Phases molecular alignment

Nucleation can occur either homogeneously or heterogeneously. Homogeneous nucleation occurs when random molecular motion in the molten state results in the alignment of a sufficient number of chain segments to form a stable ordered phase, known as a nucleus. The minimum number of unit cells required to form a stable nucleus decreases as the temperature falls. Thus, the rate of nucleation increases as the temperature of the polymer decreases. The rate of homogeneous nucleation also increases as molecular orientation in the molten polymer increases. This is because the entropy difference between the molten and crystalline states diminishes as molecular alignment in the molten state increases. 

The half-widths of 37-39 and 78-88 Hz, respectively, for the crystalline and amorphous phases are significantly larger than 18 and 38 Hz for those of the bulk-crystallized linear polyethylene (cf. Table 1). This is caused by incorporation of minor ethyl branches. The molecular alignment in the crystalline phase is slightly disordered, and the molecular mobility in the amorphous phase will therefore be promoted. With broadening of the crystalline and amorphous resonances, the resonance of the interphase also widens in comparison to that of bulk-crystallized linear polyethylene samples. This shows that the molecular conformation is more widely distributed from partially ordered trans-rich, conformation to complete random conformation, characteristic as the transition phase from the crystalline to amorphous regions. 

As pointed out above with relation to the data at 87 °C, the Tic of the crystalline-amorphous interphase is appreciably longer than that of the amorphous phase, suggesting the retention of the helical molecular chain conformation in the interphase. We also note that a Tic of 65-70 s for the crystalline phase is significantly shorter than that for other crystalline polymers such as polyethylene and poly-(tetramethylene oxide), whose crystalline structure is comprised of planar zig-zag molecular-chain sequences. In the crystalline region composed of helical molecular chains, there may be a minor molecular motion in the TiC frame, with no influence on the crystalline molecular alignment that is detected by X-ray diffraction analyses. Such a relatively short TiC of the crystalline phase may be a character of the crystalline structure that is formed by helical molecular chain sequences. 

The use of birefringence to determine the behavior of 5( 7) is a natural choice since the principal characteristic of the nematic phase is optical birefringence i.e., the refractive index differs for light polarized parallel (/ n) or perpendicular (%) to the axis of molecular alignment. Eor a nematic liquid crystal, the director n specifies this optical z axis and / n = and = Dg are called the extraordinary and ordinary refractive indices, respectively. In general, rig > rig and the difference is the refractive index anisotropy (birefringence)... 

Yamamoto, T., Hasegawa, M. Kanazawa, A., Shiono, X, and Ikeda, T. Phase-type gratings formed by photochemical phase transition of polymer azobenzene liquid crystals Enhancement of diffraction efficiency by spatial modulation of molecular alignment. ]. Phys. Chem. B 1999, 103, pp. 9873-9878. 

In general, for side chain liquid-crystalline polymers, macroscopic molecular alignment is not easy and therefore clear evidence of electronic charge carrier transport was confirmed first in liquid crystals with low molecular weight. In the 1990s, fast electronic conduction was verified in discotic columnar phases of triphenylene derivatives [79,80] and hexabenzocoronene derivatives [81,82] as well as smectic phases of 2-phenylbenzothiazole [83, 84] and 2-phenylnaphthalene derivatives [85], as shown in Fig. 14. Carrier... 

The liquid crystallinity of poly(3-alkylthiophene) has been pointed out [121]. Enhancement of crystallinity by molecular alignment in a liquid crystal phase is prominent in poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b] thiophene) exhibiting a lamellar mesophase. When a thin film of the polymer fabricated by the spin-coating method is annealed at 100 °C, domain size remarkably extends from several tens of nanometers to a several micrometers, maintaining molecular alignment within domains because of the thermal motion of the polymer chains. The hole mobility of the thin film transistors based on this polymer reached 0.7 cm2 V-1 s 1 [122]. 

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