Combustion Synthesis of AlON–BN Composites under Low Nitrogen Pressure

Hexagonal boron nitride (hBN) and aluminum oxinitride (AlON) composites were synthesized by combustion reaction of powder mixtures of Al–B₂O₃–AlN systems under a low pressure of nitrogen gas (0.5 MPa). Explosive combustion reaction of Al–B₂O₃ systems under the same nitrogen pressure produced alumina, aluminum borate, AlN, and AlON depending on the binary mixing ratio, but no trace of BN phases could be identified. Most of the elemental boron product remained unreacted and amorphous. On the other hand, AlN addition as a diluent in the range of 15–30 wt% was effective in producing hBN phase and forming AlON–BN composites. In the composition range of the ternary mixture of Al, B₂O₃, and AlN, where significant BN formation was identified, the primary role of AlN was to react with B₂O₃ to produce BN and α-Al₂O₃. The temperature profile obtained during the combustion reaction by a thermocouple imbedded in the middle of the powder bed revealed that the initial nitridation reaction of aluminum metal provides the heat required for the combustion reaction, creating a state of a "chemical oven." The reaction product, α-Al₂O₃, reacted subsequently with AlN to produce AlON phases to give final AlON–BN composites. The combustion reaction was highly unstable and followed a mixed mode with a regularly reversing spinning mode for aluminum nitridation reaction in the surface region and an oscillatory mode for the BN formation reaction in the subsurface region.     

Blends of chlorinated isotactic polypropylene with poly(ethylene-co-vinyl acetate) I. Effect of component polymers composition on the blend miscibility

Chlorinated isotactic polypropylenes (CPP) having various chlorine contents were blended with poly(ethylene-co-vinyl acetate)s (EVA) having various vinyl acetate (VA) contents. The blends were made by casting films from dilute THF solutions and miscibility of the blends was identified by single glass transition temperature, which was confirmed by DSC and dynamic mechanical measurements. Based on the miscibility data from a large number of CPP/EVA combinations, a miscibility map was depicted where CO equivalent weight (CO-EQW) of EVA was plotted against chlorine equivalent weight (Cl-EQW) of CPP. Though an attractive interaction between CPP and EVA could be detected in all the miscible and immiscible blend pairs, miscibility of the CPP/EVA blends could solely be observed in a relatively narrow range of Cl-EQW ca. 65–100 and CO-EQW ca. 170–230.     

Improved mechanical properties of shape‐memory polyurethane block copolymers through the control of the soft‐segment arrangement

High‐performance shape‐memory polyurethane block copolymers, prepared with two types of poly(tetramethylene glycol) (PTMG) used as soft segments, were investigated for their mechanical properties. Copolymers with a random or block soft‐segment arrangement had higher stresses at break and elongations at break than those with only one kind of PTMG. Random copolymers with fewer interchain interactions showed higher elongation than block copolymers. All the copolymers had shape‐recovery ratios higher than 80%. In dynamic mechanical testing, the glass‐transition behavior clearly depended on the soft‐segment arrangement: random copolymers had only one glass‐transition peak, whereas block copolymers showed two separate glass‐transition peaks. Overall, the control of the soft‐segment arrangement plays a vital role in the development of high‐performance shape‐memory polyurethane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2410–2415, 2004     

Kinetics of cellobiose decomposition under subcritical and supercritical water in continuous flow system

The effects of reaction temperature, pressure and residence time were investigated with a flow apparatus. Cellobiose decomposition kinetics and products in suband supercritical water were examined at temperatures from 320 to 420 °C at pressures from 25 to 40 MPa, and at residence times within 3 sec. Cellobiose was found to decompose via hydrolysis and pyrolysis. The yield of desired hydrolysis product, glucose, was the maximum value of 36.8% at 320 °C, 35 MPa, but the amount of 5-(hydroxymethyl)furfural (HMF), fermentation inhibitor increased too because residence time increased in the subcritical region owing to decrease of reaction rate. Meanwhile, though the yield of glucose is low in the supercritical region, the yield of HMF decreased compared with the subcritical region; and at the minimum yield of HMF (380 °C, 25 MPa), the yield of glucose was 21.4%. The decomposition of cellobiose followed first-order kinetics and the activation energy for the decomposition of cellobiose was 51.05 kJ/mol at 40MPa.     

Preparation and characterization of eugenol‐grafted chitosan hydrogels and their antioxidant activities

The hydrogels composed of chitosan and eugenol were prepared to enhance and sustain antioxidant activities. The vinyl groups of eugenol monomer were directly grafted on the amino groups of chitosan, using ceric ammonium nitrate. The graft of eugenol onto chitosan was confirmed by using Fourier‐transform infrared and proton nuclear magnetic resonance spectroscopies. Results from the swelling behavior, thermal stability, and wide‐angle X‐ray diffraction revealed that the equilibrium water content decreased with increase of graft yields, because of the hydrophobicity of eugenol, although the introduction of eugenol as a side chain disturbed the ordered arrangement of chitosan's crystalline structure. The eugenol‐grafted chitosan hydrogels showed lower pH sensitivity in comparison with chitosan alone, because the amino groups, which were pH sensitive, of chitosan were grafted with eugenol. The scavenging activity of the tested hydrogels increased with graft yield of eugenol, because phenolic groups in the eugenol could play a major role as potent free‐radical terminators, in the results of improved antioxidant activity in eugenol‐grafted chitosan hydrogel in comparison with chitosan alone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3500–3506, 2006     

Synthesis, structure and magnetic properties of β-MnO 2 nanorods

We present synthesis, structure and magnetic properties of structurally well-ordered single-crystalline β-MnO₂ nanorods of 50–100 nm diameter and several μm length. Thorough structural characterization shows that the basic β-MnO₂ material is covered by a thin surface layer (∼2.5 nm) of α-Mn₂O₃ phase with a reduced Mn valence that adds its own magnetic signal to the total magnetization of the β-MnO₂ nanorods. The relatively complicated temperature-dependent magnetism of the nanorods can be explained in terms of a superposition of bulk magnetic properties of spatially segregated β-MnO₂ and α-Mn₂O₃ constituent phases and the soft ferromagnetism of the thin interface layer between these two phases.     

Mobile phase composition for resolving whey proteins in reversed-phase high performance liquid chromatography

Reversed-phase high-performance liquid chromatography was successfully developed for the simultaneous and rapid separation for the main whey proteins, α-Lactalbumin and β-Lactoglobulin. This method consisted of a linear gradient of the two mobile phases of 0.1% trifluoroacetic acid in water and 0.1% trifluoroacetic acid in acetonitrile. The total run time for this separation was approximately 30 min, and α-Lactalbumin was eluted followed byβ- Lactoglobulin. The injection volume was fixed at 20 μl and the flow rate was 1 ml 1/min. The optimum mobile phase composition and gradient conditions to separate α-Lactalbumin and β-Lactoglobulin (A+B) were experimentally obtained at the 15 μm particle with a pore size of 300 Å on the linear-gradient mode.     

Effects of Acetic Acid on the Crystallization Temperature of Sol–Gel-Derived MgO Nano-Powders and Thin Films

The influences of acetic acid addition to Mg-methoxide on the stability of the precursor and the crystallization behavior of sol–gel-derived MgO nano-powders and thin films were investigated using X-ray powder diffraction, transmission electron microscopy, Fourier-transformed infrared spectroscopy, and thermogravimetry. The addition of acetic acid enhanced the stability of the alkoxide against precipitation. Moreover, during postheat treatment of the gel powders treated with acetic acid, a significantly lowered crystallization temperature (250°C) was observed as compared to the untreated counterpart (350°C). The low-temperature crystallization of MgO, induced by the modification of Mg-methoxide with acetic acid, was related to the decomposition of organics at a lower temperature. These results could be explained in terms of the decrease of the O–R bond strength depending on the increase in the alkyl group size. MgO thin films having a high degree of crystallinity were successfully obtained from the Mg-methoxide treated with acetic acid at 300°C. The low-temperature crystallization of sol–gel-derived MgO thin films showed the feasibility for their application as a protective layer in alternative current plasma display panel cells.     

Comparative study of chemical and electrochemical Fenton treatment of organic pollutants in wastewater

The technological and economic aspects of using the Fenton process to treat industrial wastewater containing morpholyne and diethylethanolamine, as well as sodium salts of naphthalene sulfonic acid and of ethylenediaminetetraacetic acid based on data obtained in pilot tests are discussed. Chemical Fenton technology was tested using commercial 30–35% solutions of H₂O₂ and iron (II) salts, which was followed by the additional electrochemical destruction of organic pollutants in an undivided reactor with catalytic stable anodes (CSA) and 1 g L⁻¹ NaCl as a supporting electrolyte and a source of active chlorine. An alternative electrochemical method involving the electrogeneration of hydrogen peroxide in polluted water at the gas -diffusion cathode was studied both with the addition of ferrous salt to the electrolyte prior to electrolysis (in-cell electro-Fenton) as well as with the post-electrolysis addition of Fe²⁺ in another reactor (ex-cell electro-Fenton). The accumulation of hydrogen peroxide in concentrations sufficient for the mineralization of organic pollutants was achieved in both cases with near 100% current efficiency. In comparison with wastewater treatment processes which use a purchased hydrogen peroxide reagent, the Fenton-like processes achieved an economic savings of as much as 64.5% in running costs due to the on-site electrochemical generation of H₂O₂. Preparative electrolysis in the membrane reactor showed higher current efficiencies and lower specific energy consumptions for H₂O₂ electrogeneration in comparison with the results of tests carried out in an undivided cell.     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.