Process Intensification of Living Cationic Polymerization of Isobutylene by a Flow Reaction System

Increasing the reaction temperature of the living cationic polymerization of isobutylene is crucial for industrial production due to the cost of refrigeration. The reaction temperature increase was achieved with an accelerated reaction rate using a flow reaction system. The polymerization conditions, including the flow reactor design, were based on the results of kinetic studies. Utilizing a milli‐scale flow reactor, polyisobutylene, which has a narrow molecular weight distribution, was obtained within a considerably short residence time at a high temperature. Furthermore, it was confirmed that the value of M_w/M_n correlates with the product of the Reynolds number and the angle of collision.     

Graphite formation on Ni film by chemical vapor deposition

Thin film formation of graphite by chemical vapor deposition using 2-methyl-1,2′-naphthyl ketone as a starting material was carried out on Ni film substrates. On Ni films directly deposited on quartz glass, the graphite films were obtained when the Ni film thickness was above 1 000 Å and above 5 000 Å at 700 °C and 1 000 °C, respectively. Depositions on thinner Ni film substrates comprise amorphous carbon (a-C) or graphite tubes which was owing to the thermal coagulation of the Ni film into droplets. On the other hand, graphite film was obtained on the Ni film with thickness 10 Å when a-C was inserted between the Ni film and the quartz glass. The coagulation of the Ni film is considered to be avoided by inserting a-C layer.     

Copolymerization of phenylacetylene with various acetylenes by W- and Mo-based catalysts

In the copolymerization of phenylacetylene with various acetylenes catalysed by WCl₆·Ph₄Sn, the relative reactivity of monomer decreased with increasing steric effect of monomer, e.g. HC  Cn-Bu, HC  Cn-Hex > HC  CPh, HC  Cs-Bu > HC  Ct-Bu, MeCCPh, CICCPh. While 1-chloro-2-phenylacetylene (a disubstituted acetylene) showed high reactivity in the homopolymerization by Mobased catalysts, the reactivity was remarkably depressed in the presence of phenylacetylene as comonomer. Based on these results, the relative reactivity of the acetylenic monomers in copolymerization was explained in terms of competitive coordination of monomers to the propagating end.     

Effect of gamma-ray irradiation on the TSC in polyethersulfone

When polyethersulfone was irradiated by γ rays and then poled at 37°C, a new TSC (thermally stimulated current) peak appeared at ~100°C. This new peak and other peaks near 40 and 150°C increase with an increase in dose of ~0.6 kGy, and this is considered to be due to trapped charges and other ionic carriers becoming mobile when rearrangement of scissioned chains occurs. However, if the dose exceeds 0.6 kGy, the peak magnitude decreases. Furthermore, if the TSC was poled at 120°C, only the peak near 150°C appeared and this peak monotonically decreased with an increase in the irradiation dose. A similar decreasing tendency was also observed in the conduction current and in the residual voltage. These decreasing features are considered to be caused by the radiation-induced change that rearrangement of scissioned chains decreases free volume for ionic transport     

Role of number of consecutive voltage zero-crossings in propagation of water trees in polyethylene

Effects of superposition of a low-frequency (0.1 to 50 Hz) voltage and a high-frequency 2 kHz voltage on the growth of water trees in polyethylene are examined. It has become clear that both the number of total voltage zero-crossings during the whole voltage application period and the number of consecutive voltage zero-crossings in the instant of the polarity reversal of the low-frequency voltage play important roles in the length and shape of water trees. Namely, the water tree length becomes longer as the number of total zero-crossings increases. Furthermore, among the voltages with the same number of total zero-crossings, the length becomes even longer with a prolonged shape in the direction of electric field as the number of consecutive zero-crossings increases. Effects of superposition of a high-frequency voltage onto a dc voltage are also examined. In this case, the dc voltage seems not to have any influence to the tree growth. By assuming the presence of space charge around the water-tree tip, the effective zero-crossings become only sensitive to the high-frequency component. Therefore, this result also indicates that the number of voltage reversals at the tree tip plays a crucial role in the growth of water trees.     

Surface degradation of polyamide nanocomposites caused by partial discharges using IEC (b) electrodes

Partial discharge (PD) degradation of polyamide both without nanoscale fillers (nanofillers) and with 2,4 and 5 wt% additions of nanofillers was investigated. Such materials were subjected to PDs using the IEC (b) electrodes for evaluation. Comparisons were made as to the surface roughness observed by scanning electron microscopy and atomic force microscopy. It was found that the change in the surface roughness is far smaller in specimens with nanofillers than those without nanofillers, and that the 2 wt% addition is sufficient for improvement of the surface roughness. Furthermore, it was elucidated that the difference of surface roughness of the degraded area due to PDs among the specimens originates from the difference in their crystalline structures. These results indicate that polyamide nanocomposite is more resistance to PDs than polyamide without nanofillers.     

Study on FBR core concepts to increase proliferation resistance of plutonium in LWR–FBR transition period

The possibility to enhance proliferation resistance of discharged plutonium in fast breeder reactor (FBR) has been investigated in terms of reactor core-design aspects. The provisional target for proliferation resistance measures based on Saito's attractiveness (ATTR) is defined. It is found that a few percent of plutonium loading and/or Am/Cm loading, which come from various types of spent fuel, might satisfy the provisional target with a minimum impact on the core neutronic performances. On Am/Cm loading core, decay heat constraints for fuel-handling aspects are found to be important and should be considered in design. There is not significant change on the current developing scenarios for light water reactor–FBR transition period by applying the measures based on Saito's ATTR. It is found that applying Kimura's proposal, 15% ²³⁸Pu content requires about 7% MA loading fraction both in the core and the blanket, and it only can be applied at limited case. The period to consume minor actinides is shorter than to consume plutonium.     

Catalytic Performance of Aged Rh/CeO2–ZrO2 for NO–C3H6–O2 Reaction Under a Stoichiometric Condition

The activity of Rh/CeO₂ for NO reduction by C₃H₆ was gradually deceased by mixing with ZrO₂ until 68 mol%. Rh supported on CeO₂–ZrO₂ with higher OSC was found to show lower catalytic activity. High OSC of CeO₂–ZrO₂ would probably stabilize the surface of Rh in oxidized state, resulting in low activity and low efficiency of C₃H₆ utilization for NO reduction. In situ FT-IR spectroscopy suggested that mononitrosyl species such as Rh(NO)^δ? and Rh(NO)^δ+ are reaction intermediates in the NO–C₃H₆–O₂ reaction over Rh/CeO₂–ZrO₂ catalysts.