Linear viscosity in the nematic phase

The zero shear viscosity of flexible linear polymers varies experimentally with and theoretically with [20]. Due to the highly restricted rotational diffusion, the viscosity of TLCPs is much more sensitive to the molecular weight than that of ordinary thermoplastics as discussed in section 3. Doi and Edwards predicted that the viscosity of rod-like polymers in semi-dilute solutions scales with A/ [see Equation (12)] [2]. Such a high power dependence of viscosity on the molecular weight has been experimentally observed both for lyotropic LCPs [14,15] and for TLCPs [16-18]. The experimental values of the exponent range from 4 to 7 depending on the chemical structure, the chain stiffness, and the domain or defect structure of the liquid crystalline solution or melt. The anisotropicity of the liquid seems to have little effect on the exponent. A slightly smaller exponent for the nematic phase than for the isotropic phase (6 in the nematic phase versus 6.5 in the isotropic... 

Figure 9. The shear stress (left) Jind viscosity as functions of the shear rate for Ak = 1-25 and k = 0, in the nematic phase, at the temperature = 0, in a linear plot for shear rates between 1 and 5. All data points stem from calculations with constant shear rates, the maximum shear deformation is 750.

If one follows the solution viscosity in concentrated sulfuric acid with increasing polymer concentration, then one observes first a rise, afterwards, however, an abrupt decrease (about 5 to 15%, depending on the type of polymers and the experimental conditions). This transition is identical with the transformation of an optical isotropic to an optical anisotropic liquid crystalline solution with nematic behavior. Such solutions in the state of rest are weakly clouded and become opalescent when they are stirred they show birefringence, i.e., they depolarize linear polarized light. The two phases, formed at the critical concentration, can be separated by centrifugation to an isotropic and an anisotropic phase. A high amount of anisotropic phase is desirable for the fiber properties. This can be obtained by variation of the molecular weight, the solvent, the temperature, and the polymer concentration. 

A central part of the application-oriented evaluation of liquid crystals are so-called virtual clearing temperatures, electrooptic properties, and viscosities. These data are obtained by extrapolation from a standardized nematic host mixture. 7 Af, An, and jy are determined by linear extrapolation from a 10% iv/iv solution in the commercially available Merck mixture ZLI-4792 (Tfji = 92.8°C, Af = 5.27, An = 0.0964). For the pure substances the mesophases are identified by optical microscopy and the phase transition temperatures by differential scanning calorimetry (DSC). The transition temperatures in the tables are cited in °C, numbers in parentheses denote monotropic phase transitions which occur only on cooling the sample C = crystalline, S = smectic A, Sg = smectic B, S = smectic G, S> = unidentified smectic phase, N = nematic, I = isotropic. 

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