An electrochemical ionic liquid membrane reactor for NO x selective separation under excess oxygen conditions

A novel electrochemical ionic liquid membrane reactor capable of separating NO from a mixture of NO and oxygen with high current efficiency at low temperatures was designed and tested. This reactor consists of a combination of an ionic liquid and a thin film of anodised alumina with two platinum electrodes. During operation of the reactor, NO is electrically transported from the cathode side to the anode side.     

Active sites deterioration of MgCl2‐supported catalyst induced by the electron donor extraction by alkylaluminium

To investigate the role of the internal donor in a Ziegler–Natta catalyst, the nature and existing states of the internal donor were intentionally varied by alkylaluminium treatment before polymerization, and the catalytic properties during propene polymerization were accurately evaluated using the stopped‐flow method. A significant decrease in the amount of the remaining internal donor was observed during the initial stage of the extraction. The polymerization results show a gradual decrease in the polymer isotacticity with an increase in the extraction time. These different patterns, as a function of the extraction time, indicate that the amount of the remaining internal donor is not directly related to the isotacticity of the produced polymer. © 2002 Society of Chemical Industry     

Examination of the role of oxygen in the photografting of methacrylic acid on a polyethylene film with a mixed solvent consisting of water and organic solvents

The photografting of methacrylic acid (MAA) on a linear low‐density polyethylene film (thickness = 30 μm) under air and nitrogen atmospheres was investigated at 60°C in mixed solvents consisting of water and an organic solvent, with xanthone as a photoinitiator. The organic solvents used were acetone, methanol, tetrahydrofuran, and dioxane. A maximum percentage of grafting occurred at a certain concentration of the organic solvent in the mixed solvent. This was observed for the systems under both air and nitrogen. The grafting reaction under air exhibited an induction period, but the rate of grafting after the period was greater than that under nitrogen. The formation of poly(ethylene peroxide)s by photoirradiation seemed to be a factor for the accelerated photografting under air. On the basis of attenuated total reflection infrared spectroscopy and scanning electron microscopy of the grafted film, the MAA‐grafted chains of the sample prepared under air tended to penetrate more deeply inside the film than those of the sample prepared under nitrogen. The resulting grafted films exhibited a pH‐responsive character: the grafted films shrank in an acidic medium but swelled in alkaline medium. This was evaluated from measurements of dimensional changes in the grafted films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 992–998, 2003     

Piezoelectric properties of langasite group based on the ionic size of cation

As langasite A₃BC₃D₂O₁₄ compounds group with piezoelectric properties has no phase transition up to the melting point of 1400–1500 °C, they have been applied for the combustion pressure sensor. As they also have a larger electromechanical coupling factor compared to quartz and nearly the same temperature stability as quartz, the surface acoustic wave (SAW) filters are expected based on the digital transformation of wider bandwidth and higher-bit rates. In the case of three-element compounds such as [R₃]_A[Ga]_B[Ga₃]_C[GaSi]_DO₁₄ (R=La, Pr and Nd), the piezoelectric constant increases with the ionic radius R. In the case of four-element compounds such as [A₃]_A[B]_B[Ga₃]_C[Si₂]_DO₁₄ (A=Ca or Sr, B=Ta or Nb), |d₁₁| and k₁₂ values as a function of A_L/B_L ratio showed a linear relationship completely. There are two effects for the substitutions of A- and B-site cations: the substitution of Sr for Ca brings expansion toward [100] and enlargement in |d₁₁| and k₁₂. On the other hand, as the substitution of Ta for Nb brings not much change, the properties are similar. In this study, five-element compounds such as La_3?xSr_xTa_yGa_5?x+ySi_1+x?2yO₁₄ (0≤x≤3, 0≤y≤1) solid solutions analysed by a single crystal X-ray diffraction are compared with the three- and four-element compounds on the coordinates of oxygen ions. As the coordinates positions are located on the extended line of coordinate positions on the three-element compounds as increasing ionic radius of R-ions in A-site, the piezoelectric properties |d₁₁| and k₁₂ are expected become large.     

Annealing effect on temperature coefficient of resistivity in La1−xSrxMnO3 ceramics

We investigated annealing effects of La_1?xSr_xMnO₃ (x = 0–0.6) on electrical resistivity and the temperature coefficient of resistivity (TCR). The annealed samples’ resistivity was lower than those of non-annealed samples. For example, annealing changed the resistivity of x = 0.3 at 25 °C from 4.50 × 10^?5 to 3.71 × 10^?5 Ω m. Remarkable difference in TCR was observed after annealing, for x = 0.3, 0.45, and 0.5. For x = 0.3, the TCR after annealing was 4000 ppm/°C, which was 1250 ppm/°C greater than that before annealing. We investigated (1) crystal phase, (2) Mn average valence, (3) Mott insulator–metal transition temperature, and (4) microstructure. The microstructure was remarkably varied for annealed x = 0.3 and 0.5. The average grain size of the x = 0.3 increased from 1.60 up to 2.38 μm. Results show that annealing affects resistivity and TCR because of grain growth during annealing.     

Kinetic study on free radical polymerization of alkyl acylamidoacrylates by pulsed laser polymerization using nitrogen laser

Radical polymerization of captodatively substituted alkyl acylamidoacrylates was studied by pulsed laser polymerization using a N₂ laser. Propagation rate coefficient of the acrylates was varied with solvents used in spite of a radical mechanism, but little varied with methyl, n-propyl, and isopropyl substituents on the acrylates. Arrhenius parameters for the propagation indicated that a solvent affected mostly on a frequency factor rather than a activation energy. In addition, it was suggested that these captodatively substituted propagating radicals were thermodynamically persistent but kinetically active in propagation, which resulted in rather smooth propagation in spite of bulky 1,1-disubstituted olefins. The mechanism of the polymerizations was discussed in detail on the basis of the kinetic studies and ESR spectroscopy.     

Preparation of Ultrafine Fe–Pt Alloy and Au Nanoparticle Colloids by KrF Excimer Laser Solution Photolysis

We prepared ultrafine Fe–Pt alloy nanoparticle colloids by UV laser solution photolysis (KrF excimer laser of 248 nm wavelength) using precursors of methanol solutions into which iron and platinum complexes were dissolved together with PVP dispersant to prevent aggregations. From TEM observations, the Fe–Pt nanoparticles were found to be composed of disordered FCC A1 phase with average diameters of 0.5–3 nm regardless of the preparation conditions. Higher iron compositions of nanoparticles require irradiations of higher laser pulse energies typically more than 350 mJ, which is considered to be due to the difficulty in dissociation of Fe(III) acetylacetonate compared with Pt(II) acetylacetonate. Au colloid preparation by the same method was also attempted, resulting in Au nanoparticle colloids with over 10 times larger diameters than the Fe–Pt nanoparticles and UV–visible absorption peaks around 530 nm that originate from the surface plasmon resonance. Differences between the Fe–Pt and Au nanoparticles prepared by the KrF excimer laser solution photolysis are also discussed.     

Enzyme-Assisted Synthesis of Titania under Ambient Conditions

A low-temperature procedure for the synthesis of TiO₂ was developed using a water-soluble titanium complex and enzymes. Titanium–lactate and titanium–glycolate complexes were used as precursors of TiO₂. Digestive enzymes were chosen as biocatalysts for the synthesis of TiO₂ in aqueous solutions. TiO₂ powders were deposited from reaction solutions having optimal pH values for the enzymes to exhibit their catalytic activities for their original substrates. TiO₂ has been synthesized by an enzymatic reaction in an aqueous solution under ambient conditions. The XRD measurements indicated that TiO₂ powders thus obtained usually have an amorphous phase. However, after calcination at 550°C, the anatase phase was confirmed. Interestingly, the minor phase of TiO₂, brookite, was found in the sample obtained from the titanium–glycolate complex catalyzed by lipase at pH 10 after calcination at 550°C.     

Superplastic behaviour of Ti-48at.%Al two-phase titanium aluminide compacts made from mechanically alloyed powder

An HIP compact of MA-processed powder having a nominal composition of Ti-48at.% Al was produced. The compact consisted of a large amount of TiAl(λ) and a small amount of Ti₃Al (₂), in a completely ultra-fine equiaxed grain structure. This two-phase compact showed typical superplastic deformation behaviour. A maximum elongation of 550% was obtained. A strain exponent, n = 2, and grain size exponent, p = 2, were determined from the results of a strain-rate-change test and a creep test at constant initial stress using samples having various grain sizes, respectively. The activation energy for creep, Q_c at constant stress was calculated to be 350 kJ/mole. It is concluded that the superplastic deformation mechanism of the material under study is grain boundary sliding controlled by lattice diffusion in the TiAl phase.     

Ingestion of gelatinized potato starch containing a high level of phosphorus decreases serum and liver lipids in rats

Potato starch is known to have a higher concentration of phosphate than other starches. The presence of phosphate groups in amylopectin results in resistance to digestion by amylase. Therefore, there is a possibility that potato starch is slowly digested, inducing a physiological effect similar to that of resistant starch and indigestible oligosaccharides. The amount of phosphate group in starch differs with potato cultivar. In the present study, we investigated the effects of gelatinized potato starch containing a high level of phosphorus on lipid metabolism in rats. For this purpose, we determined lipid levels in the serum and liver in rats fed two kinds of gelatinized potato starches with different phosphorus contents. Four groups of male Sprague-Dawley rats were fed a 60% sucrose diet (control) or one of three diets containing cornstarch (CS), Benimaru (BM) potato starch or Hokkaikogane (HK) potato starch. Fat pad weight was slightly decreased in the HK diet group compared with that in the other groups. Free fatty acids in serum were significantly lowered by dietary HK starch compared with control, and serum triglyceride in rats fed the HK diet was also decreased. In the BM and HK diet groups, triglyceride levels in the liver were decreased compared with that in the control and CS groups. As for hepatic total cholesterol level, there were no significant differences among three starch diet groups. Fecal bile acid excretion was greater in the two potato starch groups than in the control group. On the other hand, there were no significant differences in cecal short-chain fatty acid content or pH. Thus, we conclude that dietary gelatinized potato starch reduces free fatty acid and triglyceride in serum and hepatic triglyceride, but does not affect cecal fermentation.