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.     

Baffled membrane bioreactor (BMBR) for efficient nutrient removal from municipal wastewater

Submerged membrane bioreactors (MBRs) are now widely used for various types of wastewater treatment. One drawback of submerged MBRs is the difficulty in removing nitrogen because intensive aeration is usually carried out in the tank and the MBRs must therefore be operated under aerobic conditions. In this study, the feasibility of treating municipal wastewater by a baffled membrane bioreactor (BMBR), particularly in terms of nitrogen removal, was examined. Simultaneous nitrification/denitrification in a single and small reaction tank was possible by inserting baffles into a normal submerged MBR as long as wastewater was fed in the appropriate way. To examine the applicability of the BMBR, pilot-scale experiments were carried out using real municipal wastewater. Although neither external carbon addition nor mixed liquor circulation was carried out in the operation of the BMBR, average removal rates of total organic carbon (TOC), total phosphorus (T-P) and total nitrogen (T-N) reached 85%, 97% and 77%, respectively, with the hydraulic retention time (HRT) of 4.7h. Permeability of the membrane could be maintained at a high level throughout the operation. It was found that denitrification was the limiting step in removal of nitrogen in the BMBR in this study. Various types of monitoring carried out in the BMBR also demonstrated the possibility of further improvements in its performance.     

Transition in fouling mechanism in microfiltration of a surface water

The main disadvantage of membrane filtration is membrane fouling, which remains as the major obstacle for more efficient use of this technology. Information about the constituents that cause fouling is indispensable for more efficient operation. We examined the changes in both foulant characteristics and membrane morphology by performing the pilot-scale filtration test using one microfiltration membrane. During the operation, we cut the membrane fibers three times, and the components that caused irreversible fouling were extracted by acid or alkaline solution. We found that the characteristic of inorganic matter extracted by acid solution completely differed depending on the filtration period. A large amount of iron was extracted in the second chemical cleaning, while manganese was the dominant component of the extracted inorganic matter in the third chemical cleaning. The analysis of Fourier transform infrared (FTIR) and cross polarization magic angle spinning carbon-13 (CPMAS (13)C) nuclear magnetic resonance (NMR) demonstrated that the contribution of humic substances and carbohydrate in the organic foulant had increased as fouling developed. The changes in the major foulant have no relation with the fluctuation in feed water. The analysis of membrane morphology illustrated that the cake layer started to build up after the blockage of membrane pores. Based on the above results, we hypothesized the following fouling mechanism: the pores were covered or narrowed with relatively large particles such as iron, carbohydrate or protein; small particles such as manganese or humic substances blocked the narrowed pores; and finally an irreversible cake layer started to build up on the membrane surface.     

Evaluation of the impact of bioaugmentation and biostimulation by in situ hybridization and microelectrode

Three rotating disk biofilm reactors were operated to evaluate whether bioaugmentation and biostimulation can be used to improve the start-up of microbial nitrification. The first reactor was bioaugmented during start-up period with an enrichment culture of nitrifying bacteria, the second reactor received a synthetic medium containing NH(4)(+) and NO(2)(-) to facilitate concomitant proliferation of ammonia- and nitrite-oxidizing bacteria, and the third reactor was used as a control. To evaluate the effectiveness of bioaugmentation and biostimulation approaches, time-dependent developments of nitrifying bacterial community and in situ nitrifying activity in biofilms were monitored by fluorescence in situ hybridization (FISH) technique and microelectrode measurements of NH(4)(+), NO(2)(-), NO(3)(-), and O(2). In situ hybridization results revealed that addition of the enrichment culture of nitrifying bacteria significantly facilitated development of dense nitrifying bacterial populations in the biofilm shortly after, which led to a rapid start-up and enhancement of in situ nitrification activity. The inoculated bacteria could proliferate and/or survive in the biofilm. In addition, the addition of nitrifying bacteria increased the abundance of nitrifying bacteria in the surface of the biofilm, resulting in the higher nitrification rate. On the other hand, the addition of 2.1mM NO(2)(-) did not stimulate the growth of nitrite-oxidizing bacteria and did inhibit the proliferation of ammonia-oxidizing bacteria instead. Thus, the start-up of NO(2)(-) oxidation was unchanged, and the start-up of NH(4)(+) oxidation was delayed. In all the three biofilm reactors, data sets of time series analyses on population dynamics of nitrifying bacteria determined by FISH, in situ nitrifying activities determined by microelectrode measurements, and the reactor performances revealed an approximate agreement between the appearance of nitrifying bacteria and the initiation of nitrification activity, suggesting that the combination of these techniques was a very powerful monitoring tool to evaluate the effectiveness of bioaugmentation and biostimulation strategies.     

Advanced HSLA Steels for Automotive Use

Characteristic HSLA steels for automotive use are introduced in which both of precipitation and microstructure is controlled to obtain suitable mechanical properties.For outer panels such as fender,the combination of low yield strength,high tensile strength and deep-drawability were realized by controlling the distribution of NbC and precipitation free zone.The other steel,developed for chassis parts such as lower arm,utilizes extremely fine interphase precipitation to obtain high yield strength and excellent hole expansionability.Both steels have contributed to the reduction of weight in car body.     

Development of function-graded proton exchange membrane for PEFC using heavy ion beam irradiation

The graded energy deposition of heavy ion beam irradiation to polymeric materials was utilized to synthesize a novel proton exchange membrane (PEM) with the graded density of sulfonic acid groups toward the thickness direction. Stacked Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films were irradiated by Xe⁵⁴⁺ ion beam with the energy of 6 MeV/u under a vacuum condition. The induced trapped radicals by the irradiation were measured by electron spin resonance (ESR) spectroscopy. Irradiated films were grafted with styrene monomer and then sulfonated. X-ray photo-electron spectroscopy (XPS) spectra showed that the densities of sulfonic acid groups were controlled for injection “Surface” and transmit “Back” sides of the fabricated PEM. The membrane electrode assembly (MEA) fabricated by the function-graded PEM showed improved fuel cell performance in terms of voltage stability. It was expected that the function-graded PEM could control the graded concentration of sulfonic acid groups in PEM.     

Polymer electrolyte membrane with nanomatrix channel prepared by sulfonation of natural rubber grafted with polystyrene

High‐proton‐conductive polymer electrolyte with a nanomatrix channel was prepared by graft copolymerization of styrene onto deproteinized natural rubber followed by sulfonation with chlorosulfonic acid. First, natural rubber latex was purified with urea in the presence of surfactant to remove almost all proteins present in the rubber. Second, graft copolymerization of styrene onto deproteinized natural rubber was carried out with tert‐butyl hydroperoxide/tetraethylenepentamine as an initiator at 30°C in latex stage. The graft‐copolymerized natural rubber (DPNR‐graft‐PS) was sulfonated with chlorosulfonic acid in chloroform solution at an ambient temperature. The resulting sulfonated DPNR‐graft‐PS was characterized by FTIR spectroscopy, solid state ¹³C CP/MAS NMR spectroscopy, elemental analysis, and transmission electron microscopy. High proton conductivity of about 0.1 S/cm, less water uptake of 24 wt % and comparatively good stress at break of 9 MPa were accomplished at suitable contents of styrene units and sulfur, i.e., 32 wt % and 75 mol %, respectively. The high proton conductivity, excellent stability, and good mechanical properties were associated with not only the formation of the nanomatrix channel but also a specific concentration of sulfuric acid group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.