Molten mesophases

The melt-spinning process used to convert mesophase pitch into fiber form is similar to that employed for many thermoplastic polymers. Normally, an extruder melts the pitch and pumps it into the spin pack. Typically, the molten pitch is filtered before being extruded through a multi-holed spinnerette. The pitch is subjected to high extensional and shear stresses as it approaches and flows through the spinnerette capillaries. The associated torques tend to orient the liquid crystalline pitch in a regular transverse pattern. Upon emerging from the... 

Besides this, the remarkable properties of gold(I) compounds, which often give rise to aurophilic interactions and/or to luminescence, are of interest when these properties are transported into the liquid crystal field. Although there is much still to be studied, it is already clear that luminescence can survive in the condensed but mobile state of a mesophase, and even in the isotropic liquid state of a molten gold compound. It also seems that aurophilicity can contribute in some cases to the formation of mesophases. 

The organic molten salt mesophases I referred to are ordered liquid crystals with strong electrostatic constraints between the layers. 

In the domain structures found for mesophases of molten alkali carbox-ylates, isomerism of the fatty acid chain makes an enormous difference to domain size for example, it is much larger for n than for isoalkane carboxylates. 

Characterization Techniques for Pitch Materials. Among a number of characterization techniques developed in Japan, the technique due to the members of the Society of Heavy Oil, led by Kunugi, stands out as particularly useful. The analytical data are treated by computer methods to construct average molecular structures for the carbonaceous materials. Sanada s group in Hokkaido University used high-temperature NMR and ESR data obtained by in situ measurements of pitch materials in molten salt (21). Much information on mesophase behavior during the heat-treatment process was obtained in this way. 

One of the most surprising observations was that the X-ray diffraction pattern of the azoxy polymers showed crystalline-like d-spacings in the liquid crystalline melt while in the isotropic region the polymers showed the expected amorphous halo. A possible explanation of such a highly ordered mesophase was the retention of much of the order of the solid in the molten state. A highly structured mesophase occurs in the smectic E state where directional and layered order are maintained in the melt... 

Typical polarized optical micrographs of the molten samples were shown in Figure 1. Microscopic analyses were earned out at temperatures in the range 25 - 390 C, and threaded textures, a characteristic optical texture of nematic mesophase, were observed above LCITs over the investigated composition range. The nematic to isotropic transitions were not observed up to 390 C. 

Poly(2,5-di-n-dodecyl-l,4-phenylene) of 73000-94000 show a single anisotropic liquid crystalline mesophase in the molten state and macromolecules with Mw 44000—73000 gave coexisting isotropic/anisotropic phases [17]. 

An examination of the composition and physical state of sebum suggests that several cleaning mechanisms can operate during its removal from hair. Since sebum is completely molten at body temperature [122], it can be effectively removed by the roll-back mechanism. Also, the presence of approximately 25% free fatty acids in sebum indicates, as discussed in Section IV.C.3, that it is subject to removal by emulsification and mesophase formation. Finally, because the concentration of detergents during shampooing is well above their critical micelle concentrations, sebum can also be cleaned from hair by solubilization. 

Such a mobility does not exist in layered LC-main chain polymers (Fig. 1 IB). The mobility required for the definition and existence of a molten state results in LC-main-chain polymers exclusively from a gliding of chains along each other. Such a motion is only possible when the intermolecular forces between the mesogens are relatively weak. Therefore only smectic -A and smectic -C phases are true LC-phases. In contrast to small molecules smectic -B (and higher ordered smectic phases) are solid mesophases. The difference between a solid smectic mesophase and a smectic crystalline phase lies in the extent of the three dimensional order and is usually difficult to determine experimentally (see Sect. 7). 

The polycarbonates 62a-f and 63a-f were prepared by transesterification of the corresponding diols with the biscarbonate 55 in the molten state. At least after annealing all members of both series were semicrystalline showing a melting endotherm in the DSC heating traces. Unfortunately, DSC curves of 62a-f were not published. An unidentified birefringent mesophase was mentioned for 62a-e, whereas a nematic melt was reported for 62f. However, the published texture of this melt is not a typical nematic Schlieren texture, but looks like a suspension of solid particles in an isotropic melt. For all members of series 63a-f a nematic... 

If it is straightforward to understand why columnar mesophases are easily obtained with disk-like shaped molecules (the columns are formed by the piling of the flat cores of the molecules, the molten aliphatic chains filling the space between the columnar cores), it may appear rather surprising, at first sight, to observe columnar mesophases with polycatenar calamitic molecules. 

Over recent years the question of whether or not surfactants form aggregates similar to micelles and mesophases in other polar solvents has received considerable attention [168-191]. The solvents concerned are polar liquids such as glycerol, ethylene glycol, formamide or ethyl ammonium nitrate (a molten electrolyte at ambient temperature). The answer is yes, but the thermodynamics of the aggregation process is somewhat different. Figures 40 and 41 show measurements of EMF in hexadecylpyridinium bromide solutions where water and ethylene glycol are solvents. 

There are two principal categories of mesophases, thermotropic and lyotropic. Thermotropic liquid crystals are formed within a particular range of temperature in a molten material, with no solvent present, whereas lyotropic liquid crystals are formed by some substances when they are dissolved in a solvent. Within each of these categories there are three distinct classes of mesophases, which were first identified by Friedel in 1922. The simplest of these to describe are the nematic and smectic classes, illustrated schematically in fig. 12.16. These phases are formed by long thin rigid molecules which tend to line up parallel to each other. 

Mesophase reveals intermediate order between amorphous and crystaUine phases. In the first studies it was labelled as smectic (Natta Corradini, 1960) or paracrystalline (Miller, 1960). Further studies revealed that mesophase is made up of bundles of parallel chains, which maintain typical for all polymorphic forms of polypropylene three-fold helical conformation. Bundles are terminated in the direction of the chain axis by helix reversals or other conformational defects (Androsch et al., 2010). In the bundles long range ordering maintains only along the chain axes, whereas in lateral packing a large amount of disorder is present (Natta Corradini, 1960). The mesophase is formed by quenching of the molten polypropylene (Miller, 1960 Wyckoff, 1962) or by deformation of the crystalline structure (Saraf Porter, 1988 Qiu, 2007). As for the fibres, the mesophase was observed in fibres taken at low take-up velocity (Spruiell White, 1975 Jinan et al., 1989, Bond Spruiell, 2001) in fibres intensively cooled in water with addition of ice or in the mixture of dry ice... 

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