Molecular Theory for the Rheology of Polymeric Nematics

At low enough shear rates, polymeric nematics ought to obey the same Leslie-Ericksen continuum theory that describes so well the behavior of small-molecule nematics. The main difference is that polymers have a much higher molecular aspect ratio than do small molecules, which leads to greater inequalities in the the numerical values of the various viscosities and Frank constants and to much higher viscosities. 

Because of the difficulty with which polymeric nematic monodomains are prepared, there are few measurements of Leslie viscosities and Frank constants for LCPs reported in the literature. The most complete data sets are for PBG solutions, reported by Lee and Meyer (1990), who dissolved the polymer in a mixed solvent of 18% dioxane and 82% dichloromethane with a few percent added dimethylformamide. Some of these data, measured by light scattering and by the response of the nematic director to an applied magnetic field, are shown in Figs. 11-19 and 11-20 and in Table 11-1. While the twist constant has a value of around K2 0.6 x 10 dyn, which is believed to be roughly independent of concentration and molecular weight, the splay and bend constants ATj and K3 are sensitive to concentration and molecular weight. 

2 X C2. Although these ratios are not consistent with data for PBG solutions, they are consistent with measurements of the Frank constants of suspensions of the tobacco mosaic virus (Lee and Meyer 1986), which is an extremely rigid particle. Thus, discrepancies between theory and measurements for PBG are most likely due to the partial flexibility of PBG molecules. 

A Landau-de Gennes theory for the Frank constants of long semiflexible worm-Uke chains at low order parameter S gives (Shimada et al. 1988) K = K7, = 0K2 = 

100 nm, of concentration such that vkgT 0.8. Although the Landau-de Gennes theory is, in 

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