Functional monomers and polymers, 64. Synthesis of poly-β-alanine from β-alanine, β-alanyl-β-alanine,and β-alanyl-β-alanyl-β-alanine 4-dodecanoyl-2-nitrophenyl esters

Active 4-dodecanoyl-2-nitrophenyl esters of β-alanine, β-alanyl-β-alanine, and β-alanyl-β-alanyl-β-alanine were prepared, and tried to polymerize in various solvents. Nonpolar solvents were found to be convenient for the polycondensation reaction. The yield of the polycondensation was high for the monopeptide ester, and less for the dipeptide and tripeptide esters. The effect of temperature on the polycondensation reaction was also studied.     

Sintering of Ceria-Doped Tetragonal Zirconia Crystallized in Organic Solvents, Water, and Air

Amorphous CeO₂–ZrO₂ gels were prepared by coprecipitation in ammonia solutions. The onset of crystallization of the gels, from calcining in air, was 420°C, while 200° to 250°C in the presence of water and organic solvents such as methanol and ethanol. The sintering behaviors of CeO₂–ZrO₂ powders were sensitive to the crystallizing conditions, since hard agglomerates formed when the precipitated gels were crystallized by normal calcination in air, whereas soft agglomerates formed when they were crystallized in water or organic solvents. CeO₂–ZrO₂ powders crystallized in methanol and water at 250°C were sintered to full theoretical density at 1150° and 1400°C, respectively, whereas that crystallized by calcination in air at 450°C was sintered to only 95.2% of theoretical density, even at 1500°C.     

Preparation of poly(p-phenylene terephthalamide)/poly(vinyl chloride) molecular composite and its thermal and mechanical properties

Poly(p-phenylene terephthalamide) (PPTA) was blended with poly(vinyl chloride) (PVC) by solution-blending method. PPTA was metalated for dissolving in dimethyl sulfoxide. Dimethyl sulfoxide was used as a common solvent. In PPTA/PVC composite, PPTA accelerated the thermal degradation of PVC. PPTA molecules are aggregated as microfibrillar form in PVC matrix. Such microfibrils are dispersed homogeneously in PVC matrix, according to polarizing microscopic observation. The average diameter of the microfibrils becomes smaller in the composite with lower content of PPTA. In the surface region of PPTA microfibrils the intermolecular hydrogen bonds between C? Cl of PVC and N? H of PPTA are formed. Young's modulus and the yield stress at room temperature were higher in the composites than those in PVC. The modulus of the composites was higher, especially at the high temperatures above their glass transition temperatures, than that in PVC. The temperature dependence of modulus can be calculated by using the mechanical model equivalent to the quasi-3-dimensional microfibrillar model which will be approximately applied to the composite structure. It becomes apparent that the modulus of the PPTA microfibrils evaluated by using the mechanical model is higher in the higher molecular weight PPTA.     

Preparation of silk fibroin and polyallylamine composites

Composite films made of silk fibroin (SF) and polyallylamine (PAA) are prepared that contain various compositional ratios. These materials are analyzed to elucidate the resulting physical properties and to assess their potential toward advanced applications as industrial materials. The composite films are obtained from a SF and PAA binary system by dry casting from aqueous solution. These composite films exhibit excellent processability such as film forming capabilities, and the elongation at break is increased in the wet state. The differential scanning calorimetry (DSC) curves of the composites suggest that a mutual interaction takes place between the SF and PAA. This interaction is believed to occur because the endothermic peak, corresponding to the individual polymer, shifts with increasing SF content. The random coil conformation of the SF is present, regardless of the PAA blending, as confirmed by FTIR and DSC measurements. Additionally, living cells from Antheraea pernyi and Bombyx mori insect tissues are shown to grow effectively on the composite films. Maximum growth levels occur when the cultivation flask is coated with the material in SF/PAA ratios of 75:25 to 25:75. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1963–1970, 2002; DOI 10.1002/app.10491     

Carbon molecular sieve membranes derived from trimethylsilyl substituted poly(phenylene oxide) for gas separation

Carbon molecular sieve membranes for gas separation prepared using poly(phenylene oxide) (PPO) as precursor have been examined. The PPO precursor was modified by introducing a trimethylsilyl (TMS) substituent and its effect on the gas transport property of the resulting carbon membrane was examined. TMS-substituted PPO (TMSPPO) was prepared in a high yield by a simple one-step reaction, and its carbon membrane was successfully fabricated. The modification improved the gas permeability of the resulting membrane which also exhibited excellent O₂/N₂ and CO₂/CH₄ separation performance comparable to those of polyimide-derived carbon membranes. From the analysis of the microstructure of the TMSPPO carbon membranes, it is believed that the TMS groups improve gas diffusivity by increasing the micropore volume.     

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.     

Engineering Analysis and Design with ALE-VMS and Space–Time Methods

Flow problems with moving boundaries and interfaces include fluid–structure interaction (FSI) and a number of other classes of problems, have an important place in engineering analysis and design, and offer some formidable computational challenges. Bringing solution and analysis to them motivated the Deforming-Spatial-Domain/Stabilized Space–Time (DSD/SST) method and also the variational multiscale version of the Arbitrary Lagrangian–Eulerian method (ALE-VMS). Since their inception, these two methods and their improved versions have been applied to a diverse set of challenging problems with a common core computational technology need. The classes of problems solved include free-surface and two-fluid flows, fluid–object and fluid–particle interaction, FSI, and flows with solid surfaces in fast, linear or rotational relative motion. Some of the most challenging FSI problems, including parachute FSI, wind-turbine FSI and arterial FSI, are being solved and analyzed with the DSD/SST and ALE-VMS methods as core technologies. Better accuracy and improved turbulence modeling were brought with the recently-introduced VMS version of the DSD/SST method, which is called DSD/SST-VMST (also ST-VMS). In specific classes of problems, such as parachute FSI, arterial FSI, ship hydrodynamics, fluid–object interaction, aerodynamics of flapping wings, and wind-turbine aerodynamics and FSI, the scope and accuracy of the FSI modeling were increased with the special ALE-VMS and ST FSI techniques targeting each of those classes of problems. This article provides an overview of the core ALE-VMS and ST FSI techniques, their recent versions, and the special ALE-VMS and ST FSI techniques. It also provides examples of challenging problems solved and analyzed in parachute FSI, arterial FSI, ship hydrodynamics, aerodynamics of flapping wings, wind-turbine aerodynamics, and bridge-deck aerodynamics and vortex-induced vibrations.     

Preparation of Porous Ceramics with Calcium Metaphosphate Fiber Skeleton for Biomedical Use

High-strength calcium metaphosphate fibers for biomedical applications are extracted from crystallized products of calcium ultraphosphate glasses by aqueous leaching. In the present work, new types of porous ceramics with a skeleton composed of the crystalline fibers are prepared by heating the fibrous products extracted. The fibers in the ceramic are interlinked to each other by glassy phases formed during the heating. This porous material has a large porosity of >60%. The surface of the skeleton can be successfully converted into new calcium phosphate phases such as apatite by heating the porous material treated with a molten salt mixture of CaCl₂-Ca(NO₃)₂.     

Stability of fine water droplet clouds

The rate of evaporation of monodisperse water droplets was first evaluated by solving numerically the modified Maxwell equation, assuming the cellular model for a droplet clouds. The results are discussed in comparison with those for a single isolated droplet, which can be obtained analytically. The critical conditions for the droplet cloud to be stable are then evaluated as a function of droplet number concentration, droplet size and initial conditions of the surrounding air. Secondly, the equilibrated system, where a water droplet cloud is steadily mixed with unsaturated air, was analysed on the basis of enthalpy and material balance of the system to evaluate the total volume change of the droplets. Some of these analyses were verified by experiment, using an ultramicroscopic technique which is useful for droplet size analysis.     

Phase behavior of N‐isopropylacrylamide/acrylic acid copolymer hydrogels prepared with ultrasound

N‐Isopropylacrylamide/acrylic acid copolymer hydrogels were synthesized with ultrasound. The thermoresponsive phase behaviors of gels synthesized with ultrasound (US gels) were investigated and compared with those of gels synthesized in the absence of ultrasound (FR gels). The US gels showed thermoresponsive swelling behavior with a large hysteresis over a wide range of temperatures around its phase‐transition temperature. The hysteresis became larger with an increasing copolymerized acrylic acid content. The US gels were also characterized from the viewpoint of chemical, hydration, and macroscopic physical structures. Little difference was observed in the chemical and hydration structures of the FR gels and US gels. The macroscopic physical structure of the US gels was, however, distinct from that of the FR gels. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2449–2452, 2003