Synthesis of polyethylene oxide end‐capped with perfluoroalkyl groups/polystyrene prototype brushes

Polystyrene (PS)/poly(ethylene oxide) (PEO) prototype brushes were prepared by alternating free‐radical copolymerization of methacryloyl‐terminated PS and α‐vinylbenzyl‐ω‐hydroxy or α‐vinylbenzyl‐ω‐perfluoroalkyl (R_f) PEO macromonomers with the addition of Lewis acid (SnCl₄). It was found from their dilute‐solution properties that PS/PEO end‐capped with R_f (PBR_f), and PS/PEO having OH groups at terminal ends (PBOH) prototype brushes formed a single molecule in benzene and aggregates in chloroform, respectively. However, the brush PBOH formed a single molecule in N,N‐dimethylformamide. Such aggregation behaviors seemed to be caused by the interaction between hydroxy groups of PEO chain ends. The brush PBOH was also converted into PBR_f‐type brush by chemical modification, using corresponding acid chloride. The substitution of R_f groups was ～70% due to slipping of terminal hydroxy groups into PEO internal domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 772–778, 2006     

Studies of tetrazoles as rubber chemicals. II. Reactivities and antioxidation activities of reactive antioxidants based on tetrazoles

The chemical reactivities of novel reactive antioxidants based on tetrazoles for carbon–carbon double bonds of liquid polybutadiene and their antioxidation activities toward isoprene rubber were evaluated. These antioxidants, i.e., 2-substituted phenyl-5-(3′,5′ -di-tert-butyl-4′-hydroxyphenyl)tetrazoles (PHPT), were pyrolyzed in liquid polybutadiene at 160–170°C for 30 min to attach to rubber in extents of 61–85% of the nitrileimines formed from PHPT by 1,3-dipolar addition reaction. The reactivities of PHPT followed the order p-Cl > m-Cl > H > p-CH₃ > m-CH₃, p-OC₂H₅, suggesting that PHPT reacts with diene rubber in electrophilic reaction and p-derivatives exhibit higher contents of binding than m-derivatives due to steric hindrance. From oxygen absorption data, the antioxidation activities of PHPT for isoprene rubber vulcanizates followed the order m-Cl, m-CH₃ > H, p-Cl, p-Cl, p-CH₃ > p-OC₂H₅. Isoprene rubber vulcanizates, obtained after pretreatment with PHPT by heating, were extracted with acetone, followed by aging to show that there was good retention and appreciable antioxidation activities of PHPT, especially, p-CH₃ and p-Cl substituted PHPT.     

Experimental analyses for electronic structure of barium zirconate-strontium zirconate proton-conducting solid solution

In proton-conducting oxides, analyses for their electronic structure contribute to the understanding of interactions between defects in them. In this study, electronic band alignment of (1−x)BaZr_0.8Y_0.2O_3−δ(BZY)–xSrZr_0.95Y_0.05O_3−δ(SZY) proton-conducting solid-solution system (BSZY) which has high defect concentration and the deep valence band is experimentally investigated. By using thin-film specimens for optical absorption measurements, absorption edges derived from electron transition from the valence band to the conduction band which was insensitive to the proton incorporation were clearly observed in spite of the high defect concentration. The obtained optical band gap energy increased from 5.61 to 5.89 eV with increasing x, which was consistent with a composition dependence of Zr(Y)O₆ octahedral tilting. Ultraviolet photon-yield spectroscopy (UV-PYS) measurements under vacuum condition revealed that BZY and SZY had ionization energy of 6.98 and 7.31 eV, respectively, and thus the absolute energy levels of the valence band maximum and the conduction band minimum of BSZY were experimentally clarified. We propose that the combination of the optical absorption measurements using thin-film specimens and the UV-PYS measurements under vacuum condition is effective in evaluating fundamental electronic structures of proton-conducting oxides.     

Evaluation of cost reduction potential for 1 kW class SOFC stack production: Implications for SOFC technology scenario

Recently, a commercial version of a residential solid oxide fuel cell (SOFC) system with a flat tubular cell has been developed. However, the system cost still remains very high, which is a barrier to its widespread use. In this study, the potential for cost reductions in SOFC stack production was investigated in order to contribute to the viability of the widespread use of such residential SOFC systems in future. A cost analysis of 700 W SOFC stack production based on a process integration modeling was conducted. The present bottom–up approach enabled us to perform a sensitivity analysis with a variety of parameters in terms of cell design, the production process and cell performance. This allowed us to investigate the effects of these factors on the production cost, thereby revealing the quantitative impact of each technological improvement on the cost reduction potential. The present analysis also revealed innovation pathways which could result in technology scenarios where residential SOFC systems could reach a break-even point in comparison with the baseload electricity cost. The analysis of the cost reduction potential presented here provides a useful viewpoint for developing a research strategy for state-of-the-art SOFC technology.     

Random fuzzy multi-objective linear programming: Optimization of possibilistic value at risk (pVaR)

This paper considers multiobjective linear programming problems (MOLPP) where random fuzzy variables are contained in objective functions and constraints. A new decision making model optimizing possibilistic value at risk (pVaR) is proposed by incorporating the concept of value at risk (VaR) into possibility theory. It is shown that the original MOLPPs involving random fuzzy variables are transformed into deterministic problems. An interactive algorithm is presented to derive a satisficing solution for a decision maker (DM) from among a set of Pareto optimal solutions. Each Pareto optimal solution that is a candidate of the satisficing solution is exactly obtained by using convex programming techniques. A simple numerical example is provided to show the applicability of the proposed methodology to real-world problems with multiple objectives in uncertain environments.     

SOLUBILITY IN ORGANIC DILUENTS AND EXTRACTION BEHAVIOR OF CALIX[4]ARENE CARBOXYLATES WITH DIFFERENT ALKYL CHAINS

ABSTRACT

Two types of alkylcalix[4]arene carboxylates with different alkyl chains, together with three types with the same alkyl chains were synthesized to investigate their solubility in four different organic diluents. The solubility was found to be enhanced by using the calixarene compounds with longer alkyl chains and by using mixtures of compounds with different alkyl chains. The order of solubility in the different organic diluents was found to be:

chloroform > toluene ? EXXSOL D80 ≈ hexane.

The stoichiometry of the copper complex with the compounds having the same alkyl chains was also determined and the maximum loading capacity of copper with each extractant was estimated.