moisture into the Insulation of FR-EPDM Cables for Nuclear Power Plants.

The polymeric insulation used in nuclear power plants (NPPs) carries the risk of molecular breakage due to oxidation and hydrolysis in the event of an accident. With this in mind, tubular specimens of flame-retardant ethylene-propylene-diene rubber (FR-EPDM) insulation were obtained by taking conductors out of a cable harvested from an NPP. Similar tubular specimens were made from a newly manufactured cable and those aged artificially using a method called the "superposition of time-dependent data." The inner and outer surfaces of each tubular specimen were subjected to various instrumental analyses to examine their oxidation, moisture uptake, and cross-linking. As a result, it has become clear that oxygen penetrates the cable through gaps between the twisted conductor strands. Meanwhile, water vapor diffuses more often through the sheath than through gaps between the conductor strands. Of the two methods used to simulate design-based accidents in NPPs, the one used to simulate the designed loss-of-coolant accident is more severe to FR-EPDM than the one used to simulate the designed severe accident. In addition, the validity of the method called the "superposition of time-dependent data," which is used to give artificial aging treatments to cable samples, was confirmed. Measurements of spin-spin relaxation time and residual dipolar coupling using time-domain nuclear magnetic resonance were found suitable to use to obtain information on the cross-linking of FR-EPDM insulation.

How to Install TEMPO in Dielectric Polymers-Their Rational Design toward Energy-Storable Materials.

Polar groups and the charge-transport capability play significant roles in the dielectric properties of organic polymers, and thus influence the electric energy density upon application as a capacitor material. Here, the dielectric properties and electric conductivity of a series of polymers containing 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals are investigated. The neat radical polymer poly(TEMPO methacrylate) (PTMA) has a high dielectric constant but poor breakdown strength. Poly(methyl methacrylate) (PMMA) is introduced as an insulating polymer with high resistivity on breakdown, along with molecular design of PTMA. Copolymers of TEMPO methacrylate and methyl methacrylate, P(TMA-r-MMA), exhibit high breakdown strengths but low dielectric constants. PMMA blended with TEMPO exhibits the highest electric energy density of 7.4 J cm-3 (that of PTMA is 0.48 J cm-3 as a control), with both a high dielectric constant (≈6.8) and a high breakdown strength (≈500 MV m-1 ). It benefits from long-range but not bulk charge transport in the blends, which is different from the bulk charge transport in PTMA and the short-range charge transport in P(TMA-r-MMA). These results indicate that the TEMPO moiety located in the high breakdown matrix leads to a high energy-storage density in the capacitor.

Development of a TiO2/SiO2 waveguide-mode chip for an ultraviolet near-field fluorescence sensor.

Aimed at detecting fluorescent-labeled biological substances sensitively, a sensor that utilizes near-field light has attracted much attention. According to our calculations, a planar structure composed of two dielectric layers can enhance the electric field of UV near-field light effectively by inducing waveguide-mode (WM) resonance. The fluorescence intensity obtainable by a WM chip with an optimized structure is 5.5 times that obtainable by an optimized surface plasmon resonance chip. We confirmed the above by making a WM chip consisting of TiO2 and SiO2 layers on a silica glass substrate and by measuring the fluorescence intensity of a solution of quantum dots dropped on the chip.

Dielectric and relaxation properties of composites of epoxy resin and hyperbranched-polyester-treated nanosilica.

Hyperbranched polyester is effective for enhancing molecular bond strength and improving the mechanical behavior of nanofilled polymers. This study examines the dielectric and polarization relaxation characteristics of epoxy resin composites filled with nanosilica 30 nm in diameter, which is treated by terminal carboxyl hyperbranched polyester. TEM and SEM analysis indicate that the nanosilica surface is grafted with a functional polymer layer ranging in thickness from several to tens of nanometers, and the nanosilica agglomeration in epoxy resin is remarkably inhibited. Measurements of thermally stimulated depolarization current and differential scanning calorimetry show that, deep traps with an energy of 1.09 eV are present in the nanocomposites, and the glass transition temperature (T g) is increased by 11 °C at most at filler concentrations from 1 to 7 wt%. Moreover, the room-temperature relative permittivity and dielectric loss factor of the composites at 50 Hz are decreased by 0.22 and 1.3‰, respectively. Conductivity at 10 mHz to 1 kHz and dc conductivity are also significantly decreased when the operating temperature is below T g. The polarization relaxation process of the nanocomposite is dominated by regional carrier migration, interfacial and dipole polarization. The relaxation frequency of dipole polarization at high temperature (>T g) is transformed to satisfy the Vogel-Tammann-Fulcher law. This research suggests that both the dielectric and the polarization relaxation properties of the epoxy resin composites can be modified by filling hyperbranched-polyester-treated nanosilica, because it enhances the bond strength of the inorganic-organic interface and enlarges the molecular scale of the composites via cross-linking reactions.

Optimization of a waveguide-mode sensing chip for an ultraviolet near-field illumination biosensor.

A waveguide-mode sensor with a planar sensing chip, consisting of two waveguiding layers and a glass substrate, is a promising candidate for a near-field illumination biosensor. Aiming at using fluorescent labeling induced by ultraviolet light, we optimize the structure of a waveguide-mode sensing chip, based on the mechanism for enhancing ultraviolet near-field light revealed by numerical calculations. Candidates of optimal materials are also presented. The chip optimized as above should be able to enhance the intensity of ultraviolet near-field light 25 times as high as an Al surface plasmon resonance sensing chip.

Dielectric and Carrier Transport Properties of Silicone Rubber Degraded by Gamma Irradiation.

Silicone rubber (SiR) is used as an insulating material for cables installed in a nuclear power plant. Gamma rays irradiated SiR sheets for various periods at temperatures of 145 and 185 °C, and the resultant changes were analyzed by examining complex permittivity spectra and surface potential decay characteristics. Three different processes, namely, instantaneous polarization, electrode polarization due to the accumulation of ions to form double charge layers at dielectric/electrode interfaces, and DC conduction caused by directional hopping of ions, contribute to the complex permittivity. By fitting the spectra to theoretical equations, we can obtain the dielectric constant at high frequencies, concentration and diffusion coefficient of ions and DC conductivity for the pristine and degraded samples. The instantaneous polarization becomes active with an increase of dose and ageing temperature. The thermal expansion coefficient estimated from the temperature dependence of dielectric constant at high frequencies becomes smaller with an increase in dose, which is in good agreement with the experimental results of the swelling ratio. Additionally, trap distributions are calculated from surface potential decay measurements and analyzed to explain the variation in conductivity. Trap energy increases firstly, and then decreases with an increase in dose, leading to a similar change in DC conductivity. It is concluded that generations of both oxidative products and mobile ions, as well as the occurrence of chain scission and crosslinking are simultaneously induced by gamma rays.

Detection of norovirus virus-like particles using a surface plasmon resonance-assisted fluoroimmunosensor optimized for quantum dot fluorescent labels.

A highly sensitive biosensor to detect norovirus in environment is desired to prevent the spread of infection. In this study, we investigated a design of surface plasmon resonance (SPR)-assisted fluoroimmunosensor to increase its sensitivity and performed detection of norovirus virus-like particles (VLPs). A quantum dot fluorescent dye was employed because of its large Stokes shift. The sensor design was optimized for the CdSe-ZnS-based quantum dots. The optimal design was applied to a simple SPR-assisted fluoroimmunosensor that uses a sensor chip equipped with a V-shaped trench. Excitation efficiency of the quantum dots, degree of electric field enhancement by SPR, and intensity of autofluorescence of a substrate of the sensor chip were theoretically and experimentally evaluated to maximize the signal-to-noise ratio. As the result, an excitation wavelength of 390nm was selected to excite SPR on an Al film of the sensor chip. The sandwich assay of norovirus VLPs was performed using the designed sensor. Minimum detectable concentration of 0.01ng/mL, which corresponds to 100 virus-like particles included in the detection region of the V-trench, was demonstrated.

Parallel-incidence-type waveguide-mode sensor with spectral-readout setup.

A waveguide-mode sensor of the spectral-readout type can be used to detect changes in the complex refractive index in the vicinity of the surface of a sensing plate by observing the change in the spectrum of light reflected on the surface. The sensor's configuration can be simplified by adopting a parallel-incidence-type optical setup. To obtain a high sensitivity, the optimization of the sensing-plate structure, incidence angle, and detection wavelength band is essential for the sensor. In the present report, the results predicted by simulations are compared with experimental results in order to evaluate their validity. A discussion of the optimal design for the parallel-incidence-type sensor is also presented, according to the results obtained.

Optimal design of a spectral readout type planar waveguide-mode sensor with a monolithic structure.

Optical planar waveguide-mode sensor is a promising candidate for highly sensitive biosensing techniques in fields such as protein adsorption, receptor-ligand interaction and surface bacteria adhesion. To make the waveguide-mode sensor system more realistic, a spectral readout type waveguide sensor is proposed to take advantage of its high speed, compactness and low cost. Based on our previously proposed monolithic waveguide-mode sensor composed of a SiO2 waveguide layer and a single crystalline Si layer [1], the mechanism for achieving high sensitivity is revealed by numerical simulations. The optimal achievable sensitivities for a series of waveguide structures are summarized in a contour map, and they are found to be better than those of previously reported angle-scan type waveguide sensors.

Shape-sensitive reflectance by nanostructured metal attached on an optical waveguide-mode sensor.

The optical reflectance of He-Ne laser light on a waveguide-mode sensor was measured as a function of light incident angle, in the case of either a metal (Au, Cr or Pt) film or nanoparticles being attached to the waveguide surface of the sensor. A dip appears in the reflectance spectrum as a function of incident angle at the angle where waveguide-mode excitation is induced. It is found that the dip moves toward a lower angle in the case that the attached metal is of a film shape, while it shifts toward a higher angle when the metal is an ensemble of nanoparticles. This difference in the direction of shift can be explained well by theoretical calculations using average refractive indices of the metal-containing layers. The present result indicates that one can estimate whether a metal nanostructure is film-like or an ensemble of spherical nanoparticles by the sensor.

Detection of colored nanomaterials using evanescent field-based waveguide sensors.

We have developed an optical system designed for detecting colored nanomaterials in aqueous solutions, using the concept of evanescent-field-coupled waveguide-mode sensors. In this study, we found that the waveguide modes induced in the sensor are intrinsically sensitive to a change in optical absorption, or a 'change in color'. The system detects less than one gold nanoparticle (diameter: 20 nm) adsorbed per square micrometer. It is also demonstrated that significant signal enhancement due to adsorption of molecules is achieved using a dye. The developed sensor rarely suffers from a drawback of impurity adsorption. The system is expected to be applied as an effective sensing tool for metal colloids, nanoparticles, and colored biomolecules in solution.

Plasmonic activity on gold nanoparticles embedded in nanopores formed in a surface layer of silica glass by swift-heavy-ion irradiation.

Silica glass was irradiated by swift heavy ions by selecting the ion species and its energy in order to induce the largest damaged regions. These regions were then selectively etched by hydrofluoric acid vapour to form nanopores on the glass surface. Subsequently, gold nanoparticles were embedded into the nanopores by vacuum evaporation, followed by thermal treatment. In the new plasmonic structure obtained with these procedures, the localized surface plasmon excitation wavelength induced around the gold nanoparticles was found to show a redshift, which agreed well with the theoretical calculation, when water was introduced into the nanopores. This indicates that the fabricated structure can be used as a sensing element to detect the adhesion of substances such as biomolecules to the nanoparticles by measuring the redshift.

Proposal of a grating-based optical reflection switch using phase change materials.

We have proposed a novel grating-based optical reflection switch using a phase change material (PCM). The device switches on/off light or shifts the light propagation direction by switching the PCM grating between its amorphous and crystalline states. Thus, the switching status is non-volatile and the device is promising for realizing low power consumption. The device structure was designed and optimized by numerical simulations to obtain high switching efficiency. It is shown that there exists a parameter window where high efficiency is achievable. The static switching characteristics were confirmed by finite-difference time-domain (FDTD) simulations. The design scheme can also be applied to other planar dielectric gratings.

Monitoring surface-assisted biomolecular assembly by means of evanescent-field-coupled waveguide-mode nanobiosensors.

Biological self-assembly is a natural process that involves various biomolecules, and finding the missing partner in these interactions is crucial for a specific biological function. Previously, we showed that evanescent-field-coupled waveguide-mode sensor in conjunction with a SiO(2) waveguide, the surfaces which contain cylindrical nanometric holes produced by atomic bombardment, allowed us to detect efficiently the biomolecular interactions. In the present studies, we showed that the assembly of biomolecules can be monitored using the evanescent-field-coupled waveguide-mode biosensor and thus provide a methodology in monitoring assembly process in macromolecular machines while they are assembling.

Influence of nanometric holes on the sensitivity of a waveguide-mode sensor: label-free nanosensor for the analysis of RNA aptamer-ligand interactions.

Evanescent-field-coupled (EFC) waveguide-mode sensors can be used to detect nucleic acids or proteins from the changes in the local index of refraction upon adsorption of the target molecule on a waveguide surface. We recently described an EFC waveguide-mode sensor in which nanometric holes on a waveguide film resulted in an improved sensitivity in the analysis of the interactions of biomolecules. In the present study, we have shown that sensitivity depends upon the diameter of the holes, where increase in diameter of holes increases spectral shift resulting in an improved sensitivity. Using this improved EFC waveguide-mode sensor, we could detect interactions between RNA and a small ligand, cyanocobalamin (vitamin B 12), and between RNA and a protein (human coagulation factor IXa). These two interactions were monitored on surfaces modified with biotin-streptavidin-biotin and N-(2-trifluoroethanesulfonatoethyl)- N-(methyl)triethoxysilylpropyl-3-amine, respectively.

Silica-based monolithic sensing plates for waveguide-mode sensors.

We developed a monolithic sensing plate for a waveguide-mode sensor. The plate consists of a SiO(2) glass substrate and a thin silicon layer the surface of which is thermally oxidized to form a SiO(2) glass waveguide. We confirmed that the sensing plate is suitable for high-sensitivity detection of molecular adsorption at the waveguide surface. In addition, a significant enhancement of the sensitivity of the sensor was achieved by perforating the waveguide with holes with diameters of a few tens of nanometers by selective etching of latent tracks created by swift heavy-ion irradiation. Possible strategies for optimizing the plate are discussed.

A plasmonic photocatalyst consisting of silver nanoparticles embedded in titanium dioxide.

Titanium dioxide (TiO2) displays photocatalytic behavior under near-ultraviolet (UV) illumination. In another scientific field, it is well understood that the excitation of localized plasmon polaritons on the surface of silver (Ag) nanoparticles (NPs) causes a tremendous increase of the near-field amplitude at well-defined wavelengths in the near UV. The exact resonance wavelength depends on the shape and the dielectric environment of the NPs. We expected that the photocatalytic behavior of TiO2 would be greatly boosted if it gets assisted by the enhanced near-field amplitudes of localized surface plasmon (LSP). Here we show that this is true indeed. We named this new phenomenon "plasmonic photocatalysis". The key to enable plasmonic photocatalysis is to deposit TiO2 on a NP comprising an Ag core covered with a silica (SiO2) shell to prevent oxidation of Ag by direct contact with TiO2. The most appropriate diameter for Ag NPs and thickness for the SiO2 shell giving rise to LSP in the near UV were estimated from Mie scattering theory. Upon implementing a device that took these design considerations into account, the measured photocatalytic activity under near UV illumination of such a plasmonic photocatalyst, monitored by decomposition of methylene blue, was enhanced by a factor of 7. The enhancement of the photocatalytic activity increases with a decreased thickness of the SiO2 shell. The plasmonic photocatalysis will be of use as a high performance photocatalyst in nearly all current applications but will be of particular importance for applications in locations of minimal light exposure.

The design of evanescent-field-coupled waveguide-mode sensors.

An evanescent-field-coupled waveguide-mode sensor with a multilayer structure consisting of a dielectric waveguide, a thin reflecting layer, and a glass substrate illuminated under the Kretschmann configuration operates as a sensor that is capable of detecting modifications in the dielectric environment near the waveguide surface with superior sensitivity by measuring the change in reflectivity. The sensitivity of the sensor is strongly dependent on the optical constants of the reflecting layer. Numerical simulations show that a sensor having a reflecting layer with a small value of the real part of the complex refractive index shows a good sensitivity for both S- and P-polarized light. Materials with values of the real and imaginary parts of the complex refractive index of >4 and ∼0.5, respectively, are suitable for use as reflecting layers when S-polarized light excites only the lowest order waveguide mode. The simulations were experimentally confirmed using sensors with Au, Cu, Cr, W, a-Si, or Ge reflecting layers deposited by radiofrequency magnetron sputtering by observation of specific adsorption of streptavidin on biotinyl groups using an S-polarized laser beam with a wavelength of 632.8 nm. From the results, guidelines are given for the fabrication of preferred sensor configurations.

High sensitivity sensors made of perforated waveguides.

Sensors based on surface plasmons or waveguide modes are at the focus of interest for applications in biological or environmental chemistry. Waveguide-mode spectra of 1 mum-thick pure and perforated silica films comprising isolated nanometric holes with great aspect ratio were measured before and after adhesion of streptavidin at concentrations of 500 nM. The shift of the angular position for guided modes was nine times higher in perforated films than in bulk films. Capturing of streptavidin in the nanoholes is at the origin of that largely enhanced shift in the angular position as the amplitude of the guided mode in the waveguide perfectly overlaps with the perturbation caused by the molecules. Hence, the device allows for strongly confined modes and their strong perturbation to enable ultra-sensitive sensor applications.