Organic–inorganic nanomatrix structure and properties of related naturally occurring rubbery macromolecules

The outstanding mechanical properties of soft materials i.e. natural rubber are partly due to the organic–inorganic nanomatrix structure because numerous organic microparticles are dispersed in a small amount of an inorganic nanomatrix composed of inorganic nanoparticles and organic macromolecules. Here we form an organic–inorganic nanomatrix using graft-copolymerization of a vinyl monomer with an inorganic oxide precursor onto natural rubber particles with an average diameter of 1 μm dispersed in water. The inorganic oxide precursor is converted into inorganic oxide nanoparticles through hydrolysis and condensation, forming chemical linkages between natural rubber microparticles and inorganic oxide nanoparticles. Transmission electron microscopy indicates that the organic–inorganic nanomatrix is densely filled with inorganic oxide nanoparticles and the natural rubber microparticles are dispersed in the nanomatrix. This nanomatrix composite realizes both energetic elasticity and entropic elasticity of a soft material, opening a novel field of building block chemistry with respect to a pair of organic microparticles and inorganic nanoparticles.     

On-off switching properties of one-dimensional photonic crystals consisting of azo-functionalized polymer liquid crystals having different methylene spacers and polyvinyl alcohol

In this paper, photoresponsive behavior of multi-bilayered films having precisely controlled layer thickness prepared by stacking an azo-functionalized polymer liquid crystal, PMAzXAc, and polyvinyl alcohol alternatively, PVA, is described. The multi-bilayered films were found to reflect a light of specific wavelength depending on the layer thickness and refractive index, and showed the reversible change in the reflection intensity by irradiation with visible and UV lights. The change in the reflection intensity was brought about by change in the molecular orientation of PMAzXAc between an out-of-plane orientation and a photo-induced isotropic state, and was strongly dependent on the number of methylene spacer of PMAzXAc linking the azobenzene side group with the acrylate polymer main chain. PMAz6Ac with hexa-methylene spacer showed the largest change in the reflection intensity, while smaller change in the reflection intensity was observed for PMAzXAc having shorter or longer methylene spacer than 6. The effect of the methylene spacers on the photochemical change in the molecular orientation of azobenzene chromophores in the multi-bilayered films will be discussed.     

Perpendicular oriented cylinders via directional coalescence of spheres embedded in block copolymer films induced by solvent annealing

Polystyrene-b-poly(methyl acrylate) (PS-b-PMA) block copolymer with PS volume fraction of 25.2 vol% was synthesized by atom transfer radical polymerization. Non-pretreated silicon wafers were used as the substrates to prepare perpendicular oriented PS cylinders in PMA matrix via solvent annealing which could induce the transformation of spheres to vertically oriented and hexagonally packed cylinders. The spherical microdomains were formed after the evaporation of solvents from the solutions of the block copolymer in selective solvents mixed from methanol, acetone and dichloromethane. The thickness of films could be as thick as 1000 nm, which were much thicker than usual cases and the cylinders came from the directional coalescence of the spheres, thus any pre-treatments of the substrates were not required for perpendicular orientation. The structures were characterized by small angle X-ray scattering (SAXS), transmission electron microscope (TEM), atom force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS).     

A Moment Method of the Log-Normal Size Distribution with the Critical Size Limit in the Free-Molecular Regime

The present work proposes new formulations of the moment in the free-molecular size regime involving (1) boundary equations at the critical size for evaporation, condensation, and nucleation, and (2) b coefficient functions for coagulation that are improved by two parameters (standard deviation and nondimensional critical size). Using these formulations based on the error function, the critical particle size is readily introduced into the log-normal moment method for applications in general aerosol dynamics. In the situation that the particle size distribution is located near the critical size, the proposed moment method (which considers the critical size limit) improves predictions of total particle number and particle volume concentrations as compared with previously well-used log-normal moment methods for sizes ranging from 0 to ∞. However, as the size distribution approaches to the continuum size regime, the influence of the critical size becomes smaller. Thus, the new formulations are expected to improve microphysical parameterization in the free-molecular regime in aerosol-transport models.

Copyright 2014 American Association for Aerosol Research     

Synthesis of 4‐Aryl‐2‐Quinolones via Copper‐Catalyzed Hydroarylation of (o‐Aminophenyl)propiolates with Arylboronates

4‐Aryl‐2(1H)‐quinolones were efficiently synthesized via copper‐catalyzed hydroarylation of (o‐aminophenyl)propiolates with arylboronic acid neopentyl glycol esters. The substrate propiolates were prepared from the corresponding silylalkynes with carbon dioxide by Kondo’s carboxylation method using N,N‐dimethylformamide as a solvent. Hydroarylation was performed in the presence of 3 mol% copper(II) acetate in methanol at 28 °C for 12 h and subsequent deprotection using trifluoromethanesulfonic acid (3.0 equiv.) at 65 °C for 2 h in the same pot to afford the desired 4‐aryl‐2(1H)‐quinolones in 39–89% yields.

     

Fire Safety Performance of Japanese Traditional Wood/Soil Walls and Implications for the Restoration of Historic Buildings in Urban Districts

Grass-root research activities to clarify fire safety performance of Japanese traditional wooden construction are introduced. The activities aim to resolve conflict between the restoration of historic buildings and the reduction of risk and hazard of urban fires. Among various activities, scope and results of fire resistance tests on traditional soil wall assemblies supported by timber frame are reported in detail. The test results indicate an encouraging prospect for the rational fire safety assessment of historic buildings and further development of fire-safe traditional constructions for the restoration of historic buildings and historic urban districts.     

Effect of pitting corrosion on strength of web plates subjected to patch loading

Pitting corrosion is typical corrosion observed on coated hold frames in way of cargo holds of bulk carriers, which exclusively carry coal and iron ore. Extensive survey on the effect of pitting corrosion on structural strength under a wide variety of loading conditions is necessary to clarify the relationship between pitting intensity and residual strength in detail. In the present study, a series of tests has been conducted on structural models which consist of web, shell and face plates to investigate the effect of pitting corrosion on strength of web plates subjected to patch loading. In these tests, artificial pitting was made on the web plates and two equal concentrated loads have been applied vertically at the one third points of simply supported models. It was found that web crippling behavior is strongly affected by the pit distribution on the web plates. According to the FE-analyses following the experiment, ultimate strength of the web plates with pitting under patch loading is a little smaller than or almost the same as that of the web plates with uniform corrosion in terms of average thickness loss.     

The Fe3O4-formation by the ‘Ferrite Process’: Oxidation of the reactive Fe(OH)2 suspension induced by sucrose

A mechanism of the formation of small particles of iron oxide in the wastewater treatment system ‘Ferrite Process’ is described. Small particles consisting of the Fe₃O₄−γ-Fe₂O₃ solid solution having slightly higher content of γ-Fe₂O₃ were obtained by the aerial oxidation of Fe(OH)₂ suspension in the presence of a weak dispersing reagent, sucrose, at pH 9.0. The increase of γ-Fe₂O₃ content is caused by a further oxidation of the Fe₃O₄ particles in the course of the reaction. The further oxidation was accelerated below 1000 Å of the particle size. When SO²⁻₄ ion coexisted with sucrose in the reaction medium, the further oxidation was reduced and the treatment of the wastewater was improved. At a temperature interval of 40°–65°C, the formation of α-FeOOH was completely inhibited by a small amount of sucrose and only Fe₃O₄ was obtained.     

Bioaugmented membrane bioreactor (MBR) with a GAC-packed zone for high rate textile wastewater treatment

The long-term performance of a bioaugmented membrane bioreactor (MBR) containing a GAC-packed anaerobic zone for treatment of textile wastewater containing structurally different azo dyes was observed. A unique feeding strategy, consistent with the mode of evolution of separate waste streams in textile plants, was adopted to make the best use of the GAC-zone for dye removal. Dye was introduced through the GAC-zone while the rest of the colorless media was simultaneously fed through the aerobic zone. Preliminary experiments confirmed the importance of coupling the GAC-amended anaerobic zone to the aerobic MBR and also evidenced the efficacy of the adopted feeding strategy. Following this, the robustness of the process under gradually increasing dye-loading was tested. The respective average dye concentrations (mg/L) in the sample from GAC-zone and the membrane-permeate under dye-loadings of 0.1 and 1 g/L.d were as follows: GAC-zone (3, 105), permeate (0, 5). TOC concentration in membrane-permeate for the aforementioned loadings were 3 and 54 mg/L, respectively. Stable decoloration along with significant TOC removal during a period of over 7 months under extremely high dye-loadings demonstrated the superiority of the proposed hybrid process.     

Formation of bromo-substituted triclosan during chlorination by chlorine in the presence of trace levels of bromide

The side reactions of triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether, TC) and chlorine in the presence of sodium chloride were investigated. In the absence of sodium chloride, three chloro-derivatives of TC, 2',3,4,4'-tetrachloro-2-hydroxydiphenyl ether (3-Cl-TC), 2',4,4',5-tetrachloro-2-hydroxydiphenyl ether (5-Cl-TC), and 2',3,4,4',5-pentachloro-2-hydroxydiphenyl ether (3,5-Cl(2)-TC) were formed, whereas in the presence of sodium chloride, 3-bromo-2',4,4'-trichloro-2-hydroxydiphenyl ether (3-Br-TC), 5-bromo-2',4,4'-trichloro-2-hydroxydiphenyl ether (5-Br-TC), (3 or 5)-bromo-2',4,4',(5 or 3)-chloro-2-hydroxydiphenyl ether ((3,5)-(BrCl)-TC), and 3,5-dibromo-2',4,4'-trichloro-2-hydroxydiphenyl ether (3,5-Br(2)-TC) were additionally formed. Radiochemical neutron activation analysis indicated that 1g of commercially available sodium chloride contained 73 microg of bromide and the bromide ion was determined to be the source of the side reactions. The rate of decrease of TC due to reaction with chlorine was greatly accelerated by the presence of bromide ion in the system: the rate with only 1 x 10(-5) M bromide ion was three times the rate in the absence of bromide.