Molecular nematics

Jelley EE. 1937. Molecular, nematic and crystal states of l,l -diethyl- /-cyanine chloride. Nature 139 631-632. 

Similarly with low-molecular nematics is manifested in that the nematic polymers may form equally well schlieren texture, typical for low-molecular nematics (Fig. 18a) (polymers B.3.3-B.3.4, Table 9). The enthalpy of transition from LC state to isotropic melt is also close to that for low-molecular nematics. At the same time, there also exist definite structural differences. X-ray patterns of the same polymers, even in unoriented state, display certain elements of structural ordering in the arrangement of side branches (a weak diffuse halo at small angles), which could indicate a sibotactic nematic type of ordering. These differences are most distinct for oriented polymer films. As an example Fig. 18b, c, present X-ray patterns of unoriented and oriented samples of one and the same nematic polymer 121 l24. In fact two sharp small angle... 

Such polymers adopt, when affected by a mechanical field, an optically uniaxial homeotropic structure polymers B.1.2, B.1.7, B.1.8 (Table 8) have positive birefringence polymers B.1.1, B.1.8. (Table 9) have negative birefringence, which has not been reported to our knowledge, for low-molecular nematic liquid crystals. Although the authors do not comment on the cause for the observed phenomenon, the fact in itself is sufficiently uncommon. 

For a nematic polymer in a transition region from LC to isotropic state, maximal viscosity is observed at low shear rates j. For a smectic polymer in the same temperature range only a break in the curve is observed on a lgq — 1/T plot. This difference is apparently determined by the same reasons that control the difference in rheological behaviour of low-molecular nematics and smectics 126). A polymeric character of liquid crystals is revealed in higher values of the activation energy (Ef) of viscous flow in a mesophase, e.g., Ef for a smectic polymer is 103 kJ/mole, for a nematic polymer3 80-140kJ/mole. 

For low-molecular nematic liquid crystals three major kinds of electrooptical effects, shown on Fig. 24 2 are distinguished. 

It was shown that polymers with a short spacer (n = 2) exhibit low threshold voltages of reorientation (4-5 V) which are close to the corresponding values for low-molecular nematics, while for polymers with longer spacer groups (n = 6) the observed... 

For low molecular liquid crystals, htp is usually within the 0.5-1 x 10 2 nm" range. Approximate evaluation of htp for cholesterol-containing monomers has given the values of 0.5 x 10 2 nm l in ChA-5/AM-5 copolymers. This gives reason to assert that the mechanism of cholesteric mesophase formation is the same as in blends of low molecular nematics and cholesterics. 

The values given in Table 2 exceed the activation energy of the rotational viscosity of CN-containlng low molecular nematics, which is equal to 36-52 kJ/mole6. At the same time, they are close to the E values of processes... 

Polymers may exhibit liquid crystalline, ordered structures similar to those of small molecular liquid crystals. As polymer chains are very long, containing about 10 -10 monomer units, only parts of them or side groups can be ordered in oeir tic. cholesteric, and different kinds of smectic structures. As in small-molecular nematic liquid crystals, in nematic polymer structures groups of cylindrical-like symmetry are arranged statistically with their long axes along a certain direction. 

As mentioned, a lot of theoretical and experimental studies have been performed to understand physics and rheological properties of lyotropic LCPs. The molecular Doi approach with many improvements and experimental tests is well presented in the literature (e.g., see Ref. [5]). But the thermotropic LCPs were poorly understood till recently, in spite of many attempts to develop either nematodynamic or molecular description of their flow properties. The beauty of continuum approach is that it can be applied to molecular nematics ofboth different types, as well as to the nonyielding suspensions with shaped particles. Yet, general nematodynamic theories are multi-parametric. For example, the general LEP continuum LC theory contains five constitutive parameters [2]. Similarly, de Gennes potential proposed for the monodomain description of general weakly elastic behavior of LCE has also five parameters [37]. Because viscoelasticity is a combination of elastic and viscous effects, it is expected that even in easy theoretical schemes, the continuum approach to viscoelastic polymer nematodynamics should involve at least 10 constitutive parameters. 

New mathematical techniques [22] revealed the structure of the theory and were helpful in several derivations to present the theory in a simple form. The assumption of small transient (elastic) strains and transient relative rotations, employed in the theory, seems to be appropriate for most LCPs, which usually display a small macromolecular flexibility. This assumption has been used in Ref [23] to simplify the theory to symmetric type of anisotropic fluid mechanical constitutive equations for describing the molecular elasticity effects in flows of LCPs. Along with viscoelastic and nematic kinematics, the theory nontrivially combines the de Gennes general form of weakly elastic thermodynamic potential and LEP dissipative type of constitutive equations for viscous nematic liquids, while ignoring inertia effects and the Frank elasticity in liquid crystalline polymers. It should be mentioned that this theory is suitable only for monodomain molecular nematics. Nevertheless, effects of Frank (orientation) elasticity could also be included in the viscoelastic nematody-namic theory to describe the multidomain effects in flows of LCPs near equilibrium. 

Identification of nematic polymeric mesophases is a more complex problem than identification of polymer smectics. The structural data are usually limited to finding the absence of small-angle reflections in the x-rays of unoriented samples. The low enthalpy of the transition from the anisotropic to the isotropic phase (Table 6.9), close to the corresponding values characteristic of low-molecular nematic liquid crystals, and the absence of layered reflections indicate the one-dimensional type of ordering, although these data are insufficient for a complete description of the structure of nematic polymers, which can be both similar to and (Afferent from low-molecular-weight nematics. 

Later, electroiuc conduction by electrons in a discotic liquid crystal had been observed [7] and this finding was used to establish the electronic conductivity in a low molecular nematic liquid crystal phase [8], Furthermore, these findings illustrate why until lately electiOTuc conduction had not been found in liquid crystal material and why only ionic conduction in liquid crystals had been supported by the experimental results so far. 

It is occasionally desirable to retain a small proportion of molecular orientation, in order to quantitate the dipolar interactions present, whilst minimizing their contribution to the linewidth. Partial orientation may be achieved by using a nematic solvent. In large, magnetically anisotropic molecules it may occur naturally at the highest magnetic fields. 

Allen M P, Warren M A, Wilson M R, Sauron A and Wiliam S 1996 Molecular dynamics calculation of elastic constants in Gay-Berne nematic liquid crystals J. Chem. Phys. 105 2850-8... 

As witli tlie nematic phase, a chiral version of tlie smectic C phase has been observed and is denoted SniC. In tliis phase, tlie director rotates around tlie cone generated by tlie tilt angle [9,32]. This phase is helielectric, i.e. tlie spontaneous polarization induced by dipolar ordering (transverse to tlie molecular long axis) rotates around a helix. However, if tlie helix is unwound by external forces such as surface interactions, or electric fields or by compensating tlie pitch in a mixture, so tliat it becomes infinite, tlie phase becomes ferroelectric. This is tlie basis of ferroelectric liquid crystal displays (section C2.2.4.4). If tliere is an alternation in polarization direction between layers tlie phase can be ferrielectric or antiferroelectric. A smectic A phase foniied by chiral molecules is sometimes denoted SiiiA, altliough, due to the untilted symmetry of tlie phase, it is not itself chiral. This notation is strictly incorrect because tlie asterisk should be used to indicate the chirality of tlie phase and not tliat of tlie constituent molecules. 

Continuum theory has also been applied to analyse tire dynamics of flow of nematics [77, 80, 81 and 82]. The equations provide tire time-dependent velocity, director and pressure fields. These can be detennined from equations for tire fluid acceleration (in tenns of tire total stress tensor split into reversible and viscous parts), tire rate of change of director in tenns of tire velocity gradients and tire molecular field and tire incompressibility condition [20]. 

Humphries R L, James P G and Luckhurst G R 1972 Molecular field treatment of nematic liquid crystals J. Chem. Soc. Faraday Trans. II 68 1031-44... 

Luckhurst G R, Zannoni C, Nordic P L and Segre U 1975 A molecular field theory for uniaxial nematic... 

Luckhurst G R 1985 Molecular field theories of nematics systems composed of uniaxial, biaxial or flexible molecules Nuclear Magnetic Resonance of Liquid Crystals ed J W Emsiey (Dordrecht Reidel)... 

Stannarius R 1998 Elastic properties of nematic liquid crystals 1998 Handbook of Liquid Crystals Vol 2A. Low Molecular Weight Liquid Crystals led D Demus, J Goodby, G W Gray, Fl-W Speiss and V Vill (New York Wiley-VCH)... 

The cholesteric phase maybe considered a modification of the nematic phase since its molecular stmcture is similar. The cholesteric phase is characterized by a continuous change in the direction of the long axes of the molecules in adjacent layers within the sample. This leads to a twist about an axis perpendicular to the long axes of the molecules. If the pitch of the heHcal stmcture is the same as a wavelength of visible light, selective reflection of monochromatic light can be observed in the form of iridescent colors. 

C. Characteristically, these nematic melts show the persistence of orientational order under the influence of elongational flow fields which result in low melt viscosities under typical fiber formation conditions even at high molecular weights. 

Chiral Smectic. In much the same way as a chiral compound forms the chiral nematic phase instead of the nematic phase, a compound with a chiral center forms a chiral smectic C phase rather than a smectic C phase. In a chiral smectic CHquid crystal, the angle the director is tilted away from the normal to the layers is constant, but the direction of the tilt rotates around the layer normal in going from one layer to the next. This is shown in Figure 10. The distance over which the director rotates completely around the layer normal is called the pitch, and can be as small as 250 nm and as large as desired. If the molecule contains a permanent dipole moment transverse to the long molecular axis, then the chiral smectic phase is ferroelectric. Therefore a device utilizing this phase can be intrinsically bistable, paving the way for important appHcations. 

Disk-shaped molecules based on a metal atom possess discotic Hquid crystal phases. An example is octasubstituted metaHophthalocyanine. FiaaHy, metallomesogens which combine both rod-like and disk-like features iato a single molecule adopt the biaxial nematic phase. In addition to there being a preferred direction for orientation of the longest molecular axis as is tme for the nematic phase, perpendicular to this direction is another preferred direction for orientation of the shortest molecular axis (12). NonmetaHomesogens which combine both rod- and disk-like features iato a single molecule also adopt a biaxial nematic phase, but at least ia one case the amount of biaxiaHty is very small (15). 

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). 

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. 

---