Mesophase melting

The same reaction carried out with amines leads to diaminocarbenes (Figure 7.12) [11]. Only complexes prepared from primary amines show smectic A mesophases (melting points from 113 to 137 °C), although they gradually decompose before the clearing points. 

As most polyimides are extremely high melting (>500 °C) with aromatic symmetric spacers, the introduction of linear aliphatic spacers is one successful strategy for producing meltable and soluble polymers. PEIs derived from highly symmetrical imide units (e.g. pyromellitic imide, naphthalene 1,4,5,8 imide units) give rise to isotropic and not mesophasic melts [8-11]. However, PEIs containing N, W -dihydroxypyromellitimide (1) have been reported to contain broad nematic phases in the melt [12]. 

For the remaining members of the series Ci2EO, and C12EO0 (dodecanol) no mesophases occur, only separate water and am-phiphile phases which show slight miscibility. With all the C12 surfactants no meso-phase exists above 80 °C, while the maximum mesophase melting temperature varies much less than the cloud temperatures. 

The polymers were formed by condensation of 4,4dihydroxy-benzene and 2,2 -dimethyl-4,4 dihydroxyazoxybenzene with various diacid chlorides acting as flexible spacer groups Polydisperse homopolymers and copolymers, sharp fractions of homopolymers and mixtures of polydisperse polymers with a low mass mesogen were investigated. Supercooling at the mesophase-isotropic and solid-mesophase transitions, sharpness of the nematic-isotropic transition (range of N+I biphase), polymer crystallization from the mesophase melt, and enhancement of crystallinity upon addition of a low mass nematic, were studied. 

Higher contents of CDM (above 50%) led to sharper melting endo-therms and clearing points could be observed. Actually only a portion of the mesophase melted isotropically while the remaining portion remained unchanged. We ascribe this to the inhomogeneity of the copolymer samples. The diol components will deviate in reactivity in the copolyester preparation resulting in compositional variations in the products prepared by the batch polymerizations. The sequence distributions in the polymers are not known. In addition to the variation between the aliphatic and the aromatic component the cisjtrans distribution of the former may also vary. 

No coherent threadline could be maintained and the extmdate flew off the windup as short, brittle, crystalline lengths. Not until many years later did other workers show that this polymer on cooling exhibits a mesophase transition directly from the isotropic melt to a smectic A phase. Good sources of information on Hquid crystals and Hquid crystal polymers are available (212—216). 

The mesophase pitch is then extmded and melt spun through spinnerettes into fibers. The flow pattern of the mesophase during fiber formation has a strong influence on the morphology of the fiber (52—54) and can result in fibers with radial, onion-skin, or random microstmctures. Commercially available PBCFs have a round cross section, but this can be easily modified by changing the cross section of the spinnerette holes. Multilobal and C-shaped fibers have been produced with exceptional mechanical properties (55). 

Many cellulose derivatives form Hquid crystalline phases, both in solution (lyotropic mesophases) and in the melt (thermotropic mesophases). The first report (96) showed that aqueous solutions of 30% hydroxypropylceUulose [9004-64-2] (HPC) form lyotropic mesophases that display iridescent colors characteristic of the chiral nematic (cholesteric) state. The field has grown rapidly and has been reviewed from different perspectives (97—101). 

Fibers produced from pitch precursors can be manufactured by heat treating isotropic pitch at 400 to 450°C in an inert environment to transform it into a hquid crystalline state. The pitch is then spun into fibers and allowed to thermoset at 300°C for short periods of time. The fibers are subsequendy carbonized and graphitized at temperatures similar to those used in the manufacture of PAN-based fibers. The isotropic pitch precursor has not proved attractive to industry. However, a process based on anisotropic mesophase pitch (30), in which commercial pitch is spun and polymerized to form the mesophase, which is then melt spun, stabilized in air at about 300°C, carbonized at 1300°C, and graphitized at 3000°C, produces ultrahigh modulus (UHM) carbon fibers. In this process tension is not requited in the stabilization and graphitization stages. 

A relatively new class of high-performance carbon fibers is melt-spun from mesophase pitch, a discotic nematic liquid crystalline material. This variety of carbon fibers is unique in that it can develop extended graphitic crystallinity during carbonization, in contrast to current carbon fibers produced from PAN. 

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... 

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. 

A very unusual characteristic of mesophase pitch is the extreme dependency of its viscosity on temperature [19,34,35]. This factor has a profound influence on the melt-spinning process (described above), as a mesophase pitch fiber will achieve its final diameter within several millimeters of the face of the spinnerette, in sharp contrast to most polymeric fibers. 

Martin [25] has also shown that ammonium salts display similar behavior. [Cetyltrimethylammonium]2[ZnCl4], for example, first melts to an Sc-type liquid crystal at 70 °C and then to an S -type mesophase at 160 °C. The broad diffraction features observed in the liquid-crystalline phases are similar to those seen in the original crystal phase and show the retention on melting of some of the order originating from the initial crystal, as shown in Figure 4.1-6. 

In the case of monotropic behavior, the isotropiza-tion endotherm and the corresponding thermodynamic parameters for the mesophase-isotropic transition can be obtained by isolating the mesophase when cooling from the melt and holding the temperature in a region where the transformation into the crystal is very slow... 

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