Electrical Breakdown Properties and Space Charge Formation in High Temperature Region in Ultraviolet Ray Irradiated PVC

Polyvinyl chloride (PVC) is the most popular insulating material for electric wiring instruments. However, an exothermic reaction above 150 °C may cause deterioration of the insulating properties of PVC. Therefore, it is important to clarify the heat degradation in PVC, not only to investigate the ignition of electrical wiring products but also to use electrical products safely. It is known that ultraviolet (UV) irradiation causes chemical deterioration of PVC and an increase in its conductivity. Generally, it has been thought that the electrical breakdown properties, electrical conduction, and insulating performance are affected by space charge accumulation in an insulating material. A high temperature pulsed electroacoustic (PEA) system usable up to 250 °C has been developed, and the PEA system can measure the space charge distribution and conduction current in the high temperature range simultaneously. In this investigation, the space charge distribution and conduction current were measured up to electrical breakdown in a non‐UV irradiated sample (normal PVC) and in 353 nm and 253 nm UV‐irradiated PVC samples in the range from room temperature to 200 °C in a DC electric field. In the short wavelength UV irradiated PVC sample (253 nm, 300 h), a deterioration of breakdown strength at 90 °C to 150 °C and negative packet‐like charges were observed at 60 °C and 100 °C, a positive charge accumulated in front of both the anode and cathode above 90 °C, and a higher electric field near the cathode side because the positive charge of the cathode side was greater.     

Synthesis of thermoresponsive block and graft copolymers via the combination of living cationic polymerization and RAFT polymerization using a vinyl ether-type RAFT agent

A novel vinyl ether-type RAFT agent, benzyl 2-(vinyloxy)ethyl carbonotrithioate (BVCT) was synthesized for various block copolymers via the combination of living cationic polymerization of vinyl ethers and reversible addition−fragmentation chain transfer (RAFT) polymerization. The novel BVCT–trifluoroacetic acid adduct play an important role to produce well-defined block copolymers, which is both as a cationogen under EtAlCl₂ initiation system in the presence of ethyl acetate for living cationic polymerization and a RAFT agent for blocks by RAFT polymerization. The resulting polymer, poly(vinyl ether)s, by living cationic polymerization had a high number average α-end functionality (≥0.9) as determined by both ¹H NMR and MALDI-TOF-MS spectrometry. In addition, this poly(vinyl ether)s worked well as a macromolecular chain transfer agent for RAFT polymerization. The RAFT polymerization of radically polymerizable monomers was conducted in toluene using 2,2′-azobis(isobutyronitrile) at 70 °C. For example, a double thermoresponsive block copolymer (MOVE₆₁-b-NIPAM₁₅₀) consisting of 2-methoxyethyl vinyl ether (MOVE) and N-isopropylacrylamide (NIPAM) was prepared via the combination of living cationic polymerization and RAFT polymerization. The block copolymer reversibly formed and deformed micellar assemblies above the phase separation temperature (T_ps) of poly(NIPAM) block in water. This BVCT is not only functioned as an initiator, but also acted as a monomer. When BVCT was copolymerized with MOVE by living cationic polymerization, followed by graft copolymerization with NIPAM via RAFT polymerization, well-defined graft copolymers (MOVE_n-co-BVCT_m)-g-NIPAM_x (n = 62–73, m = 1–9, x = 19–214) were successfully obtained. However, no micelle formed in water above T_ps of poly(NIPAM) graft chain unlike the case of block copolymers.     

Catalytic Aerobic Photo‐oxidation of a Methyl Group on a Heterocycle to Produce an Aldehyde via Homolytic C?I Bond Cleavage caused by Irradiation with Visible Light

A new catalytic method was developed for photo‐oxidizing the methyl group on aromatic heterocycles such as benzothiazole, benzoxazole, and quinoline to produce the corresponding aldehyde. This is the first report of the metal‐free catalytic synthesis of benzothiazole‐2‐carboxaldehydes using molecular oxygen as the terminal oxidant.

     

Microanalysis of anionic surfactants in waste water by infrared spectroscopy

Infrared spectroscopy was applied to identify and determine microamounts of anionic surfactants contained in sewage or river waters. The surfactants tested were linear alkylbenzene sulfonate (LAS), branched alkylbenzene sulfonate (ABS), alpha olefine sulfonate (AOS), fatty alcohol sulfate (AS) and fatty alcohol ethoxy sulfate (AES).Anionic surfactants in waters were extracted by chloroform as methylene blue complexes and sulfate type surfactants, i.e. AS and AES were then removed by subsequent hydrolysis. Residual sulfonate type surfactants were first released from methylene blue complexes by ion exchange technique and then changed to sulfonyl chloride derivatives for infrared spectroscopy. Key bands for the identification of sulfonate type surfactants are 640, 618 and 524 cm⁻¹ for LAS, ABS and AOS, respectively. Sulfate type surfactants was calculated from the difference of methylene blue active substance contents before and after hydrolysis.     

软土地基上道路桥头跳车缓解工法的设计与工程实践

针对软土地基上道路行车的“桥头跳车”现象，列举了在日本经常使用的几种桥头接坡过渡段地基处理的方法：(1)设钢筋混凝土连接搭板；(2)沥青混凝土路面的加铺维修；(3)切短桩头的办法重建构筑物。分析了这几种传统的桥头接坡处理方法的优缺点及经济性。在日本佐贺平原有明软粘土地基上的桥头接坡段地基处理工程实例的基础上，介绍了缓解桥头跳车现象的设计施工法——CA工法；给出了CA工法的设计内容及参数确定的方法，包括搅拌桩的长度与接坡段的处理范围；最后通过现场监测结果说明所提出的设计法的有效性。     

Liposome‐Based in Vitro Evolution of Aminoacyl‐tRNA Synthetase for Enhanced Pyrrolysine Derivative Incorporation

Methanosarcina species pyrrolysyl‐tRNA synthetase (PylRS) attaches Pyl to its cognate amber suppressor tRNA. The introduction of two mutations (Y384F and Y306A) into PylRS was previously shown to generate a mutant, designated LysZ‐RS, that was able to attach N‐benzyloxycarbonyl‐L ‐lysine (LysZ) to its cognate tRNA. Despite the potential of LysZ derivatives, further LysZ‐RS engineering has not been performed; consequently, we aimed to generate LysZ‐RS mutants with improved LysZ incorporation activity through in vitro directed evolution. Using a liposome‐based in vitro compartmentalization (IVC) approach, we screened a randomly mutagenized gene library of LysZ‐RS and obtained a mutant that showed increased LysZ incorporation activity both in vitro and in vivo. The ease and high flexibility of liposome‐based IVC should enable the evolution of not only LysZ‐RS that can attach various LysZ derivatives but also of other enzymes involved in protein translation.     

High-temperature formation phases and crystal structure of hot-pressed thermoelectric compounds with chalcopyrite-type structure

In this study, we introduced the temperaturedependent formation phases and crystallographic parameters of hot-pressed silver gallium telluride AgGaTe_2 and copper gallium telluride CuGaTe_2 with chalcopyrite structure from 300 to 800 K. These two compounds are potential thermoelectric materials in the intermediate temperature range; however, the temperature-dependent formation phases and crystallographic parameters of hotpressed samples have not yet been analyzed in detail. The crystal structure analysis based on synchrotron X-ray diffraction(SXRD) measurements clarifies that impurity phases such as Te and Ag_2 Te in the AgGaTe_2 matrix and Te and CuTe in the CuGaTe_2 matrix appear at some temperature regions above 300 K. The existence of such impurity phases could be correlated with the increases of the electrical resistivity and Seebeck coefficient of the samples after multiple measurement cycles of the temperature-dependent transport properties from 300 to 800 K.The tetragonal lattice parameters a and c, tetragonal lattice volume, thermal expansion coefficients, tetragonal distortion, anion displacement parameter, and isotropic displacement parameter of the hot-pressed AgGaTe_2 and CuGaTe_2 were also analyzed. These crystallographic parameters are expected to substantially affect the thermoelectric properties of AgGaTe_2 and CuGaTe_2. Our results provide prospect of the long-term high-temperature stability and clues of the detailed analysis on the transport properties of hot-pressed AgGaTe_2 and CuGaTe_2, which should aid their development for thermoelectric applications.