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.     

Formation Processes of β-C2S by the Decomposition of Hydrothermally Prepared C-S-H with Ca(OH)2

A mixture of CaO and silicic acid prepared with a Ca/Si ratio of 2.0 was hydrothermally synthesized at 80° to 200°C, and the thermal decomposition behavior of the products (C-S-H with Ca(OH)₂) was analyzed using XRD, ²⁹Si MAS NMR, and the trimethylsililation method (TMS). It was found that the main silicate anion structure of C-S-H was a mixture of a dimer and a single-chain polymer (larger than Si₅O₁₆) and that polymerization advanced with an increase of the synthesizing temperature. On heating, the products decomposed to form β-C₂S. It was found that the decomposition was gradual and that the-higher the temperature of hydrothermal synthesis, the lower was the temperature of the decomposition into β-C₂S. Although the decomposition proceeded to form a monomer (β-C₂S) from the polymer and dimer, this dimer was resistant to heat and did not decompose unless heated to above 400°C.     

High adhesion of diamond-like carbon thin film to an aluminum alloy achieved by substrate sputtering and redeposition method

A novel technique to improve the adhesion of a diamond-like carbon (DLC) film to an Al alloy was demonstrated in this study. DLC films were deposited by diode rf bias sputtering. The Al component in the substrate was initially deposited on a graphite target during the sputter-cleaning of the substrate. Then the graphite target and the deposited Al were simultaneously sputtered to form an interface layer between the DLC film and the substrate in the early stage of deposition. We call this method substrate sputtering and redeposition (SSRD), which enhanced the antiwear lifetime of DLC/Al alloy samples. X-ray photoelectron spectroscopy clarified that a thicker mixed layer of Al and C was formed around the interface in the case of a longer substrate sputtering duration in the SSRD method. This interface structure could account for the strong adhesion of the DLC film to the substrate and the reduced delamination of the film obtained using the SSRD method.     

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.     

Sinterability and properties of Ti(N1−x,O x ) y -(V,Ta)C-Ni sintered alloys having a golden colour

The effect of oxygen and carbide addition on the sinterability of TiN _y (0.42<y<1)-Ni alloys, in which part of the nitrogen is replaced by oxygen was investigated. It was found that sinterability increased as the oxygen and carbide content increased, but the strength of the resultant sintered alloys was significantly reduced due to the presence of Ni₃Ti and Ti₂O₃ phases when the oxygen content exceeded 50 mol %. The sintered alloy with the highest hardness was found whenx=0.7,y=0.78 and the (V,Ta)C content was 18% by weight and this alloy was characterized by having a low density, good corrosion resistance and the colour of gold.     

Baseband Feedback Frequency-Division Multiplexing with Low-Power dc-SQUIDs and Digital Electronics for TES X-Ray Microcalorimeters

We are developing frequency-division multiplexing (FDM) systems with baseband feedback for TES X-ray microcalorimeter arrays for use with the DIOS mission. To meet the requirement of limited cooling capacity at cryogenic temperatures, we developed low-power and FDM-optmized dc-SQUIDs. To make maximum use of the SQUIDs, we also developed digital electronics using FPGA evaluation boards and ADC/DAC FMC daughter cards, and evaluated signal-to-noise ratios and gain-bandwidth products.     

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.     

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 C-S-H from Highly Reactive β-Dicalcium Silicate Prepared from Hillebrandite

β-dicalcium silicate synthesized by thermal dissociation of hydrothermally prepared hillebrandite (Ca₂(SiO₃)(OH)₂) exhibits extremely high hydration activity. Characterization of the hydrates obtained and investigation of the hydration mechanism was carried out with the aid of trimethylsilylation analysis, ²⁹Si magic angle spinning nuclear magnetic resonance, transmission electron microscopy selected area electron diffraction, and XRD. The silicate anion structure of C-S-H consisted mainly of a dimer and a single-chain polymer. Polymerization advances with increasing curing temperature and curing time. The C-S-H has an oriented fibrous structure and exhibits a 0.73-nm dreierketten in the longitudinal direction. On heating, the C-S-H dissociates to form β-C₂S. The temperature at which βC₂S begins to form decreases with increasing chain length of the C-S-H or as the Ca/Si ratio becomes higher. The high activity of β-C₂S is due to its large specific surface area and the fact that the hydration is chemical-reaction-rate-controlled until its completion. As a result, the hydration progresses in situ and C-S-H with a high Ca/Si ratio is formed.