Search

Three types of amorphous phases (ferroelectric metastable phase A with large remanent polarization, ferroelectric metastable phase B with small remanent polarization and paraelectric stable phase C) are identified in as-quenched and/or annealed nylon 6 films on the basis of the thermal data obtained by light-modulated differential scanning calorimetry (LMDSC) as well as X-ray data, which show different glass transition temperatures and d -spacings. The irreversible exothermic anomaly at 328 K observed through heating process in the conventional DSC is attributed to transition from phases A and/or B to nematic phase. The transition from phase A to phase B is considered to complete after 15 min annealing at 320 K on the basis of the LMDSC data, which corresponds to abrupt diminution of the remanent polarization by the correspondent annealing condition. Such results suggest that ferroelectricity of nylon 6 film is mainly attributed to phase A (frozen state of the melt) formed in the quenched nylon 6 thin film.

Temperature dependence of crystal structures is examined with X-ray diffraction at normal pressure or elevated pressures for solution-grown nylons with octamethylene moiety between amino or carboxy groups (nylons 82, 410, 610, 810). Although octamethylene moiety between amino groups has the potential to cause the phase transition, the low melting point veils the transition appearance. Considering this comprehensively with previous results, it is concluded for all even–even nylons, that the phase transition in the two-dimensional methylene layer system can be experimentally observed only in nylon 6Y (Y≤8) crystals at normal and/or high pressures, where the hexamethylene moiety between amino groups plays an intrinsic role. The so-called `Brill transition' widely reported for melt-crystallized nylons is not a phase transition but an abrupt thermal expansion.

Vinylidene fluoride/trifluoroethylene (VDF/TrFE) copolymer crystals were grown from the dilute solution on cleaved (0001) surface of highly oriented pyrolytic graphite (HOPG). Using transmission electron microscopy, the orientational relation between the copolymer crystals and cleaved (0001) surface of HOPG is clarified, as well as the supperlattice matching. Electron diffraction (ED) patterns with 6-fold symmetry were observed for the copolymer crystals with VDF molar contents of 59, 65, and 71%. It suggests that a rectangular array of (20\bar1) plane for the high-temperature phase (HP) of the copolymer crystal faces HOPG(0001) plane, from which the molecular chains tilt by 46.7°. The ED pattern with such 6-fold symmetry is attributed to superposition of diffractions from the HP crystallites with three different orientations on HOPG. Such results suggest that epitaxial growth of HP occurred and it was frozen or stabilized even at room temperature due to epitaxial effect or interaction between copolymer m...

The structure formation of a single polymer chain in solution with explicit solvent molecules is investigated by molecular dynamics simulation. The orientationally ordered structure is formed at a low temperature by quenching from a random conformation at a high temperature. The growth of the global and local orientational order proceeds in a stepwise manner at T ≥350 K, whereas it proceeds in a gradual manner at T =300 K. From the detailed analyses of the parallel ordering process, it is found that a conformational change of the polymer chain occurs at first, and then parallel ordering starts to take place. In comparison with the simulation results of an isolated polymer chain in vacuum, it is ascertained that the stem length of the orientationally ordered structure formed in solution becomes 2–3 times longer than that formed in vacuum.