Curing of epoxy resin by ultrafine silica modified by grafting of hyperbranched polyamidoamine using dendrimer synthesis methodology

Hyperbranched polyamidoamine–grafted silica was prepared according to dendrimer synthesis methodology. The modified silica was dispersed uniformly in epoxy resin, and the curing of epoxy resin proceeded successfully by heating in the presence of the modified silica; the gel fraction of the epoxy resin cured by the hyperbranched polyamidoamine–grafted silica (grafting = 80.2%) reached 77% at 170°C after 48 h. The gel fraction increased with increasing terminal amino group content of the hyperbranched polyamidoamine–grafted silica. In addition, the curing ability of the silica increased by complexation of the terminal amino groups of the grafted polyamidoamine with boron trifluoride. The modulus of elasticity of the curing materials obtained using the modified silica as a curing agent was lower than that using conventional a curing agent such as ethylenediamine in the presence of untreated silica. On the other hand, the heat resistance of the curing product using the modified silica was superior to that using ethylenediamine, but no difference in glass‐transition temperature was observed. It is expected that hyperbranched polyamidoamine grafted‐silica is incorporated uniformly with chemical bonds in the matrix of the epoxy resin. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 573–579, 2001     

Effects of Atmospheric Composition on the Molecular Structure of Synthesized Silicon Oxycarbides

The dependence of silicon oxycarbides' chemical composition and molecular structure on their reaction conditions was tested by varying the atmosphere under which pyrolysis was performed. To obtain the silicon oxycarbides, densely cross‐linked silicone resin particles with an averaged diameter of 2 μm were pyrolyzed in various atmospheres of H₂, Ar, and CO₂, in the temperature range 700°C–1100°C. The residual mass of resin after pyrolysis was almost constant at 700°C, although their apparent colors varied distinctly. The sample obtained from the H₂ atmosphere was white, whereas that obtained from the CO₂ atmosphere was dark brown. Fourier‐transform infrared (FT‐IR) spectra of the residues suggested that the Si–O–Si network evolution was accelerated in the CO₂ atmosphere. Beyond 800°C, the chemical compositions of the compounds obtained from a H₂ atmosphere increasingly approached near‐stoichiometric SiO₂–xSiC composition with increasing the pyrolysis temperature. Compounds from a CO₂ atmosphere approached a composition of SiO₂–xC with no free SiC as the pyrolysis temperature increased. In the products from an Ar atmosphere, SiO₂–xSiC–yC compositions were typically obtained. The observed effects of the pyrolysis atmosphere on the resulting chemical compositions were analyzed in terms of thermodynamic calculations. Electron spin resonance (ESR) spectra revealed broad and intense signals from products obtained from either Ar or CO₂. Estimating from the signal intensity, the residual spin concentrations were in the range 10¹⁸–10¹⁹ g^?1. Meanwhile, the spectra from the samples obtained in H₂ showed weak and sharp signals with estimated spin concentrations ranging from 10¹⁶–10¹⁷ g^?1. This signal attenuation may have been due to the hydrogen capping of dangling bond formed during pyrolysis.     

Hydrogen and carbon dioxide adsorption with tetra‐n‐butyl ammonium semi‐clathrate hydrates for gas separations

Gas adsorption rates of H₂, CO₂, and H₂‐CO₂ gas mixture (H₂/CO₂ = 3.4) with tetra‐n‐butyl ammonium salt (bromide, chloride, and fluoride) semi‐clathrate hydrate particles were measured at 269 K to assess their properties for gas separation. Equilibrium gas occupancies in the S‐cages of the particles were in order of (high to low) for hexagonal structure‐I, tetragonal structure‐I, and superlattice of cubic structure‐I structures with the maximum fractional occupancy by CO₂ being about 40%. The CO₂ diffusion rate depended on the anion size of the salt, which is attributed to distortion of the S‐cage that is close to the molecular size of CO₂. Simulations of semi‐clathrate hydrate particles with theory showed that H₂/CO₂ selectivities could be as high as 36 (3.0 mol% TBAF) and that selectivities for an ideal membrane (3.3 mol% TBAF) could be >100 (269 K, 0.3–4.5 MPa). Semi‐clathrate hydrates have wide application as separation media for gas mixtures. © 2014 American Institute of Chemical Engineers AIChE J, 61: 992–1003, 2015     

High tensile strength fiber of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] processed by two‐step drawing with intermediate annealing

High tensile strength fibers of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] [P(3HB‐co‐3HH)], a type of microbial polyesters, were processed by one‐step and two‐step cold‐drawn method with intermediate annealing. Thermal degradation behaviors were characterized by differential scanning calorimeter and gel permeation chromatography measurements. Thermal analyses were revealed that molecular weights decreased drastically within melting time at a few minute. One‐step cold‐drawn fiber with drawing ratio of 10 showed tensile strength of 281 MPa, while tensile strength of as‐spun fiber was 78 MPa. When two‐step drawing was applied for P(3HB‐co‐3HH) fibers, the tensile strength was led to 420 MPa. Furthermore, the optimization of intermediate annealing condition leads to enhance the tensile strength at 552 MPa of P(3HB‐co‐3HH) fiber. Wide‐angel X‐ray diffraction measurements of these fibers suggest that the fibers with high tensile strength include much amount of the planer‐zigzag conformation (β‐form) as molecular conformation together with 2₁ helix conformation (α‐form). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41258.     

Predicting nitrogen leaching with the modified LEACHM model: validation in soils receiving long-term application of animal manure composts

A variety of process-based models have been developed for predicting nitrogen (N) dynamics in agro-ecosystem; however, no reliable models have been validated for N leaching from soils receiving a long-term application of different types of animal manure composts. The Leaching Estimation and Chemistry Model (LEACHM) was recently modified by incorporating the basic structure of Rothamsted Carbon Model for extending its ability to describe soil organic matter decomposition and subsequent N leaching in soils rich in organic matter. We evaluate the applicability of the modified LEACHM in cropped Yellow soils receiving 10-year application of cattle or swine manure compost in addition to chemical fertilizers, where high-frequency field monitoring data of soil water contents, soil N contents and leachate N concentrations were available for the last 3 years. Particular attention was paid to determine all input parameters from independent measurements, parameterization from known soil properties or databases without optimisation to fit the measured field data. The model reasonably predicted temporal changes in the soil NH₄-N and NO₃-N contents, and inorganic N concentrations in the leachate as well as their differences due to different manure compost/chemical fertilizer applications. The simulations of leached N concentration yielded a Willmott index of agreement (IA) of 0.62–0.68, with those for soil moisture, soil nitrate content and crop N uptake all within an acceptable IA range. In view of the good performance without site-specific calibrations, the modified LEACHM appears to be a valuable tool for predicting N leaching from cropped soils receiving long-term manure compost applications.     

Emission of Particulate Matter 2.5 (PM2.5) from Sewage Sludge Incinerators in Japan

Because fine particulate matter ≤2.5 µm in diameter (PM2.5) causes health problems, PM2.5 emissions are of concern. However, little research on stationary sources has been conducted. To determine the concentration and filtration behavior of PM2.5, dust was collected from five fluid-bed sewage sludge incinerators (SSIs) sorted by particle size using cascade impactors. The average PM2.5 concentration was 0.00014–4.8 mg/Nm³. The total estimated amount of PM2.5 emissions from the SSIs for all plants in Japan was 0.96–8.9 tons/year. Since the SSIs with dry Electrostatic Precipitators (EP) contributed 75–99% of the total emissions, replacing dry EPs with bag filters would significantly reduce the PM2.5 emissions from SSI.     

Wettability of a microgrid‐structured polymer film with microfabrication utilizing the stick–slip phenomenon

A microgrid structure was formed on the surface of a polyethylene terephthalate (PET) film with an original microfabrication method (termed SS processing) utilizing the stick–slip (SS) phenomenon, and the effect of this surface structure on wettability was evaluated. Microgrid‐structured films could be fabricated by two‐axis SS processing. Moreover, an arbitrary parallelogram microgrid structure could be formed by selecting the direction of the second SS processing with respect to that of the first SS processing. Both water contact angle and water sliding angle of the SS‐processed film were larger than that of the PET film. Hence, the SS‐processed film showed a petal‐like effect. Furthermore, the water sliding angle of the microgrid‐structured film showed anisotropy due to the pinning effect derived from the microgrid structure. As a result, it is revealed that a hydrophobic PET film with a petal‐like effect and anisotropic wettability can be fabricated by SS processing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45140.     

Thermotropic and Barotropic Phase Behavior of Phosphatidylcholine Bilayers

Bilayers formed by phospholipids are frequently used as model biological membranes in various life science studies. A characteristic feature of phospholipid bilayers is to undergo a structural change called a phase transition in response to environmental changes of their surroundings. In this review, we focus our attention on phase transitions of some major phospholipids contained in biological membranes, phosphatidylcholines (PCs), depending on temperature and pressure. Bilayers of dipalmitoylphosphatidylcholine (DPPC), which is the most representative lipid in model membrane studies, will first be explained. Then, the bilayer phase behavior of various kinds of PCs with different molecular structures is revealed from the temperature–pressure phase diagrams, and the difference in phase stability among these PC bilayers is discussed in connection with the molecular structure of the PC molecules. Furthermore, the solvent effect on the phase behavior is also described briefly.     

Optical assessment of silicon nanowire arrays fabricated by metal-assisted chemical etching

Silicon nanowire (SiNW) arrays were prepared on silicon substrates by metal-assisted chemical etching and peeled from the substrates, and their optical properties were measured. The absorption coefficient of the SiNW arrays was higher than that for the bulk silicon over the entire region. The absorption coefficient of a SiNW array composed of 10-μm-long nanowires was much higher than the theoretical absorptance of a 10-μm-thick flat Si wafer, suggesting that SiNW arrays exhibit strong optical confinement. To reveal the reason for this strong optical confinement demonstrated by SiNW arrays, angular distribution functions of their transmittance were experimentally determined. The results suggest that Mie-related scattering plays a significant role in the strong optical confinement of SiNW arrays.     

Improvement of carrier diffusion length in silicon nanowire arrays using atomic layer deposition

To achieve a high-efficiency silicon nanowire (SiNW) solar cell, surface passivation technique is very important because a SiNW array has a large surface area. We successfully prepared by atomic layer deposition (ALD) high-quality aluminum oxide (Al₂O₃) film for passivation on the whole surface of the SiNW arrays. The minority carrier lifetime of the Al₂O₃-depositedSiNW arrays with bulk silicon substrate was improved to 27 μs at the optimum annealing condition. To remove the effect of bulk silicon, the effective diffusion length of minority carriers in the SiNW array was estimated by simple equations and a device simulator. As a result, it was revealed that the effective diffusion length in the SiNW arrays increased from 3.25 to 13.5 μm by depositing Al₂O₃ and post-annealing at 400°C. This improvement of the diffusion length is very important for application to solar cells, and Al₂O₃ deposited by ALD is a promising passivation material for a structure with high aspect ratio such as SiNW arrays.