Effect of primary polymer chain rigidity on intramolecular cyclization and intramolecular crosslinking in free‐radical crosslinking monomethacrylate/dimethacrylate copolymerizations

d‐Bornyl methacrylate (BoMA) was chosen as a typical example of bulky monomethacrylate monomers, the polymerization of which led to the formation of a rigid polymer chain. To discuss the effect of primary polymer chain rigidity on intramolecular cyclization, we compared the solution copolymerization results of BoMA with 1 mol % ethylene dimethacrylate (EDMA; n = 1) and poly(ethylene glycol dimethacrylate) [CH₂?C(CH₃)CO(OCH₂CH₂)_nOCOC(CH₃)?CH₂, n = 9 (PEGDMA‐9)] with those of methyl methacrylate (MMA) with 1 mol % EDMA and PEGDMA‐9; the dependence of the weight‐average degree of polymerization on conversion for the former BoMA copolymerization systems was completely opposed to that for the latter MMA systems, and this was a reflection of a reduced occurrence of intramolecular cyclization caused by the rigidity of the primary polymer chain. The effect of primary polymer chain rigidity on intramolecular crosslinking was discussed through a comparison of both BoMA/EDMA and MMA/EDMA copolymerizations. The correlations of the intrinsic viscosity, root‐mean‐square (rms) radius of gyration, and second virial coefficient with the molecular weight were examined for both BoMA/EDMA (90/10) and MMA/EDMA (90/10) copolymerizations in a dilute solution because microgelation was observed in solution MMA/EDMA (90/10) copolymerization as a reflection of a locally extensive occurrence of intramolecular crosslinking. The logarithmic plots of both the intrinsic viscosity and rms radius of gyration versus the molecular weight for MMA/EDMA copolymerization were compared with those for the corresponding BoMA/EDMA copolymerizations. The second virial coefficients were greater than 10^?5 mol cm³ g^?2 for BoMA/EDMA copolymers, even when the conversion was very close to the gel point, whereas they were quite low, that is, less than 10^?5 mol cm³ g^?2, for an MMA/EDMA copolymer obtained at more than 15% conversion. These were ascribed to a suppressed occurrence of intramolecular crosslinking, a reflection of the lessened flexibility of the polymer main chain and a steric effect due to the bulky d‐bornyl groups. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1086–1093, 2004     

EPR study of the electronic states of β′-(BEDT-TTF)(TCNQ)

β′-(BEDT-TTF)(TCNQ) is a compound of BEDT-TTF (=ET) and TCNQ molecules aligned orthogonally with each other, forming two-dimensional sheets and one-dimensional columns of 1/4-filled π band, respectively. It is known that the metal-insulator transition occurs at 330 K at ambient pressure. We have measured the electronic spin susceptibility by means of the EPR-NMR method at 50 MHz, and the angular dependence of g-factor and line width of EPR both at Q (34 GHz) and W (94 GHz) band. We successfully confirmed that the antiferromagnetic transition occurs in ET sheets and TCNQ columns, independently.     

Numerical study of radiation‐convection heat transfer

In this study, the authors attempted to introduce a simulation technique for radiation‐convection heat transfer in the high‐temperature fields of industrial furnaces, boilers, and gas turbine combustors. The convection effect was analyzed by a differential equation, but the radiation effect was analyzed by an integral equation. Thus, it was not easy to arrange both effects using the same type of equations. Then, the authors introduced the zone method and Monte Carlo method for the integral equation of the radiation effect and the finite difference method for the differential equation of the convection effect. A three‐dimensional analysis of the high‐temperature furnace was performed by this simulation technique to obtain its temperature distribution. Furthermore, another radiation‐convection heat transfer analysis in the low‐temperature living room was performed by the same technique. Finally, the authors tried to develop a computer software for radiation‐convection heat transfer and described their idea of software construction for the above. © 2002 Wiley Periodicals, Inc. Heat Trans Asian Res, 31(5): 391–407, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.10042     

Node pacing for small optical RAM-buffered packet-switching networks

One of the difficulties with optical packet switched (OPS) networks is buffering optical packets in the network. The only available solution that can currently be used for buffering in the optical domain is using long fiber lines called fiber delay lines (FDLs), which have severe limitations. Moreover, the research on optical RAM presently being done is not expected to achieve a large capacity soon. However, the burstiness of Internet traffic causes high packet drop rates and low utilization in very small buffered OPS networks. We therefore propose a new node-based pacing algorithm for decreasing burstiness. We show that by applying some simple pacing at the edge or core backbone nodes, the performance of very small optical RAM buffered core OPS networks with variable-length packets can be notably increased.     

Complex Hydrides for Electrochemical Energy Storage

Complex hydrides have energy storage‐related functions such as i) solid‐state hydrogen storage, ii) electrochemical Li storage, and iii) fast Li‐ and Na‐ionic conductions. Here, recent progress on the development of fast Li‐ionic conductors based on the complex hydrides is reported. The validity of using them as electrolytes in all‐solid‐state lithium rechargeable batteries is also examined. Not only coated oxides but also bare sulfides are found to be applicable as positive electrode active materials. Results related to fast Na‐ionic conductivity in the complex hydrides are presented. In the last section, the future prospects for battery assemblies with high‐energy densities, and Mg ion batteries with the liquid and the solid‐state electrolytes are discussed.     

Multivariate Analytic Comparison of Interpersonal Attitude in Singapore,Thailand, and Japan

Behaviormetrika - A questionnaire on interpersonal attitudes was administered to university students majoring engineering in Singapore, Thailand, and Japan. Examination of responses to individual...     

Effects of petrographic constituents in three Yallourn brown coal lithotypes on hydroliquefaction processes

Pale, medium-light and medium-dark lithotypes of Yallourn coal were hydrogenated with and without ZnCl₂-containing catalysts (400 °C, 9.8 MPa H₂ and 3 h). The degree of hydroliquefaction was examined petrographically. Without catalyst, the amounts of water produced can be correlated with the amounts of humodetrinite; whereas with catalyst, either humotelinite or humocollinite may contribute to coal liquefaction in addition to humodetrinite; with pale lithotypes in the presence of catalyst, three submaceral groups may be converted.     

Dynamic in situ observation of automotive catalysts for emission control using X-ray absorption fine structure

Two main pivotal subjects of research in automotive catalysts were studied by modern X-ray absorption analysis techniques. One is oxygen storage/release behaviour, and the other is sintering inhibition of Pt particles. First, three types of CeO₂–ZrO₂ (Ce:Zr = 1:1 molar ratio) compounds with different oxygen storage/release capacities and different structural properties were prepared, and the valence change of Ce as a function of temperature during oxygen release/storage processes was investigated. The reduction of surface Ce mainly occurred in the range 100–170 °C, and the reduction of bulk Ce progressed at high temperatures of 170 °C and above. The Ce reduction behaviour depended not only on the homogeneity of the Ce and Zr for bulk reduction at high temperatures but also on the particle size of the CeO₂–ZrO₂ samples for surface reduction at low temperatures. Secondly, sintering inhibition of Pt in Pt/Al₂O₃, Pt/MgO and Pt/ceria-based catalysts after 800 °C ageing in air was studied. We found that the Pt–O–M (M = Mg, Ce) bond acted as an anchor and inhibited the sintering of Pt particles on MgO or ceria-based oxide. Especially, it was noteworthy that the Pt–O–Ce⁴⁺ bond on the ceria-based support breaks easily through the reduction of Ce (Ce⁴⁺ → Ce³⁺) during the usual stoichiometric and reducing conditions.