Preparation of Matrix-Type Nickel Oxide/Samarium-Doped Ceria Composite Particles by Spray Pyrolysis

Matrix-type nickel oxide (NiO)/samarium-doped ceria (SDC) composite particles, in which NiO and SDC nano-particles were homogeneously dispersed, were synthesized by spray pyrolysis (SP) for an anode precursor of intermediate-temperature solid oxide fuel cells (IT-SOFCs). SP of an aqueous solution containing Ni, Ce, and Sm salts resulted in capsule-type composite particles that had NiO enveloped with SDC. The capsule-type composite particles actually prevent Ni aggregation between particles, but they cannot have a large contact area between nickel (Ni) and SDC. A matrix-type composite particle is expected to have a large contact area because the matrix-type composite is comprised of nanometer-sized Ni and SDC particles. An adequate addition of ethylene glycol successfully resulted in matrix-type NiO/SDC composite particles. The matrix-type composite particles also showed higher anode performance than the capsule-type composite particles in these experiments and they were effective as precursors of high-performance IT-SOFC anodes.     

Relationship between local structure and stability in hen egg white lysozyme mutant with alanine substituted for glycine

We prepared five mutant lysozymes in which glycines whose dihedralangles are located in the region of the left-handed helix, Gly49,Gly67, Gly71, Gly102 and Gly117, were mutated to an alanineresidue. From analyses of their thermal stabilities using differentialscanning calorimetry, most of them were more destabilized thanthe native lysozyme, except for the G102A mutant, which hasa stability similar to that of the native lysozyme at pH 2.7.As for the destabilized mutant lysozymes, their X-ray crystallographicanalyses showed that their global structures did not changebut that the local structures changed slightly. By examiningthe dihedral angles at the mutation sites based on X-ray crystallographicresults, it was found that the dihedral angles at these mutationsites tended to adopt favorable values in a Ramachandran plotand that the extent and direction of their shifts from the originalvalue had similar tendencies. Therefore, the change in dihedralangles may be the cause of the slight local structural changesaround the mutation site. On the other hand, regarding the mutationof G102A, the global structure was almost identical with thatof the native structure but the local structure was drasticallychanged. Therefore, it was suggested that the drastic localconformational change might be effective in releasing the unfavorableinteraction of the native state at the mutation site.     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. III. Adhesive Joint Strengths of Grafted Power Feed Copolymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. Power feed copolymer had a very broad glass transition temperature compared with random copolymer, even if grafting and/or crosslinking were introduced to the system. This tendency was almost the same as the non-grafted power feed copolymer where only low molecular weight surfactant was used.

Adhesive joint strengths of power feed copolymers were evaluated compared with random copolymers. In the case of usual linear power feed copolymer, the adhesive joint strengths were not higher than those of random copolymer, which was considered to be due to the lower film strengths of the power feed copolymer. Power feed copolymer having grafting showed slightly higher adhesive joint strengths over a wide range of temperatures than random copolymer. When crosslinking was introduced to the system, power feed copolymer showed much higher adhesive joint strengths over a wide temperature range.     

Anisotropic in vitro vessel model using poly(vinyl alcohol) hydro gel and mesh material

In the present study, the authors fabricated straight multilayer hybrid tubular in vitro vessel models (inner diameter D_in = 10 mm; thickness T = 4 mm) composed of poly(vinyl alcohol) hydrogel (PVA‐H) and anisotropic mesh materials. The authors performed tensile, stress‐relaxation and cyclic‐tensile tests using axial and circumferential test pieces as well as pressure‐diameter (P‐D) tests using tubular test piece. In the tensile and stress‐relaxation tests, the anisotropic and nonlinear mechanical properties and hysteresis characteristic of the in vitro models were confirmed. The in vitro models also showed behavior qualitatively similar to that of native arteries in cycle‐tensile and P‐D tests. These results demonstrate that the mechanical properties of native vessels can be duplicated in an in vitro model by controlling the components of the mesh material, the orientation of elastic fibers in the mesh material, and the concentration and thickness of PVA‐H layers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of polyglycerol esters of fatty acids and ethylene‐vinyl acetate co‐polymer on crystallization behavior of biodiesel

Biodiesel fuels (BDF) have many problems in the cold due to their crystallization properties. In particular, precipitation of large crystals of high‐melting fractions in BDF at low temperatures remarkably changes cold flow property of BDF and, thereby, it increases the values of cold filter plugging point. In this study, we evaluated polyglycerol esters of fatty acids (PGE) and ethylene‐vinyl acetate co‐polymer (EVA) as chemical additives to improve the cold flow property of palm oil‐based FAME (PFME). The results of solid fat content measurement indicate that the simultaneous addition of PGE and EVA showed synergistic effects on suppression of crystallization of PFME, however such effect was not observed when EVA was used alone. DSC thermograms indicated that the PGE additives not only decreased the crystallization temperature but also kinetically suppressed the crystal growth. Polarized light microscopy showed that the simultaneous addition of PGE and EVA led to the formation of considerably small and fine‐dispersed crystals of PFME. These results indicate that combined effects of PGE and EVA caused the formation of fine‐dispersed PFME crystals, which could improve the viscous properties of palm oil‐based BDF at relatively cold temperatures.     

Resolution of Epoxydienes by Reversed-Phase Chiral HPLC and its Application to Stereochemistry Assignment of Mulberry Looper Sex Pheromone

Resolution of insect pheromonal cis-epoxydiene racemates derived from (Z,Z,Z)-3,6,9-trienes was examined with a reversed-phase chiral HPLC column. The results showed that a Chiralcel OJ-R column was suitable for separating the enantiomers having a C₁₇–C₂₃ unsaturated straight chain except for 9,10-epoxydienes with a C₂₁–C₂₃ chain. To determine the absolute configuration of the separated enantiomers, each of the optically active epoxydienes was hydrogenated over Pd-BaSO₄ and its behavior was examined on this chiral column by cochromatography with the corresponding chiral epoxy compound having a saturated chain, which was prepared via a Sharpless epoxidation reaction. This analysis showed that the dextrorotatory C₁₇–C₂₃ 3,4- and 6,7-epoxydienes and C₁₇–C₂₀ 9,10-epoxydienes with shorter R _ts possess (3S,4R)-, (6S,7R)-, and (9R,10S) configurations, respectively, and the levorotatory enantiomers with longer R _ts possess the opposite configuration. An abdominal tip extract of the mulberry looper, Hemerophila artilineata Butler (Lepidoptera: Geometridae: Ennominae), included (9S,10R)-(Z,Z)-cis-9,10-epoxy-3,6-octadecadiene as a main sex pheromone component. The synthetic (9S,10R)-9,10-epoxydiene, rather than its antipode, elicited strong antennal and behavioral responses from the male moths in electrophysiological and field tests.     

Poly(4-diphenylaminostyrene) with a well-defined polymer chain structure: Controllable optical and electrical properties

The effect of polymer chain structure on the optical and electrical properties are reported for poly(4-diphenylaminostyrene) (PDAS), which was prepared by the living anionic polymerization of 4-diphenylaminostyrene (DAS) with the benzyllithium (BzLi)/N,N,N′,N′-tetramethylethylenediamine (TMEDA) system. The optical properties of PDAS are strongly affected by the stereoregularity of the PDAS polymer chain; intramolecular excimer-forming fluorescence was observed from PDAS with a syndiotactic-rich configuration. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PDAS were approximately −5.4 and −2.0 eV, respectively, regardless of the polymer chain structure. The hole and electron drift mobilities for PDAS were in the order of 10⁻⁴ to 10⁻⁵ (cm²/V s) and 10⁻⁵ (cm²/V s), respectively, with negative slopes. The distance of each triphenylamino (TPA) group in the polymer chain was a major factor influencing the drift mobility of PDAS. The current-voltage (I-V) characteristics of PDAS were controllable according to the polymer chain structure of PDAS.     

Deposition and structural analyses of molybdenum-disulfide (MoS2)–amorphous hydrogenated carbon (a-C:H) composite coatings

In this study we developed composite coatings consisting of amorphous hydrogenated carbon (a-C:H) and molybdenum-disulfide (MoS₂), and clarified their microstructure. In addition, we interpreted the tribological properties of the composite coatings in the viewpoint of a deposition-induced microstructural modification. The coatings were produced by the hybrid deposition technique of RF-generated methane and argon plasma and DC magnetron co-sputtering of MoS₂ target. The deposition parameter investigated in this study was methane flow rate. Structural analyses were performed using a transmission electron microscope (TEM) and an atomic force microscope (AFM). Friction tests were conducted using a ball-on-disk type tribometer. From an electron micrograph, it was confirmed that nano-clusters were embedded into an amorphous carbon host matrix. Surface roughness of the composite coating was ～ 0.25 nm in R_a compared to 5.0 nm in R_a of sputtered MoS₂. The concentration measurements were performed, and the results show that the sulfur and molybdenum concentration ratio, [S]/[Mo], is ～ 0.9, which indicates that the amount of sulfur was reduced due to the discharged plasma. In friction tests, composite coatings showed high friction in a vacuum condition. It was considered that lubricant MoS₂ lamellar structures showing super-low friction in a vacuum condition during friction could not be formed between ball and coating during friction because of the lack of sulfur in embedded clusters.     

Micro-/nanostructural investigation of laser-cut surfaces of single- and polycrystalline diamonds

Micrometer- to nanometer-scale structures of the cut surfaces of single- and polycrystalline diamonds by a pulsed ultraviolet laser have been thoroughly investigated by scanning and transmission electron microscopy. Within the laser-cut grooves, the processed diamond surfaces are extensively covered with laser-modified debris which consists of complex layered units of graphite with various crystallinities. The units consist of 1) highly oriented graphite, 2) corrugated graphite, and 3) nanocrystalline graphite, which are sequentially located from the surface of the underlying diamond substrate to the center of the grooves. Detailed textural examinations revealed that the highly oriented graphite unit is a product of the initial graphitization of diamond by a solid-state diffusion process, whereas the latter two units are deposition products from the liquid and/or vapor phases of carbon in the later stage. The present study demonstrates that the laser-cutting of diamonds proceeds in a two-step process: 1) extensive graphitization of laser-scanning path and 2) subsequent sublimation of the pre-formed graphite. These processes are basically identical among the three different types of diamonds (single crystal type Ib, single crystal type IIa and nano-polycrystalline aggregate) tested in this study.     

The physical character of coal char formed during rapid pyrolysis at high pressure

Rapid pyrolysis was conducted in a drop tube reactor using seven coals under various operating conditions. In addition to dense char, porous chars (network char and cenospheric char) were formed by the rapid pyrolysis under certain conditions. Porous char was mainly composed of film-like carbon and skeleton carbon. The pyrolyzed coal char particles were characterized in detail. Morphology and bulk density of porous char were quite different from the dense char formed under the same conditions, but elemental composition and BET surface area were similar to each other. CO₂ gasification reactivity of porous char was lower than dense char in the later gasification stage, and this was ascribed to the low reactivity of skeleton carbon.