Mesophases textures

Several fundamental studies have shown the importance of monomer sequence distribution on mesophase behavior (26). Simply changing the direction of ester linkages in a chain affects the transition temperatures, the range of the mesophase stability and, in some cases, even the mesophase texture (2Z). Polyester chains are susceptible to transesterification, which raises the question of which sequence structure is actually responsible for the properties observed for a given polymer. A recent study of aromatic LC polymers by neutron scattering indicates that transesterification occurs in the mesophase at rates twice that in poly(ethylene terephthalate) (28). Such behavior has also been observed to occur in other aromatic polyesters where rapid sequence redistribution was detected by nmr, see for example, the chapters by Jin and Economy et al. The temperature dependence of this effect has not been fully explored, and it may not be as pronounced in those polymers which exhibit mesophase behavior at lower temperatures, for example, those with aliphatic spacers. 

Optical observations of mesophase textures have been previously discussed in detail It is to be stressed here that they are generally in excellent agreement with thermal analysis data and indicate the existence of smectic and nematic phases in samples 42 (w=2) through i (DP =4.1). On the contrary, polymer 43 7 CBPj =8.7) displayed a weakly birefringent, possibly nematic, texture. 

The bulk polymer obtained after 80 min at 110 C in N2 atmosphere is white, veiy hard and brittle. The texture of a thin film of this polymer looks like a disordered mesophase texture. The polymer is insoluble in all the classical solvents except in the dimethylformamide. It swells in chloroform. The thermogram of this polymer does not exhibit any transition from room temperature until 260 C. 

It is interesting to comment on the mesophase texture of the LC polyesters based on HB. Literature data concludes that the polyesters with an even number of methylene groups in the spacer present smectic type textures, while the polyesters with an odd number of methylene groups... 

With some practice and the aid of published photomicrographs of mesophase textures [3, 28], it is possible to recognize features that are specific to nematic and smectic phases and, moreover, to differentiate among various smectics. Additionally, via specific surface treatments - rubbing and sometimes also chemically... 

The polyamides are soluble in high strength sulfuric acid or in mixtures of hexamethylphosphoramide, /V, /V- dim ethyl acetam i de and LiCl. In the latter, compHcated relationships exist between solvent composition and the temperature at which the Hquid crystal phase forms. The polyamide solutions show an abmpt decrease in viscosity which is characteristic of mesophase formation when a critical volume fraction of polymer ( ) is exceeded. The viscosity may decrease, however, in the Hquid crystal phase if the molecular ordering allows the rod-shaped entities to gHde past one another more easily despite the higher concentration. The Hquid crystal phase is optically anisotropic and the texture is nematic. The nematic texture can be transformed to a chiral nematic texture by adding chiral species as a dopant or incorporating a chiral unit in the main chain as a copolymer (30). 

To date, there has been relatively little work reported on the mesophase pitch rheology which takes into account its liquid crystalline nature. However, several researchers have performed classical viscometric studies on pitch samples during and after their transformation to mesophase. While these results provide no information pertaining to the development of texture in mesophase pitch-based carbon fibers, this information is of empirical value in comparing pitches and predicting their spinnability, as well as predicting the approximate temperature at which an untested pitch may be melt-spun. 

The above equations have been solved to predict the commonly observed radial and line-origin textures seen in circular and non-circular mesophase pitch-based carbon fibers [39]. 

The properties of mesophase pitch-based carbon fibers can vary significantly with fiber texture. Inspection of the cross-section of a circular mesophase fiber usually shows that the graphitic structure converges toward the center of the fiber. This radial texture develops when flow is fully developed during extrusion through the spinnerette. Endo [48] has shown that this texture of mesophase pitch-based carbon fibers is a direct reflection of their underlying molecular structure. 

Fig. 8. Observed textures of mesophase piteh-based earbon fibers (adapted from [55]).

Since PAN-based carbon fibers tend to be fibrillar in texture, they are unable to develop any extended graphitic structure. Hence, the modulus of a PAN-based fiber is considerably less than the theoretical value (a limit which is nearly achieved by mesophase fibers), as shown in Fig. 9. On the other hand, most commercial PAN-based fibers exhibit higher tensile strengths than mesophase-based fibers. This can be attributed to the fact that the tensile strength of a brittle material is eontrolled by struetural flaws [58]. Their extended graphitic structure makes mesophase fibers more prone to this type of flaw. The impure nature of the pitch preciusor also contributes to their lower strengths. 

Mochida, I., Yoon, S. H. and Korai, Y., Control of transversal texture in circular mesophase pitch-based carbon fibre using non-circular spinning nozzles, J Mat Sci, 1993,28, 2331 2336. 

Thermotropic liquid-crystalline properties of different metal alkanesulfonates are studied by microscopy and X-ray diffraction [59]. Sodium soaps show smectic polymorphism of smectic A and smectic B phases. Ammonium soaps only show smectic A phases but polymorphism in the crystalline state. Calcium soaps show columnar mesophases. In Figs. 32 and 33 some textures and x-ray diffraction patterns are depicted. 

Lyotropic liquid crystalline nanoparticles have also been described. Concentrated solutions of gold nanorods in water in the presence of a surfactant (cetyltrimethyl-ammonium bromide) display a nematic mesophase stable up to 200 °C [74[. The N mesophase was identified by optical microscopy by their typical nematic droplets texture. 

Preliminary room temperature x-ray data of 0.65 Me4C00-PECH indicates that the sample presents a highly ordered smectic mesophase which was not yet completely assigned. The textures seen by polarized optical microscopy are also typical of smectic phases. Due to the very high molecular weights involved, textures specific to mesophase in thermodynamic equilibrium could not be developed within a reasonable amount of time by annealing. 

Figure 7. Optical micrograph of VII showing texture of the mesophase at 182 °C. Magnification 320 X.

Figure 9.1 Examples of texture of the materials formed on a short range from amorphous Si02 (a) silica gel (b) hydrothermally treated silica gel (c) porous glass (d) mesoporous mesophases type of MCM-41 and (e) opal.

Hexagonal mesophases can be recognized by their typical fan-shape texture (Fig. 7a). Lamellar mesophases typically show oily streaks with inserted maltese crosses (Fig. 7b). The latter are due to defects, called confocal domains, that arise from a concentric rearrangement of plane layers. In some lamellar mesophases these defects prevail. Hence no oily streaks occur but maltese crosses are the dominant texture (Fig. 7c). 

The smectic mesophases of the thermotropic liquid crystals show a variety of textures but resemble mainly the fan-shape texture of the lyotropic hexagonal meso-phase. For further reading more comprehensive literature is recommended [11]. 

Maceral behaviour and interaction on carbonization Mesophase development during carbonization Relation of coke strength (stability) to coke texture, pore size distribution, pore wall thickness... 

The mesophases of LC diols la-lg were also observed directly in polarized optical micrographs taken immediately after melting the sample. Textures were identified only by comparison with published micrographs (2 ), and are therefore tentative. A nematic texture is observed for If (Fig. 2), while more highly ordered smectic textures are observed for Ib-le and Ig (Fig. 3). 

Note 4 At one time, a number of mesophases were identified as smectic on the basis of their optical textures, but they are in fact soft crystals characterised by very low yield stresses. Hence, these three-dimensionally ordered phases should no longer be called smectic mesophases. They are akin to plastic crystals with some elementary long-range order and are referred to by the letters E, J, G, H, and K. 

Spherical droplet that forms during a transition from an isotropic phase to a nematic mesophase. It has characteristic textures that depend on the droplet size and the director orientation at the nematic-isotropic interface. 

Note Nematic droplets display a texture characteristic of a nematic mesophase since they occur nowhere else. 

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