Macroscopic Property Evaluation of Titania Nanocomposite Polymer Capable of Drawing Double-Network Macrostructure Using Photolithography.

In this study, we developed a double-network hybrid polymer that controls the strength and density of cross-linking points by utilizing the bonds of titania and catechol groups with an o-nitrobenzyl group (ONBg) as the photoreactive cross-linking points. In addition, this hybrid material system, which is composed of thermally dissociable bonds between titania and carboxyl groups, can be molded before light irradiation. The Young's modulus increased by approximately 1000 times upon irradiation with UV light. Moreover, introducing microstructures using the photolithography technique improved the tensile strength and fracture energy by approximately 32 and 15 times, respectively, compared to the sample without the photoreaction. The improved toughness was achieved by the macrostructures, which enhanced the effective cleavage of sacrificial bonds between the carboxyl groups and titania.

Effect of Oligomer Segregation on the Aggregation State and Strength at the Polystyrene/Substrate Interface.

The interfacial strength of polystyrene (PS) with and without PS oligomers in contact with a glass substrate was examined to determine the relationship between the interfacial aggregation state and adhesion. The shear bond strength and adsorbed layer thickness of neat PS exhibited a similar dependence on the thermal annealing time: they increased to constant values within almost the same time. This implies that the adhesion of the polymer is closely related to the formation of an adsorbed layer at the adhesion interface. Nevertheless, in the case of PS with a small amount of oligomer, the shear bond strength decreased, while the adsorbed layer thickness was almost the same as that of neat PS. Based on the results of interfacial analyses, we propose that the interfacial segregation of the oligomer reduced the entanglement between the interfacial free chains in the adsorbed layer and the bulk chains.

Chiral Nucleating Agents Affecting the Handedness of Lamellar Twist in the Banded Spherulites in Poly(ε-Caprolactone)/Poly(Vinyl Butyral) Blends.

Chiral silica, which acts as a nucleating agent of poly(ε-caprolactone) (PCL), was demonstrated to induce excess handedness of lamellar twist in the banded spherulites of PCL blended with poly(vinyl butyral). The d- and l-forms of silica enhanced the right- and left-handed twists, respectively. The influences of chiral silica on the twist handedness were statistically significant. These results indicate that the handedness of twisting can be controlled upon primary nucleation. The organic substances used as chiral templates of silica had no effect on the handedness; silica was shown to govern the handedness. The possible mechanisms of the chirality transfer are discussed.

Relation between the helical twist and S-shaped cross section of the lamellar crystals of polyethylene.

The relation between the handedness of helical twist and the S-shaped cross section of the lamellar crystals is discussed for linear polyethylene. The lamellar crystals are found to rotate so that the convex surfaces of "S" push aside the melt when they advance in the growth direction. This relation, which has not been examined sufficiently so far, is found to be opposite from what was proposed earlier. A model to explain these observations is presented. This paper also demonstrates that the twist handedness can be clarified based on the stack order of crystalline lamellae without any treatment such as etching or extraction to isolate the lamellar crystals.

Thermal properties and microstructures of methylated polyrotaxane solutions.

Aqueous solutions of polyrotaxanes consisting of poly(ethylene glycol) and methylated alpha-cyclodextrins (alpha-CD) were studied by means of differential scanning calorimetry (DSC), dynamic light scattering, and X-ray diffraction in order to investigate the effect of the degree of methylation on thermoresponsive behavior. Polyrotaxanes with a degree of methylation higher than 50% had a lower critical solution temperature (LCST) and showed reversible associations and dissociations in water. In the transmittance measurements, the cloud point of methylated polyrotaxanes (MePR) shifted to a lower temperature with an increase in the degree of methylation. The heating curve obtained by DSC for the nearly permethylated polyrotaxane showed one broad endothermic peak that was associated with the microcrystallization of methylated CDs by hydrophobic interactions. On the other hand, the DSC profiles for partially methylated polyrotaxanes had several endothermic peaks, indicating multiple phase transitions of the MePR solutions. The results imply that the thermal properties of the MePR-water system are significantly affected by not only the methyl groups on alpha-CDs but also by the remaining hydroxyl groups.

Various crystalline morphology of poly(butylene succinate-co-butylene adipate) in its miscible blends with poly(vinylidene fluoride).

Poly(vinylidene fluoride) (PVDF) and poly(butylene succinate-co-butylene adipate) (PBSA) are crystalline/crystalline polymer blends with PVDF being the high-T(m) component and PBSA being the low-T(m) component, respectively. PVDF/PBSA blends are miscible as shown by the decrease of crystallization peak temperature and melting point temperature of each component with increasing the other component content and the homogeneous melt. The low-T(m) component PBSA presents various confined crystalline morphologies due to the presence of the high-T(m) component PVDF crystals by changing blend composition and crystallization conditions in the blends. There are mainly three different types of crystalline morphologies for PBSA in its miscible blends with PVDF. First, crystallization of PBSA commenced in the interspherulitic regions of the PVDF spherulites and continued to develop inside them in the case of PVDF-rich blends under two-step crystallization conditions. Second, PBSA spherulites appeared first in the left space after the complete crystallization of PVDF, contacted and penetrated the PVDF spherulites by forming interpenetrated spherulites in the case of PVDF-poor blends under two-step crystallization condition. Third, PBSA spherulites nucleated and continued to grow inside the PVDF spherulites that had already filled the whole space during the quenching process in the case of PBSA-rich blends under one-step crystallization condition. The conditions of forming the various crystalline morphologies were discussed.