Synthesis of stable and soluble one-handed helical poly(substituted acetylene)s without chiral pendant groups via polymer reaction in membrane state

A soluble and stable one-handed helical conjugated polymer without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer having two hydroxyl groups followed by desubstitution of the chiral groups in a solid membrane state. The reason for the success was the polymer reaction was carried out in the membrane state. This is an alternative method to obtain such a unique chiral polymer which was obtained only by the helix-sense-selective polymerization (HSSP) we reported before. In addition the efficiency of the chiral induction was higher than that of the HSSP. It is interesting that the “Membrane state” acted like as if a protecting group.     

Grafting of poly(ethylene oxide) onto C60 fullerene using macroazo initiators

In order to improve the solubility of C₆₀ fullerene in conventional solvents, grafting of hydrophilic poly(ethylene oxide) (PEO) by utilizing the radical-trapping nature of C₆₀ fullerene was investigated. Macroazo initiators containing a poly(ethylene oxide) unit, known as Azo-PEO, were prepared at various molecular weights by the reaction of 4,4′-azobis(4-cyanopentanoyl chloride) with poly(ethylene glycol) methyl ether. PEO radicals formed by thermal decomposition of Azo-PEO were successfully trapped by C₆₀ fullerene to give PEO-grafted C₆₀ fullerene. Their structures were confirmed by FT-IR spectroscopy, size exclusion chromatography, UV-vis spectroscopy, and differential scanning calorimetry. When Azo-PEO with low-molecular weight was reacted with C₆₀ fullerene, a bis-adduct, C₆₀-(PEO)₂, and a tetrakis-adduct, C₆₀-(PEO)₄, were formed. In contrast, in reactions with Azo-PEO of higher molecular weight, only the bis-adduct was formed, and no formation of the tetrakis-adduct was observed. The structure of bis-adduct was found to be 1,4-type. The solubility of C₆₀ fullerene in water, THF, methanol, and other conventional organic solvents was remarkably improved by grafting of PEO. In addition, the thermal stability of PEO was dramatically increased by grafting onto C₆₀ fullerene.     

Ca-α SiAlON hollow spheres prepared by carbothermal reduction–nitridation from different SiO2 powders

The formation process of hollow spheres composed of nanosized Ca-α SiAlON particles was investigated using SiO₂ starting powders with different characteristics in particle size, shape and crystalline state. TEM observations showed Ca-α SiAlON hollow spheres composed of a large number of nanosized particles in the products prepared at 1450 °C for 120 min in nitrogen. In all systems, the Ca-α SiAlON hollow spheres were always produced through an intermediate Si–Al–Ca–O liquid phase in the same mechanism, regardless of the characteristics of SiO₂ starting powders used. Spherical solid particles consisted of amorphous phase containing Si, Al, Ca, O and a small amount of N were generated at the initial stage of carbothermal reduction–nitridation. These spherical solid particles changed into hollow particles with the progression of the reaction from the liquid phase to the crystalline Ca-α SiAlON with increasing temperature.     

Stereocomplex crystallization and spherulite growth behavior of poly(l-lactide)-b-poly(d-lactide) stereodiblock copolymers

The non-isothermally and isothermally crystallized stereodiblock copolymers of poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) with equimolar l-lactyl and d-lactyl units and different number-average molecular weights (M_n) of 3.9 × 10³, 9.3 × 10³, and 1.1 × 10⁴ g mol⁻¹, which are abbreviated as PLLA-b-PDLA copolymers, contained only stereocomplex crystallites as crystalline species, causing higher melting temperatures of the PLLA-b-PDLA copolymers compared to those of PLLA homopolymers. In the case of non-isothermal crystallization, the cold crystallization temperatures of the PLLA-b-PDLA copolymers during heating and cooling were respectively lower and higher than those of PLLA homopolymers, indicating accelerated crystallization of PLLA-b-PDLA copolymers. In the case of isothermal crystallization, in the crystallizable temperature range, the crystallinity (X_c) values of the PLLA-b-PDLA copolymers were lower than those of the PLLA homopolymers, and were susceptible to the effect of crystallization temperature in contrast to that of homopolymers. The radial growth rate of the spherulites (G) of the PLLA-b-PDLA copolymers was the highest at the middle M_n of 9.3 × 10³ g mol⁻¹. This trend is different from that of the PLLA homopolymers where the G values increased monotonically with a decrease in M_n, but seems to be caused by the upper critical M_n values of PLLA and PDLA chains as in the case of PLLA/PDLA blends (in other papers), above which homo-crystallites are formed in addition to stereocomplex crystallites. The disturbed crystallization of PLLA-b-PDLA copolymers compared to that of the PLLA/PDLA blend is attributable to the segmental connection between the PLLA and PDLA chains, which interrupted the free movement of those chains of the PLLA-b-PDLA copolymers during crystallization. The crystallite growth mechanism of the PLLA-b-PDLA copolymers was different from that of the PLLA/PDLA blend.     

Measurement of liquid water content in cathode gas diffusion electrode of polymer electrolyte fuel cell

Water management in cathode gas diffusion electrode (GDE) of polymer electrolyte fuel cell (PEFC) is essential for high performance operation, because liquid water condensed in porous gas diffusion layer (GDL) and catalyst layer (CL) blocks oxygen transport to active reaction sites. In this study, the average liquid water content inside the cathode GDE of a low-temperature PEFC is experimentally and quantitatively estimated by the weight measurement, and the relationship between the water accumulation rate in the cathode GDE and the cell voltage is investigated. The liquid water behavior at the cathode is also visualized using an optical diagnostic, and the effects of operating conditions and GDL structures on the water transport in the cathode GDE are discussed. It is found that the liquid water content in the cathode GDE increases remarkably after starting the fuel cell operation due to the water production at the CL. At a high current density, the cell voltage drops suddenly after starting the operation in spite of a low water content in the cathode GDE. When the GDL thickness is increased, much water accumulates near the cathode CL and the fuel cell shuts down immediately after the operation. In the final section of this paper, the structure of cathode GDL that has several grooves for water removal is proposed to prevent water flooding and improve fuel cell performance. This groove structure is effective to promote the removal of the liquid water accumulated near the active catalyst sites.     

Evaluation of high‐temperature ductility in weld metal. Study of reheat cracking in metal active‐gas welding with flux‐cored wire stainless steel weld metal (2nd Report)

The special features of the weldability of high-strength low-carbon microalloyed steels are investigated.     

Aroma Characteristic and Volatile Profiling of Carrot Varieties and Quantitative Role of Terpenoid Compounds for Carrot Sensory Attributes

The aroma characteristics and volatile profiles of 14 carrot varieties were investigated by sensory evaluations and gas chromatography–mass spectrometry volatile analyses. The sensory map obtained by principal components analysis showed that the sensory attributes comprised 3 categories: sour/green, overall carrot/harsh/ink‐like, and fruity/fresh/sweet. The Kuroda type is characterized by lower intensities of overall carrot/harsh/ink‐like and fruity/fresh/sweet notes. Furthermore, volatile profiling indicated that this type did not have significantly higher amounts of volatiles. Partial least squares regression analysis determined the quantitative contributions to ink‐like, harsh, and fruity carrot aromas; monoterpenes had significant positive correlations with these attributes, while bisabolene isomers had negative correlations. The aroma attribute intensity and contents of volatiles and nutritional compounds are relatively low in the Kuroda type than in other carrot types. This type may be useful for reducing carrot harshness during the development of new carrots with good eating qualities.     

Highwall Stability due to Punch Mining at Opencut Coal Mines

Conventional highwall mining extracts coal with an auger machine or a continuous miner from exposed seams at the base of opencut or strip operations. However, under poor strata and high stress conditions, highwall mining cannot be conducted due to pillar and roof failures. In such cases, punch highwall mining is more effective than the conventional highwall mining. This paper describes conventional highwall mining and punch highwall mining systems and discusses the stability of the highwall due to punch highwall mining at opencut coal mines.     

Fabrication and operation limit of lead-free PTCR ceramics using BaTiO3–(Bi1/2Na1/2)TiO3 system

The electric properties of BaTiO₃–(Bi_1/2Na_1/2)TiO₃ (BT–BNT) solid solution ceramics were studied as a lead-free PTCR (positive temperature coefficient of resistivity) thermistor material usable over 130°C. For determining the maximum switching temperature T _s, the phase diagram of BT–BNT binary system was clarified. Two semiconductorization processes and their electric properties are described. The lanthanum(La)-doped BBNT ceramics sintered in air still showed dielectric behaviors, but the niobium(Nb)-doped ones had a low resistivity at room temperature, ρ _RT, on the order of 10³ Ωcm and showed a PTC behavior. Sintering under a low O₂ atmosphere produces BT–BNT ceramics with less than 10² Ωcm compared to those prepared in air. Our current research produced the BBNT ceramics with T _s values around 210°C by increasing the (Bi_1/2Na_1/2) content in the ceramics.