Polymorphism of Supramolecular Charge-Transfer Complex Composed of 10,10′-dihydroxy-9,9′-biphenanthryl and p-benzoquinone

Charge-transfer (CT) complexes were prepared using racemic (rac)-10,10′-dihydroxy-9,9′-biphenanthryl, which has a large and highly π-conjugated phenanthrene ring, as the electron donor and p-benzoquinone as the electron acceptor. This CT system showed a polymorphism.     

Effects of protonation of alkyldimethylamine oxides on the dissolution temperature in aqueous media

The effects of protonation (ionization) of hexadecyldimethylamine oxides on the dissolution temperature in aqueous media were investigated by differential scanning calorimetry. Only one endothermic peak was reproducibly observed at all the degrees of ionization alpha examined that were assigned to the transition from the solid (the gel phase) to the solution containing micelles. The dissolution temperature versus alpha curves showed a maximum at alpha=0.5, strongly suggesting the formation of a stable complex of 1-to-1 composition of the nonionic and cationic species through the proposed hydrogen bond. From the shape of the dissolution curve as well as the composition analysis of the solid phase, the solid solution was found to be formed over all alpha values. Effects of alkylchain length on the dissolution temperature for a homologous series of octadecyl- (C18DAO), hexadecyl- (C16DAO), and tetradecyldimethylamine oxide (C14DAO) were also examined for alpha=0.5 and alpha=1. Both the transition temperature and the associated thermodynamic quantities DeltaH and DeltaS increased systematically with the chain length, but for alpha=0.5 smaller increases in DeltaH and DeltaS values with the chain length were observed [DeltaH/CH2 (kJ mol(-1))=7.2+/-0.2 and 2.2+/-0.5 for alpha=1 and alpha=0.5, respectively, and DeltaS/CH2 (J mol(-1) K(-1))=21.9+/-1.8 for alpha=1 and 4.6+/-1.9 for alpha=0.5]. By annealing procedures, the metastable nature of the gel phase was demonstrated for the C16DAO (alpha=1) solid.     

Mechanical properties of oriented polyvinylchloride composites filled with ultrafine particles

The tensile stress-strain behaviour of undrawn and drawn polyvinylchloride (PVC) composites filled with ultrafine SiO₂ and micron sized glass particles were discussed as functions of filler content and size. For the undrawn PVC composites filled with ultrafine SiO₂ particles, Young's moduli, yield and breaking stresses increased with filler content and decreasing filler size. Whereas for the composites filled with micron sized glass particles, their Young's moduli slightly increased with filler content but both the yield and breaking stresses decreased. Oriented PVC composites were made by uniaxially drawing to × 2.5 at 100 °C. Anisotropic mechanical properties of oriented specimens were discussed in terms of compliance tensor and yield stress measured in the direction of 0°, 45° and 90° to the original stretching direction at room temperature. In the case of 70A SiO₂, all the compliance decreased with filler content, whereas those of 65μ glass, this relation was reversed. The yield stress of the oriented PVC composites showed filler size dependence similar to Young's moduli. The anisotropic yield stress of oriented PVC composites were reasonably analysed by Hill's yield criterion.