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.     

Influence of Tip Clearance on Blade Vibration of Vaneless Radial Turbine

With the increasing demand of turbochargers with high performance and low turbo lag, high cycle fatigue (HCF) of radial turbine blades has become the most commo...     

Computational fluid dynamics simulation and statistical procedure for estimating wide-area distributions of airborne sea salt considering local ground conditions

Steel corrosion under atmospheric conditions is a critical issue in the maintenance of structures such as electric transmission towers and bridges during their long-term operation, which are generally located at many places over a wide area. Since a major factor causing corrosion is airborne salt particles coming from the sea, wide-area distributions of the long-term cumulative amount of sea salt deposited on surfaces are needed. Moreover, since the amount of airborne sea salt varies locally with the topography, it is also important to consider the effects of topography. In this paper, a method combining a computational fluid dynamics model and a statistical procedure is proposed to efficiently estimate wide-area distributions of the cumulative amount of airborne sea salt by considering the local topography. The predicted amount of airborne sea salt decreases with increasing distance from the coast and varies with the topography and the offshore wind. A comparison between predicted and observed amounts revealed that: (1) this method appropriately estimates topographical effects on sea-salt transport and enables the estimation of deposited sea salt on structure surfaces, and (2) consideration of the trapping efficiency of sea-salt particles on structure surfaces improves the prediction accuracy.     

Liquid‐phase sintering of highly Na+ ion conducting Na3Zr2Si2PO12 ceramics using Na3BO3 additive

Na₃Zr₂Si₂PO₁₂ (NASICON) is a promising material as a solid electrolyte for all‐solid‐state sodium batteries. Nevertheless, one challenge for the application of NASICON in batteries is their high sintering temperature above 1200°C, which can lead to volatilization of light elements and undesirable side reactions with electrode materials at such high temperatures. In this study, liquid‐phase sintering of NASICON with a Na₃BO₃ (NBO) additive was performed for the first time to lower the NASICON sintering temperature. A dense NASICON‐based ceramic was successfully obtained by sintering at 900°C with 4.8 wt% NBO. This liquid‐phase sintered NASICON ceramic exhibited high total conductivity of ~1 × 10^?3 S cm^?1 at room temperature and low conduction activation energy of 28 kJ mol^?1. Since the room‐temperature conductivity is identical to that of conventional high‐temperature‐sintered NASICON, NBO was demonstrated as a good liquid‐phase sintering additive for NASICON solid electrolyte. In the NASICON with 4.8 wt% NBO ceramic, most of the NASICON grains directly bonded with each other and some submicron sodium borates segregated in particulate form without full penetration to NASICON grain boundaries. This characteristic composite microstructure contributed to the high conductivity of the liquid‐phase sintered NASICON.     

Change in Oxygen Content of Y2O3-Nd2O3-Doped Silicon Nitride During Firing

The oxygen content of silicon nitride with 1 mol% Y₂O₃—Nd₂O₃ additive was measured after firing to determine the compositional change during gas-pressure sintering. Oxygen content decreases from 2.5 to 0.94 wt% during firing for 4 h at 1900°C and 10-MPa pressure in N₂. This decrease in oxygen results from the release of SiO gas generated by a thermaldecomposition reaction between Si₃N₄ and SiO₂. The resultant sintered silicon nitride material contains less than 1 wt% oxygen.     

Synthesis and Photoluminescence of Eu2+-Doped α-Silicon Nitride Nanowires Coated with Thin BN Film

A feasible doping strategy is introduced to synthesize Eu²⁺-doped α-Si₃N₄ nanowires coated with a thin BN film. The nanowires were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, and a fluorescence spectrophotometer. The Eu²⁺-doped α-Si₃N₄ nanowires emitted strong yellow light, which is related to the 4 f ⁶5 d –4 f ⁷ transition of Eu²⁺, upon a broad excitation wavelength range between 250 and 450 nm. The obtained nanowires provided a potential candidate for application in optical nanodevices, as well as in white LEDs.     

Mechanical properties of silicon-doped diamond-like carbon films prepared by pulse-plasma chemical vapor deposition

Silicon-doped diamond-like carbon (Si-DLC) films were prepared by dc pulse-plasma chemical vapor deposition (CVD), using a mixture of acetylene (C₂H₂) and tetramethylsilane (TMS) as the material gas. The pulse voltage was varied from − 2 to − 5 kV, and the TMS flow ratio (TMS/(C₂H₂ + TMS)) was varied from 0 to 40%. At a pulse voltage of − 2 kV, an increase in TMS flow ratio leads to a decrease in hardness. In contrast, at a pulse voltage of − 5 kV, an increase in TMS flow ratio leads to a slight increase in hardness. The high hydrogen concentration in the films due to an increase in TMS flow ratio promotes the formation of polymeric sp³ C―H bonds, resulting in the fabrication of soft films at a low pulse voltage of − 2 kV. However, an increase in the effect of ion peening on the growth face results in the formation of hard films at a high pulse voltage of − 5 kV. Then, at a pulse voltage of − 5 kV fabricating hard Si-DLC films, an increase in TMS flow ratio leads to an increase in the silicon content in the films, resulting in a decrease in the friction coefficient. Therefore, it is clarified that Si-DLC films fabricated by dc pulse-plasma CVD under a high pulse voltage and high TMS flow ratio exhibit high hardness and a low friction coefficient. Moreover, to investigate the friction coefficient of Si-DLC films fabricated by dc pulse-plasma CVD, films deposited by dc plasma CVD were also evaluated. To obtain the same low friction coefficient, dc pulse-plasma CVD requires less TMS than dc plasma CVD. Hence, it is also clarified that Si-DLC films can be fabricated at a low cost by dc pulse-plasma CVD.     

Compositional Dependence of Normal Spectral Emissivity of Molten Cu-Fe Alloy

Metallurgical and Materials Transactions B - Normal spectral emissivity of molten Cu-Fe alloy with different compositions was measured at the wavelength of 807 nm using an electromagnetic...