Network formation and swelling behavior of photosensitive poly(vinyl alcohol) gels prepared by photogenerated crosslinking

Poly (vinyl alcohol) with pendent styrylpyridinium groups (SbQ) is insolubilized by photoirradiation. An association takes place in SbQ groups. The association of polymer chains becomes marked with increasing the number of SbQ groups. Mainly intermolecular crosslinks were formed. Transparent and homogeneous macrogels consisting of several intermolecular crosslinks are obtained. The proportion of the free water to the bound water in PVA-SbQ gels was 3.3?2.9 despite of the large change in conversion of photodimerization of SbQ groups, x=0.27?0.58. The water uptake after swelling of the gels in water increased 6–27 times compared to the original weight at pH=7. The higher the degree of photocrosslinking, the lower was the degree of swelling. The water diffusion coefficients, D, were (2.2?5.8) × 10^?5 cm² S^?1 for a 88% saponified PVA with 1 . 3 mol% SbQ groups. The volume of the gel increased discontinuously about 10-fold for the 99% saponified PVA with 0 . 096 mol% SbQ and 51% water (49% acetone). The acetone concentration at the transition decreased with increasing the degree of saponification of the PVA.     

Crystallinity and electrical conductivity of sulfur-containing microcrystalline diamond thin film

Hydrogen sulfide (H₂S) was introduced into a microwave plasma chemical vapor deposition of microcrystalline diamond thin film. Secondary-ion mass spectroscopy showed that sulfur concentration was controlled from 2 × 10¹⁵ to 9 × 10¹⁷ cm^− 3 by controlling the H₂S/CH₄ ratio, while that of hydrogen concentration was around 5 × 10²⁰ cm^− 3 and was independent of the H₂S/CH₄ ratio. Electrical conductance increased linearly as the S concentration increased from 2 × 10¹⁵ to 3 × 10¹⁶ cm^− 3 without significant deterioration of film crystallinity, i.e., the amount of sp² phase did not increase. Non-ohmic conduction was converted to ohmic conduction when the S concentration reached 9 × 10¹⁷ cm^− 3 by increasing the H₂S/CH₄ ratio to 30,000 ppm. This modification was consistent to the formation of a graphitic phase by heavy S-doping, which was identified by Raman spectra and surface morphology.     

Characterization of gas flow configurations for phosphoric acid fuel cells

The cell performance and polarization distribution in the horizontal plane of a phosphoric acid fuel cell (PAFC) were studied for thirteen different types of gas flow. In all cases, the potentials of the anode and cathode in the fuel outlet area shifted to positive directions. At 90% utilization of fuel, the potential shift and the cell voltage changed significantly from one type to another. Experimental results show that the cell voltage increased, and the potential shift decreased in the following order; CROSS-FLOW < RETURN-FLOW = CO-FLOW < COUNTER-FLOW < type E2. The extent of the change between various types depended on the following three conditions. (1) The fuel gas has an opportunity to be used twice in the horizontal plane of a cell. (2) The fuel gas flow is in parallel with the air flow. (3) The fuel gas flow is opposite to the air flow. These are requirements for obtaining good and stable performance of a fuel cell. The CROSS-FLOW case has none of these three conditions, the RETURN-FLOW case has the first condition, the CO-FLOW case has the second, the COUNTER-FLOW case has the second and the third conditions, and the best gas flow type (type E2) has all.     

Transmission electron microscopic observations of nanobubbles and their capture of impurities in wastewater

Unique properties of micro- and nanobubbles (MNBs), such as a high adsorption of impurities on their surface, are difficult to verify because MNBs are too small to observe directly. We thus used a transmission electron microscope (TEM) with the freeze-fractured replica method to observe oxygen (O₂) MNBs in solutions. MNBs in pure water and in 1% NaCl solutions were spherical or oval. Their size distribution estimated from TEM images close to that of the original solution is measured by light-scattered methods. When we applied this technique to the observation of O₂ MNBs formed in the wastewater of a sewage plant, we found the characteristic features of spherical MNBs that adsorbed surrounding impurity particles on their surface.     

Highly Reactive β-Dicalcium Silicate: III, Hydration Behavior at 40–80°C

The effect of curing temperature (40°, 60°, 80°C) on the hydration behavior of β-dicalcium silicate (β-C₂S) was investigated. The β-C₂S was obtained by decomposition of hillebrandite, Ca₂(SiO₃)(OH)₂, at 600°C, has a specific surface area of about 7 m²/g, and is in the form of fibrous crystals. The dependence of the hydration reaction on temperature continues until the reaction is completed. The hydration is completed in 1 day at 80°C and in 14 days at 14°C. The hydration mechanism is different above and below 60°C, but at a given temperature, the reaction mechanism and the silicate anion structures of C-S-H do not change significantly from the initial to the late stages of the reaction. High curing temperature and long curing times after completion of reaction promote silicate polymerization. The Ca/Si ratio of C-S-H shows high values, being almost 2.0 above 60°C and 1.95 below 40°C.     

Ultra light-weight and high-resolution X-ray mirrors using DRIE and X-ray LIGA techniques for space X-ray telescopes

We are developing novel ultra light-weight and high-resolution X-ray micro pore optics for space X-ray telescopes. In our method, curvilinear micro pore structures are firstly fabricated by silicon deep reactive ion etching (DRIE) or X-ray LIGA processes. Secondly, side walls of the micro structures are smoothed by magnetic field assisted finishing and/or hydrogen annealing techniques for high reflectivity mirrors. Thirdly, to focus parallel X-ray lights from astronomical objects, these structures are elastically or plastically bent into a spherical shape. Fourthly, the bent structures are stacked to form a multi-stage X-ray telescope. In this paper, we report on fabrication and X-ray reflection tests of silicon and nickel X-ray mirrors using the DRIE and LIGA processes, respectively. For the first time, X-ray reflections were confirmed on both of the mirrors. Estimated rms roughnesses were 5 nm and 3 nm for the silicon and nickel mirrors, respectively.     

Radiation Tolerance Evaluation of the Ti/Au Bilayer TES Microcalorimeter

We have developed Ti/Au bilayer transition-edge sensor (TES) microcalorimeters for future X-ray astrophysical satellite missions such as DIOS. One possible concern on the space use of TES microcalorimeters is its radiation tolerance. We have evaluated the performance of a Ti/Au bilayer (30/40 nm thick) TES microcalorimeter with 1.5  \(\upmu \) m thick Au absorber, before and after irradiation of 150 MeV proton beam with a total dose of 10 krad, corresponding to 10 years in the low Earth orbit. No significant changes on transition temperature, sensitivity, normal resistance, and critical current were observed. The energy resolution for 5.9 keV X-rays was 5.6  \(\pm \)  0.3 eV (FWHM) after the irradiation, which was slightly worse than 5.1  \(\pm \)  0.3 eV before the irradiation. We consider that our TES has sufficient radiation tolerance in orbit.     

Formation of magnesium silicate hydrate and its crystallization to talc

Mixtures of Mg(OH)₂ and colloidal silica with Mg/Si = 0.75 were treated hydrothermally at 180° to 600°C for 4 h ? 8 weeks. Reaction seemed always to proceed through the formation of magnesium silicate hydrate to talc, which had random displacements of layers parallel to b of nb/3, and gave a decrease of the basal spacing with increase of crystallinity. The magnesium silicate hydrate gave X-ray powder patterns indicative of two-dimensional crystals without basal spacing, had a specific area of about 300 m²/g, and gave an exotherm at 830°C. Dehydration and infrared spectra for products are also described.