Development of atom probe specimen preparation techniques for specific regions in steel materials

More elaborated specimen preparation techniques for atom probe analysis were developed using a focused ion beam with a sample lift-out system so as to expand the application field in steel materials. The techniques enable atom probe analysis of sample steel at site-specific regions of interest. The preferable form of the needle specimen was provided by electrostatic field calculation using a finite element method. The new techniques were applied to the observation of a bainite-ferrite interface in a low carbon steel, and atomic-scale partitioning and segregation of alloying elements at the phase interface were directly observed in three dimensions.     

Density functional calculations on agostic ethyl-Ti (IV) complexes

First principles, density functional theory embodied in the DMol program has been applied to agostic ethyl-Ti-complexes, including the dmpe complex, [Ti(-CH₂CH₃)C1₃(dmpe)], where DMPE=(Me₂PCH₂)₂ and its model complex, [Ti(−CH₂CH₃)Cl₃(PH₃)₂]. The ethyl moiety of the complexes can adopt two limiting conformations, staggered and eclipsed. In the model complex, [Ti(−CH₂CH₃)C1₃(PH₃)₂], both conformers are found to form agostic structures upon geometry optimization subject to Cs symmetry constraint, with the agostic eclipsed structure being the lower in energy. Full geometry optimization of the dmpe complex, [Ti(−CH₂CH₃)C1₃(dmpe)], yields an agostic structure with geometrical features similar to those measured by single crystal X-ray analysis. It is shown that the HOMO orbital contributes substantially to the agostic bonding.     

Microstructure of high battery-performance Li2FeSiO4/C composite powder synthesized by combining different carbon sources in spray-freezing/freeze-drying process

Spray-freezing/freeze-drying technique was applied to the synthesis of Li₂FeSiO₄/C composite powders using solutions containing various carbon sources, water-soluble and colloidal carbon, followed by heat treatment. The effects of the carbon sources on the microstructure and battery performance of the synthesized composite powders were investigated. The microstructures of the composite powders were clearly different when different carbon sources were used, ascribed from the thermal behavior of the carbon sources during the heat treatment. It was possible to control the microstructures of Li₂FeSiO₄/C composite powders by combining different carbon sources, and the synthesized composite powders exhibited high discharge capacities by mixing with only a binder for cathode. The composite powders using glucose and Ketjenblack dispersion as carbon sources delivered 165 mAh/g at first discharge capacity at 0.1?C. The developed chain structure suitable for conducting paths in the electrodes and a higher-specific BET surface area, attributed from Ketjenblack, were likely responsible for the higher performance.     

Discrete plane segmentation and estimation from a point cloud using local geometric patterns

This paper presents a method for segmenting a 3D point cloud into planar surfaces using recently obtained discretegeometry results. In discrete geometry, a discrete plane is defined as a set of grid points lying between two parallel planes with a small distance, called thickness. In contrast to the continuous case, there exist a finite number of local geometric patterns （LGPs） appearing on discrete planes. Moreover, such an LGP does not possess the unique normal vector but a set of normal vectors. By using those LGP properties, we first reject non-linear points from a point cloud, and then classify non-rejected points whose LGPs have common normal vectors into a planar-surface-point set. From each segmented point set, we also estimate the values of parameters of a discrete plane by minimizing its thickness.     

Formation of a soluble hyperbranched polymer via initiator–fragment incorporation radical copolymerization of divinyl adipate and isobutyl vinyl ether

The copolymerization of divinyl adipate (DVA) with isobutyl vinyl ether (IBVE) was conducted at 70 and 80 °C in benzene using azobisisobutyronitrile (AIBN), at a concentration as high as 0.50 mol l^?1 as the initiator, where the concentrations of DVA and IBVE were 0.40 and 0.60 mol l^?1, respectively. The copolymerization proceeded homogeneously, without any gelation, to yield soluble copolymers in spite of the high molar ratio of DVA as an excellent cross‐linker for IBVE. The copolymer yield increased with time, and the number‐average molecular weight (M_n = 0.9–2.4 × 10⁴ g mol^?1) from gel permeation chromatography (GPC) and molecular weight distribution (M_w/M_n = 1.5–7.6) of the resulting copolymer increased with copolymer yield. The cyanopropyl group, as a fragment of AIBN, was incorporated as a main constituent in the copolymer, the fraction of which increased from ca 10 to ca 20 % with copolymer yield, hence indicating that the copolymerization is an initiator–fragment incorporation radical polymerization. The copolymers also contained IBVE units (10–30 %) and DVA units with intact double bond (8–36 %) and without double bond (45 %). The intrinsic viscosity of the copolymer was very low (0.1 dl g^?1) at 30 °C in tetrahydrofuran. The results from GPC–multi‐angle laser light scattering (MALLS), transmission electron microscopy (TEM) and MALLS revealed that individual copolymer molecules were formed as hyperbranched nanoparticles. Copyright © 2004 Society of Chemical Industry     

Discovery of Protein Disulfide Isomerase P5 Inhibitors that Reduce the Secretion of MICA from Cancer Cells

In order to regulate the activity of P5, which is a member of the protein disulfide isomerase family, we screened a chemical compound library for P5‐specific inhibitors, and identified two candidate compounds (anacardic acid and NSC74859). Interestingly, anacardic acid inhibited the reductase activity of P5, but did not inhibit the activity of protein disulfide isomerase (PDI), thiol‐disulfide oxidoreductase ERp57, or thioredoxin. NSC74859 inhibited all these enzymes. When we examined the effects of these compounds on the secretion of soluble major histocompatibility complex class‐I‐related gene A (MICA) from cancer cells, anacardic acid was found to decrease secretion. In addition, anacardic acid was found to reduce the concentration of glutathione up‐regulated by the anticancer drug 17‐demethoxygeldanamycin in cancer cells. These results suggest that anacardic acid can both inhibit P5 reductase activity and decrease the secretion of soluble MICA from cancer cells. It might be a novel and potent anticancer treatment by targeting P5 on the surface of cancer cells.