Mesophase

There has been much activity in the study of monolayer phases via the new optical, microscopic, and diffraction techniques described in the previous section. These experimental methods have elucidated the unit cell structure, bond orientational order and tilt in monolayer phases. Many of the condensed phases have been classified as mesophases having long-range correlational order and short-range translational order. A useful analogy between monolayer mesophases and die smectic mesophases in bulk liquid crystals aids in their characterization (see [182]). 

Fig. IV-17. A schematic phase diagram illustrating the condensed mesophases found in monolayers of fatty acids and lipids.

Molecules tliat are capable of fonning liquid crystal phases are called mesogens and have properties tliat are mesogenic. From the same root, tire tenn mesophase can be used instead of liquid crystal phase. A substance in a liquid crystal phase is tenned a liquid crystal. These conventions follow tliose in tire Handbook of Liquid Crystals, [4, 5 and 6] tire nomenclature of which [7] for various liquid crystal phases is adopted elsewhere in tliis section. 

NMR is not the best method to identify thennotropic phases, because the spectmm is not directly related to the symmetry of the mesophase, and transitions between different smectic phases or between a smectic phase and the nematic phase do not usually lead to significant changes in the NMR spectmm [ ]. However, the nematic-isotropic transition is usually obvious from the discontinuous decrease in orientational order. NMR can, however,... 

This range yields more highly tmncated cones. The main mesophase stmcture obtained from these units is a flexible bilayer such as that fonned in vesicles and liposomes. These arrangements are often obtained from doublechain surfactants such as lecithin, double tailed cationic surfactants and AOT. 

This parameter corresponds to cylindrical packing shapes. Surfactants and amphiphiles falling in this range often produce planar bilayers and lamellar mesophases. Such cylindrical building blocks also contribute to many... 

Figure C2.3.13. Nonnal (H, left) and inverse (H, right) hexagonal mesophases composed of rodlike micelles.

Mortensen K 1996 Structural studies of PEO-PPO-PEO triblock copolymers, their micellar aggregates and mesophases a small-angle neutron scattering study J. Phys. Condens Matters A103-A104... 

Kurst G R, R A Stephens and R W Phippen 1990. Computer Simulation Studies of Anisotropic iystems XIX. Mesophases Formed by the Gay-Berne Model Mesogen. Liquid Crystals 8 451-464. e F J, F Has and M Orozco 1990. Comparative Study of the Molecular Electrostatic Potential Ibtained from Different Wavefunctions - Reliability of the Semi-Empirical MNDO Wavefunction. oumal of Computational Chemistry 11 416-430. 

Lyophobic colloids Lyotropic liquid crystals Lyotropic mesophases Lyotropic polymers Lyral [31906-04-4]... 

The positional order of the molecules within the smectic layers disappears when the smectic B phase is heated to the smectic A phase. Likewise, the one-dimensional positional order of the smectic M phase is lost in the transition to the nematic phase. AH of the transitions given in this example are reversible upon heating and cooling they are therefore enantiotropic. When a given Hquid crystal phase can only be obtained by changing the temperature in one direction (ie, the mesophase occurs below the soHd to isotropic Hquid transition due to supercooling), then it is monotropic. An example of this is the smectic A phase of cholesteryl nonanoate [1182-66-7] (4), which occurs only if the chiral nematic phase is cooled (21). The transitions are aH reversible as long as crystals of the soHd phase do not form. 

The importance of unsaturation is illustrated by the fact that 2,4-nonadienoic acid [21643-39-0] forms a Hquid crystal phase, whereas the aHphatic carboxyHc acids do not. The two double bonds enhance the polarizabiHty of the molecule and bring iatermolecular attractions to a level that is suitable for mesophase formation. The overall linearity of the molecule must not be sacrificed ia poteatial Hquid crystal candidates. For example, whereas /n j - -aIkoxyciaaamic acids (5) are mesomorphic, the cis isomers (6) are not, a reflection of the greater anisotropy of the trans isomer. 

A variety of aromatic and extended-chain polyamides that spontaneously form a mesophase ia coaceatrated solutioas also have beea syathesized (30). Polybeozamide [24991-08-0] with the foUowiag repeat uoit, is an example. 

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). 

The number of examples of Uquid crystalline systems is limited. A simple discotic system, hexapentyloxytriphenylene (17) (Fig. 4), has been studied for its hole mobUity (24). These molecules show a crystalline to mesophase transition at 69°C and a mesophase to isotropic phase transition at 122°C (25). 

In the mesophase, the molecules exist in a discotic hexagonal columnar ordered stmcture, schematically shown in Figure 4. 

The ordered columnar arrangement of the hexapentyloxytriphenylene molecules provides good overlap of the -electrons of the triphenylene moieties along the director axis. This results in efficient hole transport in the mesophase. The hole photocurrent shows nondispersive transport with a high mobihtyup to 1 X 10 cm /Vs (24). 

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 specification requirements for electrode binder pitch, eg, high C/H ratio, high coking value, and high P-resin content, effectively ruled out pitches from gasworks or low temperature tars. The cmde tar is distilled to a medium-soft pitch residue and then hardened by heating for several hours at 385—400°C. This treatment increases the toluene-insoluble content and produces only a slight increase in the quinoline-insoluble (Ql) material, the latter by the formation of mesophase. 

Mesophase formation in coal-tar pitch is encouraged by a reduction of the natural quinoline-insoluble matter content, which resembles carbon black but is not optically anisotropic and is characterized by an atomic carbon hydrogen ratio of 4 1. In contrast, the atomic carbon hydrogen ratio of mesophase is about 2 1. 

The property of mesophase that makes it suitable for carbon fiber and premium coke manufacture is that it forms ordered stmctures under stress which persist following carbonization. However, most carbon fiber production in the 1990s is based on polyacrylonitrile (PAN). 

It was estabhshed ia 1945 that monolayers of saturated fatty acids have quite compHcated phase diagrams (13). However, the observation of the different phases has become possible only much more recendy owiag to improvements ia experimental optical techniques such as duorescence, polarized duorescence, and Brewster angle microscopies, and x-ray methods usiag synchrotron radiation, etc. Thus, it has become well accepted that Hpid monolayer stmctures are not merely soHd, Hquid expanded, Hquid condensed, etc, but that a faidy large number of phases and mesophases exist, as a variety of phase transitions between them (14,15). 

Mesogenic diols, such as 4,4 -bis( CO-hydtoxyaLkoxy)biphenyls, ate used with 2,4-TDI or 1,4-diisocyanatobenzene (PPDI) to constmct Hquid crystalline polyurethanes (7). Partial replacement of the mesogenic diols by PTMG shows that the use of lower molecular weight flexible spacers form polymers that have a more stable mesophase and exhibit higher crystallinity (8). Another approach to Hquid crystal polyurethanes involves the attachment of cholesterol to the polyurethane chain utilizing the dual reactivity in 2,4-TDI (9). 

Pitches can be transformed to a mesophase state by further chemical and physical operations. Heat treatment of conventional pitches results in additional aromatic polymeriza tion and the distillation of low molecular weight components. This results in an increase in size and concentration of large planar aromatic molecular species whereupon the precursor pitch is transformed to a mesophase state exhibiting the characteristics of nematic Hquid crystals (1). Additional heat treatment converts the mesophase pitch to an infusible aromatic hydrocarbon polymer designated as coke. 

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