Colored amorphous silica-based powder with TiN nanocrystals precipitated by ammonolysis of Ti–Si–O ternary glass

Coloration of amorphous silica powder containing titania was investigated by nitridation in an ammonia flow. The oxide precursors were obtained by the hydrolysis of a mixture of tetraethyl orthosilicate (TEOS) and tetrabutoxy titanium (TBT). The color changed with the amount of TBT in the mixture, the hydrolysis pH and the ammonolysis temperature. The original white color of the 8 mol% TBT powder hydrolyzed under basic pH conditions changed to pale goldenrod at 700°C, then to dark olive green at 800°C, and further darkened with increasing ammonolysis temperature. A steel-blue color appeared at 900°C for the powder obtained with 3 mol% TBT, and increased in darkness at 1000°C. A similar bluish color was observed for powders obtained by acidic hydrolysis after ammonolysis above 900°C, and this was independent of the amount of titania, although the chroma decreased with increasing firing temperature for the powder with 3 mol% TBT. The ammonolysis powder products were characterized using X-ray diffraction (XRD), electron probe micro analysis (EPMA), transmission electron microscopy-electron energy-loss spectroscopy (TEM-EELS), scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) and Ti–K edge X-ray absorption fine structure (XAFS). The color change was related to both precipitated TiN nanocrystals and residual titanium in the amorphous silica matrix. The TiN exhibited a goldish reflection and also plasmonic absorption from light blue to gray depending on the TiN crystallite size. The plasmonic absorption and resonance of nanocrystalline TiN will be useful similarly to that of gold in nanotechnology for various kinds of energy application.     

Multifunctional Composites of Chiral Valine Derivative Schiff Base Cu(II) Complexes and TiO2

We have prepared four new Cu(II) complexes containing valine moieties with imidazole ligands at the fourth coordination sites and examined their photo-induced reactions with TiO₂ in order of understanding the reaction mechanisms. Under a nitrogen atmosphere, the intermolecular electron transfer reactions (essentially supramolecular interactions) of these systems, which resulted in the reduction of Cu(II) species to Cu(I) ones, occurred after UV light irradiation. In this study, we have investigated the conditions of the redox reactions in view of substituent effects of aldehyde moieties. The results of cyclic voltammetry (CV) on an rotating ring-disk electrode (RRDE) suggested that the substitution effects and redox potentials were correlated. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were also performed to simulate the UV–Vis and circular dichroism (CD) spectra; the results revealed a reasonably good correlation between the substituent effects and the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals (HOMO-LUMO) gaps associated with the most intense transition bands. In addition, we summarized the substitution effects of Cu(II) complexes for their corresponding UV light-induced reactions.     

Development of Sensor and Control Systems of a Wearable Robot to Walk on a Step

The goal of our study is to develop a system for walking on a step using a wearable robot. Our system consists of (1) sensing of a step from the movement of the walker, (2) detection of the foot placement state related to the step, and (3) generation of gait patterns of climbing and stepping down for the step. In the generation of gait patterns for the step, toe trajectories are generated according to the height of the step to avoid collision of the swinging leg with the step. The hip trajectory is generated by an optimization technique that minimizes the sum of the joint angular jerk of the robot subject to constraints on the hip position and the velocity at toe liftoff. Each joint angle trajectory is calculated from the generated trajectories by means of inverse kinematic equations. We investigated the feasibility of the proposed sensor and control systems for two steps with different heights.     

Reversible Reaction with CO2 and Control of CO2 Absorption/Desorption Properties of Ba2(Fe1−xInx)2O5 Solid Solutions

Ba₂(Fe_1?xIn_x)₂O₅ was prepared by a solid‐state reaction under a N₂ flow. It was revealed that the solid solutions had a cubic perovskite structure with disordered oxygen vacancies at room temperature. Thermogravimetry and X‐ray diffraction measurements revealed that Ba₂(Fe_1?xIn_x)₂O₅ can reversibly react with CO_2. It was found that the equilibrium temperature of the reaction could be controlled by preparing solid solution.     

Total reflection X-ray spectroscopy as a rapid analytical method for uranium determination in drainage water

Uranium concentrations in drainage water are typically determined by α-spectrometry. However, due to the low specific radioactivity of uranium, the evaporation of large volumes of drainage water, followed by several hours of measurements, is required. Thus, the development of a rapid and simple detection method for uranium in drainage water would enhance the operation efficiency of radiation control workers. We herein propose a novel methodology based on total reflection X-ray fluorescence (TXRF) for the measurement of uranium in contaminated water. TXRF is a particularly desirable method for the rapid and simple evaluation of uranium in contaminated water, as chemical pretreatment of the sample solution is not necessary, measurement times are typically several seconds, and the required sample volume is low. We herein employed sample solutions containing several different concentrations of uranyl acetate with yttrium as an internal standard. The solutions were placed onto sample holders, and were dried prior to TXRF measurements. The relative intensity, otherwise defined as the net intensity ratio of the Lα peak of uranium to the Kα peak of yttrium, was directly proportional to the uranium concentration. Using this method, a TXRF detection limit for uranium in contaminated water of 0.30 µg/g was achieved.     

Multi-scale parallel finite element analyses of LDH sheet formability tests based on crystallographic homogenization method

A multi-scale parallel finite element (FE) procedure based on the crystallographic homogenization method was applied to the LDH sheet formability test analysis. For the multi-scale structure, two scales are considered. One is a microscopic polycrystal structure and the other is a macroscopic elastic plastic continuum. The analysis code can predict the formability of sheet metal in macro-scale, simultaneously the crystal texture and hardening evolutions in the micro-scale (Nakamachi E et al. Int J Plasticity 2007;23:450-8). Since huge computation time is required for the nonlinear dynamic multi-scale FE analysis, parallel computing technique based on domain partitioning of FE model for macro-continuum is introduced into the multi-scale code using the message passing interface (MPI) library and PC cluster (Kuramae H et al. In: Proceedings of the eighth international conference on computational plasticity, Part 1, 2005. p. 622-5). The explicit time stepping solution scheme in the nonlinear multi-scale FE dynamic problem is well-suited for parallel computing on distributed memory environment such as PC cluster because solving simultaneous equation is not required. We measured crystal morphologies of four automotive sheet metals, aluminum alloy sheet metals A6022-T43 and A5182-O, an asymmetrically rolled aluminum alloy sheet metal A6022-ASR, and mild steel HC220YD, by using the scanning electron microscope (SEM) with electron back scattered diffraction (EBSD) analyses, and defined a three-dimensional representative volume element (RVE) of micro polycrystal structure, which satisfy the periodicity condition of crystal orientation distribution. We evaluate not only macroscopic formability of the automotive sheet metals by the multi-scale LDH test analysis, but also microcrystalline texture evolution during plastic deformation. Furthermore, a relationship between the macroscopic formability and the microcrystal texture evolution was discussed through looking at multi-scale FE results. It is concluded that the mild steel HC220YD was the highest formability than the aluminum alloy sheet metals because of remaining and generating the γ-fiber texture, such as {1 1 1}〈1 1 0〉-{1 1 1}〈1 1 2〉 orientations, during plastic deformation.     

Thickness estimation of interface films formed on Li1−xCoO2 electrodes by hard X-ray photoelectron spectroscopy

Solid electrolyte interface (SEI) films formed on Li_1−xCoO₂ electrodes were observed with hard X-ray photoelectron spectroscopy (HX-PES). This paper particularly focuses on film thickness estimation using HX-PES with theoretical calculation. The validity of the calculation was proven by experiments using model SEI films. The native film formed on a LiCoO₂ composite electrode was estimated to be LiF with its thickness of 5 nm. Formation of Co (II) species on top of LiCoO₂ was also indicated. Storage of the electrode at 60 °C brought about considerable film growth (30-40 nm) with carbonate compounds formation. SEI film changes during charging of the LiCoO₂ electrode were also examined. The main component in the film was deduced to be LiF or a kind of fluorite, with its thickness decreased during charging. The SEI formation mechanisms are also elucidated.