Formation mechanism for hexagonal-structured self-assemblies of nanocrystalline titania templated by cetyltrimethylammonium bromide

Hexagonal-structured self-assemblies of nanocrystalline (anatase) titania templated by cetyltrimethylammonium bromide (C(16)H(33)N(CH(3))(3)Br; CTAB) (Hex-ncTiO(2)/CTAB Nanoskeleton) were formed after mixing of aqueous solutions containing CTAB spherical micelles and titanium oxysulfate acid hydrate (TiOSO(4).xH(2)SO(4).xH(2)O) as a titania precursor in the absence of any other additives. Formation mechanism of the Hex-ncTiO(2)/CTAB Nanoskeleton was examined in terms of the reaction temperature, titania precursor/CTAB mixing ratio, surfactant type, electrostatic interaction, micelle formation and molecular component. We found that crystal growth of crystalline (anatase) titania (polymorphic crystallization) was promoted with higher temperature and lower titania precursor content in aqueous solutions. In addition, we revealed that the crystalline (anatase) titania was formed in polycation, poly(allylamine hydrochloride ([CH(2)CH(CH(2)NH(2))HCl](n); PAH), and formamide (HCONH(2)) solutions. On the other hand, no titania formation was observed in anionic systems such as sodium dodecyl sulfate (CH(3)(CH(2))(11)OSO(3)Na; SDS) and poly(sodium 4-styrenesulfonate ([C(8)H(7)SO(3)Na](n); PSSS). This indicates that hydrolysis reaction of the titania precursor is initiated by not only cations but also nitrogen atoms in molecules and polymers. Hexagonally structure was formed in only cationic surfactant micellar solutions but not in polycation solutions and formamide.     

Effect of heating process on the formation of nanoparticles of elastin model polypeptide, (GVGVP)251, by gamma-ray crosslinking

Nanoparticles were prepared by the thermosensitive aggregation of the elastin model polypeptide, (GVGVP)₂₅₁, and gamma-ray crosslinking. Three different heating processes, “slow heating,” “fast heating,” and “heat shock,” were used for the aggregation of the peptide, followed by gamma-ray crosslinking. Only the “heat shock” process successfully yielded stable nanoparticles with diameters of less than ca. 150 nm and a narrow size distribution. Circular dichroism (CD) spectrometry showed that this polypeptide formed a type-II β-turn structure when the temperature was increased to above the cloudy point in the case of the “heat shock” process; suggesting that this structure might contribute to stable nanoparticle formation by gamma-rays. CD spectrometry also suggested that this structure would be affected during the formation of stable crosslinked particles.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.     

Mechanical and physical characteristics of cellulose‐fiber‐filled polyacetal composites

We investigated the mechanical and physical characteristics of composites composed of polyacetal [alternatively called polyoxymethylene (POM)] and cellulose fiber (CelF) derived from wood pulp [10–52 wt % (9.3–50.1 vol %)] without any fiber surface treatment. The modulus, deflection temperature under load, and thermal conduction coefficient of the POM/CelF composites were effectively enhanced with increasing CelF content, and the composites had an advantage of specific modulus compared to glass fiber (GF)‐filled POM. The flexural modulus of POM/CelF 40 wt % (38.2 vol %) was measured to be about 6 GPa, which was comparable to that of POM/GF 20 wt % (12.1 vol %). In the composites, the CelFs were distributed randomly as monofilaments, and the debonding of the interface between the fibers and POM matrices in the fracture faces was confirmed as less by scanning electron microscopy observation. The POM/CelF composites possessed lower specific wear rates than the POM/GF composites, and they had damping behaviors near that of neat POM. No clear dependence of the melt flow index of the base POM on these characteristics was observed, except on Charpy impact strength. The composites studied here were unique in their performance and ability to be designed in accordance with specific demands, and they could be potential replacements for mineral‐filled and GF‐filled POM composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of green compact structure on the sintering of alumina

The effect of particle agglomeration on sintering has been studied by slipcasting suspensions with pH values ranging from 2 to 11. The rate of densification has been found to depend on the degree of agglomeration. Complete dispersion of alumina primary particles has not been attained through adjustment of pH of suspensions, and agglomerates also remained in the best-dispersed suspension. Elimination of the agglomerates by sedimentation lowered the densification temperature of slip-cast compacts. The grain size-density curve is a function of temperature. High-density and small-grained sintered bodies were obtained by low-temperature long-time firing.     

Metabolic disturbance of tryptophan-nicotinamide conversion pathway by putative endocrine disruptors, bisphenol A and styrene monomer

Bisphenol A, a monomer of polycarbonate plastics, disturbed the conversion pathway of the amino acid tryptophan to the vitamin nicotinamide. The conversion ratio of tryptophan to nicotinamide was reduced to 1/15 by feeding a diet containing 1% bisphenol A. A putative disturbing reaction is kynurenine-->3-hydroxykynurenine, which is catalyzed by kynurenine monohydroxylase. This is an FAD-enzyme and requires NADPH as a coenzyme. Styrene monomer (1% addition to a normal diet) did not affect the food intake or the body weight, but slightly reduced the conversion ratio of tryptophan-nicotinamide.     

Bending of ionic polymer gel caused by swelling under sinusoidally varying electric fields

Deformation of poly(vinyl alcohol)–poly(sodium acrylate) composite hydrogel (PVA–PAA gel) under sinusoidally varying electric fields was studied in electrolyte solutions. The PVA–PAA gel was prepared by repeatedly freezing and thawing a mixed solution of PVA and polyacrylic acid. A cyclic bending–straightening motion of the PVA–PAA gel rods of about 1 mm in diameter have been observed in Na₂CO₃ aqueous solutions under the fields. The PVA–PAA gel had a response time of less than several hundreds milliseconds. The bending has also been observed in organic solvents containing an electrolyte when the organic solvent is electrolyzed. It was found that the motion of the gel under electric fields of less than 1 Hz occurred mainly through swelling due to the change of the osmotic pressure based upon the difference of the ion concentration. However, it has not been determined whether the motion at higher frequencies is caused by the osmotic effect. © 1993 John Wiley & Sons, Inc.     

Properties of copolyimides prepared from different tetracarboxylic dianhydrides and diamines

Various copolymides were prepared from two acid dianhydrides (BPDA, 3,3′,4,4′-biphenyl tetracarboxylic dianhydride; PMDA, pyromelitic dianhydride) and two diamines (PPD, p-phenylene diamine; ODA, 4,4′-oxydianiline). The thermal and mechanical properties of these polyimides were examined in detail. By appropriately selecting the ratios of the acid dianhydride component and the diamine component, polyimide films having desirable mechanical and thermal characteristics can be obtained. Further, it was proved that there is a correlation between the properties and the compositions of the copolyimides and that the properties could be estimated from the compositions by the use of multiple regression analysis. © 1996 John Wiley & Sons, Inc.     

Surface Analysis of Cr2O3‐, CoO‐, and Al2O3‐Doped Iron–Phosphate Glasses at High Temperature

Surface structures of iron–phosphate glasses were examined using X‐ray photoelectron spectroscopy (XPS). Cr₂O₃, CoO, and Al₂O₃ were introduced to the glass by the replacement of a part of Fe₂O₃, and the simulated fission products are also added. The obtained glasses showed high chemical durabilities by MCC‐1 test. In situ high‐temperature and room‐temperature XPS measurements were conducted on the polished sample surfaces and also those after 1‐week chemical durability test. Unique trends were observed in XPS spectra on heating and after the chemical durability test, respectively. Nature of the glass surface of iron–phosphate glasses was explained from the point of view of surface energy, and the origin of high chemical durability and the effect of chromium ions were discussed based on the changes on surface composition and valence states of transition‐metal ions.