Anatase Sol Prepared from Peroxotitanium Complex Aqueous Solution Containing Niobium or Vanadium

Niobium- or vanadium-doped anatase sols were prepared by hydrothermal treatment of 0.1 mol/dm³ peroxotitanium complex aqueous solutions dissolving 0–10 mol% niobium or vanadium at 100°C for 8 h. Niobium-doping caused the increase of lattice constants of anatase and the shape change of anatase crystal from spindle-like to cubic-like structure, but no change of the optical absorbance. Vanadium-doping caused the decrease of lattice constant of c -axis, the miniaturization of anatase crystal and the increase of optical absorbance at the wavelength from 350–700 nm.     

Proton conducting acid-base mixed materials under water-free condition

In recent years, a lot of attentions have been paid for a development of water-free polymer electrolyte membranes fuel cells (PEMFC) at intermediate temperatures (above 100 °C) because of many technological advantages of higher temperature operation. However, the proton conductivity of conventional polymer membranes under water-free condition is usually very low and the polymeric membranes are not stable at higher temperatures. So, the development of non-hydrous proton conducting membrane under water-free condition has been a state of the art issue in the advanced PEMFC technology. In this study, non-hydrous protonic conducting material was prepared by the mixing of acidic surfactant of mono-dodecylphosphate (MDP) and organic base of benzimidazole (BnIm). The proton conductivity and thermal stability of MDP-BnIm mixed material increased with the mixing ratio of BnIm. Maximum proton conductivity of MDP-BnIm mixed material (BnIm mixing ratio of 200 wt.%. vs. MDP) was found to be 1×10⁻³ S cm⁻¹ at 150 °C under water-free condition.     

Ru-catalyzed anode materials for direct hydrocarbon SOFCs

A solid oxide fuel cell using a thin ceria-based electrolyte film with a Ru-catalyzed anode was directly operated on hydrocarbons, including methane, ethane, and propane, at 600 °C. The role of the Ru catalyst in the anode reaction was to promote the reforming reaction of the unreacted hydrocarbons by the produced steam and CO₂, which avoided interference from steam and CO₂ in the gas-phase diffusion of the fuels. The resulting peak power density reached 750 mW cm⁻² with dry methane, which was comparable to the peak power density of 769 mW cm⁻² with wet (2.9 vol.% H₂O) hydrogen. More important was the fact that the cell performance was maintained at a high level regardless of the change in the methane utilization from 12 to 46% but was significantly reduced by increasing the hydrogen utilization from 13 to 42%. While the anodic reaction of hydrogen was controlled by the slow gas diffusion, the anodic reaction of methane was not subject to the onset of such a gas-diffusion process.     

The effect of ionic cross-links on the deformation behavior of homoblends made of poly(styrene-co-styrenesulfonic acid) and poly(styrene-co-4-vinylpyridine)

Deformation behavior of stoichiometric blends made from poly(styrene-co-styrenesulfonic acid) (SPS) and poly(styrene-co-4-vinylpyridine) (SVP) was investigated by TEM observation of strained thin films. An FTIR investigation revealed that ionic cross-links were formed between the component polymers upon blending due to intermolecular ion-ion interactions, which arose from proton transfer from sulfonic acid groups to pyridine groups. TEM observations indicate that the deformation mode of the blends changed from crazing only to crazing plus shear deformation, with the shear contribution becoming larger, as the ion content in the blends increased. Such changes in deformation mode can be understood as arising from an increase in the ‘effective’ strand density due to the formation of ionic cross-links upon blending. It was also found that the ionic cross-links via pyridinium cation/sulfonate anion ion pairs were more effective in inducing the transition of deformation mode than ionic cross-links via -SO₃⁻/Na⁺ or -SO₃⁻/Ca²⁺ ion pairs.     

Phase separation behavior and morphology development of phenolic resin/PMMA/hexamethylenetetrarnine blends

Summary In order to obtain materials with nanopores which will be applicable for many fields, the structures of the cured blends of phenolic resin (PhN), poly(methyl methacrylate) (PMMA) and curing agent were studied. After PMMA was extracted from cured blends, the structures of cured phenolic resins were observed with SEM. As a results, it was found that nanosized continuous pore structures were formed in extremely wide composition region if curing temperature was high.     

Grafted stock synthesis of ABS at the ultimate high ratio of polybutadiene to poly(styrene‐co‐acrylonitrile)

This study describes the emulsion grafting of styrene and acrylonitrile onto 60–70% polybutadiene (PB), in the presence or absence of tert‐dodecanetiol as a chain transfer reagent with a radical initiator, and the properties of the obtained grafted stock. There was no significant difference in terms of effect of the initiation mode on the grafting efficiency resulting from the high grafting reactivity of PB. However, the grafted stock with 70% PB prepared in the presence of tert‐dodecanetiol and the adequate selection of an initiation system gave a homogeneous dispersion of the PB particles into poly(styrene‐co‐acrylonitrile) (SAN) matrix. The initiation system involves tert‐butyl peroxylaurate, tert‐butyl peroxyacetate, and tert‐butyl peroxyisopropylcarbonate coupled with ferrous sulfate. The efficient coverage of the SAN grafted layer around 70% PB particles was observed by TEM to eventually give excellent impact resistance, high surface gloss, and good thermal resistance. The absence of tert‐dodecanetiol resulted in a toughness reduction of ABS. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3462–3470, 2001     

Power characteristics of unsteadily forward–reverse rotating impellers in an unbaffled aerated agitated vessel

Power characteristics of an unbaffled aerated agitated vessel with unsteadily forward‐reverse rotating impellers, ie a new type of gas–liquid agitator named ‘AJITER’, treating viscous Newtonian liquids were studied experimentally. Measurements were first made on the agitation torque, ie the torque on the drive shaft on which forward–reverse rotating impellers with four delta‐type blades were attached, and the data obtained were analyzed by fitting them to an equation consisting of two terms with respect to the resistance of the fluid, one due to viscous drag and the other due to added moment of inertia. The effects of operating conditions and physical properties of liquids on the drag and added moment of inertia coefficients were then evaluated, and empirical relationships which estimate values of these coefficients, useful to predict the unsteady behavior and magnitude of agitation torque, were presented. Furthermore, equations were developed for estimating the average and maximum power consumptions as a function of the drag and added moment of inertia coefficients. Prediction of respective power levels in AJITER by these equations was also discussed. © 2001 Society of Chemical Industry     

Effect of Ga2O3 on Sintering and Phase Stability of Sc2O3‐Doped Tetragonal Zirconia Prepared via Aqueous Solution Route

The effects of the presence of Ga₂O₃ on low‐temperature sintering and the phase stability of 4, 5, and 6 mol% Sc₂O₃‐doped tetragonal zirconia ceramics (4ScSZ, 5ScSZ, and 6ScSZ, respectively) were investigated. A series of zirconia sintered bodies with compositions (ZrO₂)_0.99?x(Sc₂O₃)_x(Ga₂O₃)_0.01, x = 0.04, 0.05, and 0.06 was fabricated by sintering at 1000°C to 1500°C for 1 h using fine powders that were prepared via the combination of homogeneous precipitation method and hydrolysis technique using monoclinic zirconia sols synthesized through the forced hydrolysis of an aqueous solution of zirconium oxychloride at 100°C for 168 h. The presence of 1 mol% Ga₂O₃ was effective in reducing sintering temperature necessary to fabricate dense bodies and enabled to obtain dense sintered bodies via sintering at 1100°C for 1 h. The phase stability, that is, low‐temperature degradation behavior of the resultant zirconia ceramics was determined under hydrothermal condition. The zirconia ceramics codoped with 1 mol% Ga₂O₃ and 6 mol% Sc₂O₃ (1Ga6ScZ) fabricated via sintering at 1300°C for 1 h showed high phase stability without the appearance of monoclinic zirconia phase, that is the tetragonal‐to‐monoclinic phase transformation was not observed in the 1Ga6ScZ after treatment under hydrothermal condition at 150°C for 30 h.     

Matrix influence on the piezoelectric properties of piezoelectric ceramic/polymer composite exhibiting particle alignment

This study was addressed to the influence of an electric field strength applied at fabrication process and matrix properties, such as the dielectric constant and the Young's modulus, on “pseudo‐1‐3 piezoelectric ceramic/polymer composite” in order to further enhance the piezoelectricity of that. The pseudo‐1‐3 piezoelectric ceramic/polymer composite consists of linearly ordered piezoelectric ceramic particles in polymer material. Silicone gel, silicone rubber, urethane rubber, and poly‐methyl‐methacrylate, which exhibit different dielectric constants and Young's modulus, were used as matrices to evaluate the matrix influence. The piezoelectricity of the pseudo‐1‐3 piezoelectric ceramic/polymer composite was evaluated using the piezoelectric strain constant d₃₃. The d₃₃ is one of the indices of the piezoelectric properties for piezoelectric materials. As a result, it was confirmed that d₃₃ of the pseudo‐1‐3 piezoelectric ceramic/polymer composite increased with the increase of the electric filed strength applied at fabrication process, though, it reached a constant value at a certain strength value. Further it was confirmed that dielectric constant of the matrix had a small influence on d₃₃ of the pseudo‐1‐3 piezoelectric ceramic/polymer composite, however, in case of matrix of lower Young's modulus, d₃₃ was increase. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41817.     

Enzymatic syntheses of N-lauroyl-β-alanine homologs in organic media

Enyzmatic amidation of the primary amines β-alanine ethyl ester and 3-aminopropionitrile with methyl laurate by means of immobilized lipase (Candida antarctica lipase, CAL) resulted in the formation in good yield of N-lauroyl-β-alanine ethyl ester and 3-(N-lauroylamino)-propionitrile, respectively. When 3-amino-propionitrile was used as substrate, diisopropyl ether was a suitable solvent. Changing the reaction temperature (12–80°C) did not affect the yields, and room temperature was a suitable temperature for this reaction. In the investigation of reaction conditions, the use of equimolar amounts (5 mmol) of substrate and ester, along with 0.5 g of CAL, in diisopropyl ether gave the best yield (99.3%) after 24 h of incubation at 24°C. The enzyme activity in the amidation reaction did not decrease even after six uses. With β-alanine ethyl ester hydrochloride as substrate, diisopropyl ether was unsuited as a solvent owing to the low solubility of the substrate in this solvent. In this reaction, the best yield (82.0%) was attained by using dioxane as solvent. CAL achieved higher extents of amide synthesis with long-chain than with short-chain ester substrates. The enzyme accepted only nonbulky primary amines as substrates.