Oxidation Resistance Evaluation of Silicon Carbide Ceramics with Various Additives

Five silicon carbide ceramics with various additives were evaluated for oxidation resistance at 1300°C in flowing dry and wet air. In the dry atmosphere, the oxidation of the five samples was diffusion-controlled, and in wet atmosphere they exhibited a linear relation beween weight gain by oxidation and water vapor content. Water vapor in the atmosphere strongly accelerated oxidation. The influence of oxidation on room-temperature strength was complex, but the samples were not as affected by oxidation.     

Synthesis of High-Purity Zirconium Fluoride for Fluoride Glass Fibers by Chemical Vapor Deposition

A technique for synthesizing ultra-high-purity ZrF₄ using chemical vapor deposition in a ZrBr₄–HF system is developed and a purification mechanism is clarified. The Fe concentration in ZrF₄ is evaluated at less than 10 ppb based on analysis of the transmission loss spectrum of a fiber prepared using synthesized ZrF₄. Purification is achieved mainly in a sublimation process of ZrBr₄, and purification efficiency is determined by sublimation temperature and activity of impurities in ZrBr₄. The concentration of transition-metal impurities in ZrF₄, synthesized by chemical vapor deposition in the ZrBr₄–HF system, is expected to be less than 1 ppb.     

Spherical-Impact Damage and Strength Degradation in Silicon Nitrides for Automobile Turbocharger Rotors

Spherical-impact damage to two silicon nitrides is investigated. Gas-pressure-sintered silicon nitride exhibits an elastic response to impact by spherical partially stabilized zirconia particles, resulting in Hertzian cone-crack initiation in the sintered body. Pressureless-sintered silicon nitride, on the other hand, demonstrated an elastic/plastic response, with median/radical-crack initiation. These differences in behavior are due to their microstructural differences as well as to the different hardness values of the silicon nitrides in relation to those of the PSZ spheres. The postimpact bend strength of silicon nitrides is also degraded when crack length exceeds the inherent flaw size.     

Sintering of the Mechanochemically Activated Powders of Hexagonal Boron Nitride

Pressureless sintering of hexagonal boron nitride (BN) was performed using a powder activated by mechano-chemical treatments. Physical properties of the sintered BN bodies depend on the type of starting powder and the conditions of the treatments. The BN body, which was obtained at 2000°C using an appropriate activated powder, was 99 wt% pure and was excellent in mechanical and physical properties, in spite of its low density (1.64 g/cm³).     

Acrylic nonaqueous dispersion using butylated melamine-formaldehyde resin as dispersant

A series of acrylic nonaqueous dispersions were prepared by using various kinds of butylated melamine–formaldehyde (BMF) resins as dispersant. The functional group composition of BMF to form stable dispersion was butoxy group more than 13 mol/BMF 1 mol, and methylol group ranged from 1 to 2.5 mol/BMF 1 mol. It is concluded that the anchoring of BMF to acrylic copolymer was due to the formation of covalent bond between methylol group in BMF and hydroxy group in acrylic copolymer.     

Production of eicosapentaenoic acid by a recombinant marine cyanobacterium, Synechococcus sp.

The eicosapentaenoic acid (EPA) synthesis gene cluster from an EPA-producing bacterium, Shewanella sp. SCRC-2738, was cloned into a broad-host range vector, pJRD215, and then introduced into a marine cyanobacterium, Synechococcus sp. NKBG15041c, by conjugation. The transconjugant cyanobacteria produced 3.7±0.2% (2.24±0.13 mg/L) EPA (n-3) and 2.5 ±0.2% (1.49±0.06 mg/L) eicosatetraenoic acid (n-3) of the total fatty acids when the cells were cultured at 23°C at a light intensity of 1,000–1,500 Lux. The EPA and eico-satetraenoic acid contents of the cells were increased to 4.6±0.6% (3.86±1.11 mg/L) and 4.7±0.3% (3.86±0.82 mg/L), and 7.5±0.3% (1.76±0.10 mg/L) and 5.1±0.2% (1.19±0.06 mg/L) when they were cultured at low temperature (18°C) and at lower light intensity (40 Lux), respectively.     

Dynamic in situ observation of automotive catalysts for emission control using X-ray absorption fine structure

Two main pivotal subjects of research in automotive catalysts were studied by modern X-ray absorption analysis techniques. One is oxygen storage/release behaviour, and the other is sintering inhibition of Pt particles. First, three types of CeO₂–ZrO₂ (Ce:Zr = 1:1 molar ratio) compounds with different oxygen storage/release capacities and different structural properties were prepared, and the valence change of Ce as a function of temperature during oxygen release/storage processes was investigated. The reduction of surface Ce mainly occurred in the range 100–170 °C, and the reduction of bulk Ce progressed at high temperatures of 170 °C and above. The Ce reduction behaviour depended not only on the homogeneity of the Ce and Zr for bulk reduction at high temperatures but also on the particle size of the CeO₂–ZrO₂ samples for surface reduction at low temperatures. Secondly, sintering inhibition of Pt in Pt/Al₂O₃, Pt/MgO and Pt/ceria-based catalysts after 800 °C ageing in air was studied. We found that the Pt–O–M (M = Mg, Ce) bond acted as an anchor and inhibited the sintering of Pt particles on MgO or ceria-based oxide. Especially, it was noteworthy that the Pt–O–Ce⁴⁺ bond on the ceria-based support breaks easily through the reduction of Ce (Ce⁴⁺ → Ce³⁺) during the usual stoichiometric and reducing conditions.     

Synthesis and Properties of Gemini-type Cationic Surfactants Containing Carbonate Linkages in the Linker Moiety Directed Toward Green and Sustainable Chemistry

Gemini-type cationic surfactants containing carbonate linkages as biodegradable and chemically recyclable segments, consisting of two long-chain alkyl groups, two quaternary ammonium groups and a linker moiety, were designed and synthesized as novel green and sustainable cationics with improved physicochemical and biological activities. The gemini-type cationics containing a carbonate linkage showed lower critical micelle concentration values compared to the corresponding single-type cationics. Also, the gemini-type cationics containing a carbonate linkage in the linker moiety showed strong antimicrobial activities. The biodegradability of the gemini-type cationics was significantly improved when a carbonate linkage was introduced into the linker moiety. The maximum biochemical oxygen demand-biodegradability of the gemini-type cationics containing a carbonate linkage in the linker moiety exceeded 70% after a 28-day incubation. Furthermore, the gemini-type cationics containing both a carbonate linkage and an n-dodecyl group showed a chemical recyclability using a lipase (E.C. 3.1.1.3).

Novel polyion complex with interpenetrating polymer network of poly(acrylic acid) and partially protected poly(vinylamine) using N-vinylacetamide and N-vinylformamide

Poly(vinylamine), the simplest polycation with primary amines, was applied to interpenetrating polymer networks (IPN) with poly(acrylic acid). N-Vinylformamide (NVF) was employed for amino-protected monomers to control electrostatic balance. pH-responsivities of IPNs varied, depending on the hydrolysis conditions and acrylic acid (AAc) concentration of the second network. Poly(N-vinylacetamide)-co-poly(N-vinylformamide) (4/6, mol/mol) was employed for the first network, subsequently hydrolyzed with 50% amide groups, and the second network was polymerized with 0.25 mol L⁻¹ AAc, extremely shrunken hydrogels with polyion complex were formed at pH 7, showing that the controlled amount of highly active primary amines are available in IPN.     

Kinetic Study of the Prooxidant Effect of α-Tocopherol. Hydrogen Abstraction from Lipids by α-Tocopheroxyl Radical

A kinetic study of the prooxidant effect of α-tocopherol was performed. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) by α-tocopheroxyl radical in toluene were determined, using a double-mixing stopped-flow spectrophotometer. The second-order rate constants (k _p) obtained are <1 × 10⁻² M⁻¹ s⁻¹ for 1, 1.90 × 10⁻² M⁻¹ s⁻¹ for 2, 8.33 × 10⁻² M⁻¹ s⁻¹ for 3, 1.92 × 10⁻¹ M⁻¹ s⁻¹ for 4, and 2.43 × 10⁻¹ M⁻¹ s⁻¹ for 5 at 25.0 °C. Fatty acid esters 3, 4, and 5 contain two, four, and six –CH₂– hydrogen atoms activated by two π-electron systems (–C=C–CH₂–C=C–). On the other hand, fatty acid ester 2 has four –CH₂– hydrogen atoms activated by a single π-electron system (–CH₂–C=C–CH₂–). Thus, the rate constants, k _abstr/H, given on an available hydrogen basis are k _p/4 = 4.75 × 10⁻³ M⁻¹ s⁻¹ for 2, k _p/2 = 4.16 × 10⁻² M⁻¹ s⁻¹ for 3, k _p/4 = 4.79 × 10⁻² M⁻¹ s⁻¹ for 4, and k _p/6 = 4.05 × 10⁻² M⁻¹ s⁻¹ for 5. The k _abstr/H values obtained for 3, 4, and 5 are similar to each other, and are by about one order of magnitude higher than that for 2. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils, fats, and low-density lipoproteins may be induced by the above hydrogen abstraction reaction.