Assembled structures of nanocrystals in polymer/calcium carbonate thin-film composites formed by the cooperation of chitosan and poly(aspartate)

Assembled structures of calcium carbonate (CaCO₃) nanocrystals have been examined for polymer/CaCO₃ thin-film composites synthesized through a self-organization process inspired by biomineralization. For the crystallization of CaCO₃, a thin-film matrix of chitosan has been used as a polymeric substrate. When the matrix is immersed into a supersaturated aqueous solution of CaCO₃ containing 1.4 × 10⁻³ wt % poly(aspartate) (PAsp), thin-film crystals of CaCO₃ are formed spontaneously. Three kinds of disklike films have been observed under a polarizing optical microscope. Electron diffraction analyses of each film have revealed that one is aragonite, displaying radial orientation of the c axes, and the others are vaterite, exhibiting different orientations. Detailed observation by scanning electron microscopy has clarified that these films are assemblies of crystalline particles 10–20 nm in size. The thin-film composites have been obtained over a PAsp concentration range of 4.4 × 10⁻⁴ to 1.0 × 10⁻² wt %. Vaterite formation becomes dominant when the concentration of PAsp is increased. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5153–5160, 2006     

Molecular distortion effect on ff-emission in a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline.

The electronic and structural behaviour of a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline, [Pr(bathophen)(2)(NO(3))(3)], is investigated with respect to the effect of configuration changes on the Pr(III) centre. [Pr(bathophen)(2)(NO(3))(3)] luminesces from the excited states of the ligand and the metal ion. The fluorescence, ff-emission ((1)D(2)-->(3)H(4)), and phosphorescence bands appear at 394, 608.2 and 482 nm, respectively, in the solid state. In acetonitrile, the complex also shows multiple emissions. From the time-resolved emission and the lifetime measurements, the excitation energy-transfer in [Pr(bathophen)(2)(NO(3))(3)] is clarified, that is, the upper excited triplet level of the ligand acts as an energy donor, while the (1)D(2) levels of Pr(III) is the acceptor. Additionally, the emission phenomena of the complex can be modified by molecular distortion, particularly by rotation of the phenyl groups in the ligand.     

Temperature dependence of activation volume on Cu content of ultra-low carbon steel

Abstract

The temperature dependence of the yield stress, effective stress and activation volume on the Cu content in steel was assessed using polycrystalline ultra-low carbon steels with 0.5, 1 and 2 mass% Cu added. A small hump was seen in the effective stress–temperature curve for ultra-low carbon steel, which has also been reported for high-purity single-crystal iron. The effective stress was found to decrease with increasing the Cu content. The activation volume was found to be linearly related to the temperature at low temperatures for all types of specimens considered. The activation volume was found to increase abruptly at a certain temperature, which increased with increasing the Cu content. The change in the relationship of the activation volume to temperature is discussed in this paper with respect to the thermally activated process of dislocation glide from the Peierls mechanism to the interaction between dislocations and solute Cu atoms.     

Platinum complexes with diamino-substituted phosphorus ligands: Synthesis,characterization, and their reactivity with a Lewis acid

Reaction of dialkyl- or diaryl-platinum complexes PtR₂(cod) (cod = η², η²-1,5-cyclooctadiene, R = Me, p-tol) with diamino-substituted phosphorus ligands P(NMeCH₂)₂(R′) (R′ = OMe, NEt₂) produced neutral complexes, cis-[Pt(R)₂{P(NMeCH₂)₂(R′)}₂]. On the other hand, reaction of dihalogeno platinum complex PtX₂(cod) (X = Cl, I) with P(NMeCH₂)₂(OMe) yielded a cationic complex [PtX{P(NMeCH₂)₂(OMe)}₃]X. A platinum complex having both methyl and halogeno ligands, PtMeX(cod), reacted with P(NMeCH₂)₂(OMe) to give a cationic methyl complex [PtMe{P(NMeCH₂)₂(OMe)}₃]X, by contrast, it reacted with P(NMeCH₂)₂(NEt₂) to yield a neutral methyl complex [PtMeX{P(NMeCH₂)₂(NEt₂)}₂]. Reaction of [PtMe{P(NMeCH₂)₂(OMe)}₃]X with BF₃·OEt₂ and then NaBPh₄ afforded [PtX{P(NMeCH₂)₂(OMe)}₃]BPh₄, showing preferential Me group abstraction on the Pt center rather than the OMe abstraction on the phosphorus atom, followed by the coordination of X to the Pt center. All new complexes were fully characterized using ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR measurements and elemental analyses. In addition, structures of several complexes were determined by single crystal X-ray diffraction studies.     

Ga‐focused ion beam time‐of‐flight secondary ion mass spectrometer analysis of the grain boundary segregation/precipitation of boron in steel

Ga‐focused ion beam time‐of‐flight secondary ion mass spectrometry (FIB‐TOF‐SIMS) analysis was performed to investigate the grain boundary segregation/precipitation of boron in steel. To overcome the low secondary ion yield from the primary Ga⁺ source and the sensitivity using a high‐resolution Ga‐FIB source, a low energy oxygen ion beam was used prior to the Ga‐FIB‐TOF‐SIMS analysis. As a result, it was found that Ga‐FIB‐TOF‐SIMS is a very powerful tool for mapping boron segregation and/or precipitation in steel with a spatial resolution of ~200 nm. In addition, the results were strongly dependent on the surface composition. Copyright © 2014 John Wiley & Sons, Ltd.     

Mass spectrometric studies of lithium-containing oxides at high temperature

The sublimation and vaporization of various lithium containing oxides have been studied by high temperature mass spectrometry. The installed Knudsen cell apparatus gave some useful information about the vapor species, appearance potentials, partial pressures and heats of reactions involved. The investigated oxides are Li₂O, Li₂O-Al₂O₃, Li₂O-MoO₂ and Li₂O-SiO₂ systems. This paper mainly presents the most recent data for the Li₂O-SiO₂ system. A relationship for the decomposition reaction of ortho-Li₄SiO₄ was deduced. The heat of the reaction was determined by the third law method.The activity of the Li₂O component in the double oxides was estimated from the partial pressures of the vapor species. γ-LiAlO₂ and meta-Li₂SiO₃ showed fairly low activities in comparison with Li₂O oxide. The activity coefficients decreased with the Li₂O mole fraction in the lithium compounds.The heats of formation and atomization of LiO and Li₂O gaseous species were determined.