Unique crystal structures and their applications as materials for Li1+x-yM1-x-3yTix+4yO3 (M = Nb or Ta, 0.07 ≤ x ≤ 0.33, 0 ≤ y ≤ 0.175)

In the Li₂O–M₂O₅–TiO₂ (M = Nb or Ta) system, Li_1+x-yM_1-x-3yTi_x+4yO₃ (LMT) forms with a superstructure known as the M-phase, in which the periodical intergrowth layers are inserted in a matrix having a trigonal structure of LiMO₃. We have been investigating this unique material focusing on its crystal structure, photoluminescence, and electrical properties.First, the formation area of the superstructure was compared between Nb- and Ta- systems and the difference was accurately analyzed.Second, to apply this unique material as a host material of phosphor, we synthesized new phosphors with various emission colors. Red phosphor, having a high PL intensity with an internal quantum efficiency of 98%, was successfully synthesized and used as a host material of the solid solution for the Ta system. Its high value was the result of the large centroid-to-cation distance of the Eu³⁺ position in the [(Li, Eu)O₁₂] polyhedral.Further still, toward application of the unique qualities of an electro-ceramic, we successfully fabricated oriented balk ceramics for the Nb system by slip casting in a strong magnetic field of 12 T. As a result, anisotropic electric properties were found along the c-axis, which were caused by the superstructure. We first clarified the mechanism showing that the anisotropic Qf value was due to anisotropic electron conductivity and anisotropic bonding strength within the superstructure.     

Research and development of liquid hydrogen (LH2) temperature monitoring system for marine applications

Monitoring the temperature in liquid hydrogen (LH₂) storage tanks on ships is important for the safety of maritime navigation. In addition, accurate temperature measurement is also required for commercial transactions. Temperature and pressure define the density of liquid hydrogen, which is directly linked to trading interests. In this study, we developed and tested a liquid hydrogen temperature monitoring system that uses platinum resistance sensors with a nominal electrical resistance of approximately 1000 Ω at room temperature, PT-1000, for marine applications. The temperature measurements were carried out using a newly developed temperature monitoring system under different pressure conditions. The measured values are compared with a calibrated reference PT-1000 resistance thermometer. We confirm a measurement accuracy of ±50 mK in a pressure range of 0.1 MPa–0.5 MPa.     

Controllable 1D Patterned Assembly of Colloidal Quantum Dots on PbSO4 Nanoribbons

Control of the 1D self‐assembly pattern of colloidal quantum dots (QDs) on PbSO₄ nanoribbon (NRb) templates is achieved. The internal structure of the NRbs is investigated by X‐ray diffraction, revealing the isotropic packing of the PbSO₄ nanoclusters in the NRbs. Colloidal QDs in a chloroform/hexane mixture are adsorbed onto the region close to the edges of the NRbs and form a 1D assembly of straight single line or double lines by controlling the amount of OAm. This is the first demonstration of a densely packed 1D self‐assembly of colloidal QDs with a straight line pattern without the use of any molecular bridge or adhesive. Atomic force microscopy measurements of the NRbs show depressions in the phase profile along the width of the NRbs, corresponding to the position of the 1D QD chain. The amount of adsorbed QDs on the NRbs in solution decreases as the addition of OAm increases, suggesting that additional OAm prevents interaction between the QDs and NRbs but facilitates the uniform adsorption of the 1D assembly. The low‐dimensional self‐assembly of colloidal QDs in this study opens up the possibility for the creation of anisotropically assembled QD superstructures.     

The activation of furfuryl alcohol polymerization by oxygen and its enhanced mechanical properties

The effect of oxygen and additional oxygen providers on furfuryl alcohol polymerization was investigated through chemical analyses and mechanical evaluation. NMR, UV–vis, Fourier transform infrared, and gas chromatography–mass spectrometry (GC–MS) results suggested that atmospheric oxygen and the further addition of an oxygen source functioned as an activator for the entire network polymerization. Interestingly, the construction of a conjugated structure on the furan linear chain, which is key to three-dimensional cross-linking, also appears to be accelerated in the presence of oxygen. Furthermore, the introduction of oxygen providers into the curing system successfully enhanced the mechanical properties of the cured furan resin.     

Data-efficient learning of robotic clothing assistance using Bayesian Gaussian process latent variable model

ABSTRACT

Motor-skill learning for complex robotic tasks is a challenging problem due to the high task variability. Robotic clothing assistance is one such challenging problem that can greatly improve the quality-of-life for the elderly and disabled. In this study, we propose a data-efficient representation to encode task-specific motor-skills of the robot using Bayesian nonparametric latent variable models. The effectivity of the proposed motor-skill representation is demonstrated in two ways: (1) through a real-time controller that can be used as a tool for learning from demonstration to impart novel skills to the robot and (2) by demonstrating that policy search reinforcement learning in such a task-specific latent space outperforms learning in the high-dimensional joint configuration space of the robot. We implement our proposed framework in a practical setting with a dual-arm robot performing clothing assistance tasks.     

Adsorption mechanism of hexavalent chromium by redox within condensed-tannin gel

We have proposed a new recovery system of hexavalent chromium Cr(VI) that is of great toxicity utilizing condensed-tannin gels derived from a natural polymer with many polyhydroxyphenyl groups. The adsorption mechanism of Cr(VI) to the tannin molecules was clarified. The adsorption mechanism consists of four reaction steps; the esterification of chromate with tannin molecules, the reduction of Cr(VI) to trivalent chromium Cr(III), the formation of carboxyl group by the oxidation of tannin molecules and the ion exchange of the reduced Cr(III) with the carboxyl and hydroxyl groups. It was found in this recovery system that a large amount of proton was consumed accompanied with the reduction of Cr(VI) so that the acidic solution containing Cr(VI) was transferred automatically to neutral one by choosing an appropriate initial pH. The carboxyl group which was created by the oxidation of tannin molecules parallel to the reduction of Cr(VI) to Cr(III) contributed to an increase in the ion-exchange sites of the reduced Cr(III). The maximum adsorption capacity of Cr(VI) reached 287 mg Cr/g dry tannin gel under the conditions of 0.77 water content of tannin gel and the initial pH = 2. This adsorption capacity was five to ten times higher than that obtained by the ion exchange between ordinary Cr(III) and tannin molecules for the tannin gels prepared under similar conditions. The system proposed here will provide an important information on a zero-emission-oriented process because it has such advantages as higher adsorption capacity of chromium and lower volume of secondary wastes compared with conventional process.     

Phragmites australis: a novel biosorbent for the removal of heavy metals from aqueous solution

Reed (Phragmites australis), a commonly used macrophyte in the wetlands constructed for water purification, was investigated as a new biosorbent for the removal of Cu(2+), Cd(2+), Ni(2+), Pb(2+) and Zn(2+) from aqueous solution. The metal adsorption capacity of reed biomass was improved significantly by water-wash, base- and acid-treatment. The maximum sorption of NaOH-pretreated reed biomass was observed near neutral pH for Cu(2+), Cd(2+), Ni(2+) and Zn(2+), while that for Pb(2+) was from an acidic range of pH 4.0 or higher. The maximum metal adsorption capacity on a molar basis assumed by Langmuir model was in the order of Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Pb(2+). Reed biosorbent showed a very high adsorption affinity value, which helps predict its high ability to adsorb heavy metals at low concentration. Desorption of heavy metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after three cycles of adsorption-elution, the adsorption capacity was regained completely and the desorption efficiency of metal was maintained at around 90%.     

Nonsalt 1‐(arylmethyloxy)pyrene photoinitiators capable of initiating cationic polymerization

Analysis of photoproducts derived from 1‐(methoxynaphthalen‐1‐ylmethyloxy)pyrene initiators and polymer end groups demonstrated that methoxynaphthalen‐1‐ylmethyl carbocation is involved in the initiation steps for both styrene (St) and cyclohexene oxide (CHO) polymerization. Charge transfer from the pyrenyloxy oxygen atom to the methoxynaphthalen‐1‐ylmethyl chromophore in the singlet excited state is assumed to be responsible for the efficient generation of the carbocation species, which also initiates the copolymerization of St and CHO. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40510.     

Asymmetric Hydrogenation of 3‐Amido‐2‐arylpyridinium Salts by Triply Chloride‐Bridged Dinuclear Iridium Complexes Bearing Enantiopure Diphosphine Ligands: Synthesis of Neurokinin‐1 Receptor Antagonist Derivatives

We describe a most straightforward synthetic method for preparing neurokinin‐1 (NK1) receptor antagonist derivatives by asymmetric hydrogenation of 3‐amido‐2‐arylpyridinium salts using dinuclear iridium complexes with enantiopure diphosphine ligands, affording the corresponding chiral piperidines in high cis‐diastereoselectivity (>95:5) and moderately high enantioselectivity (up to 86%). Deprotection treatments afforded the NK‐1 receptor antagonist (+)‐CP‐99,994 (83% ee). In addition, we observed unique additive effects of 10‐camphorsulfonic acid in the asymmetric hydrogenation of 3‐amido‐2‐arylpyridinium salts.