Leslie nematics

Furtlier details can be found elsewhere [20, 78, 82 and 84]. An approach to tire dynamics of nematics based on analysis of microscopic correlation fimctions has also been presented [85]. Various combinations of elements of tire viscosity tensor of a nematic define tire so-called Leslie coefficients [20, 84]. 

The rigid nature of the mesophase pitch molecules creates a strong relationship between flow and orientation. In this regard, mesophase pitch may be considered to be a discotic nematic liquid crystal. The flow behavior of liquid crystals of the nematic type has been described by a continuum theory proposed by Leslie [36] and Ericksen [37]. 

Leslie, F. M., "Theory of Flow in Nematic Liquid Crystals, The Breadth and Depth of Continuum Mechanics—A Collection of Papers Dedicated To J. L. Ericksen, C. M. Da-fermos, D. D. Joseph, andF. M. Leslie, Eds., Springer-Verlag, Berlin, 1986. 

Note 2 For nematics formed by low-molar-mass eompounds, the Leslie coefficients are typically in the range 10 to 10 Pa s. 

In a weak flow field, Eq. (64) can be rewritten in a form similar to that for the direct n appearing in Leslie and Ericksen s phenomenological theory [160—163] for nematic systems. Thus, we have... 

The molecular theory of Doi [63,166] has been successfully applied to the description of many nonlinear rheological phenomena in PLCs. This theory assumes an un-textured monodomain and describes the molecular scale orientation of rigid rod molecules subject to the combined influence of hydrodynamic and Brownian torques, along with a potential of interaction (a Maier-Saupe potential is used) to account for the tendency for nematic alignment of the molecules. This theory is able to predict shear thinning viscosity, as well as predictions of the Leslie viscosity coefficients used in the LE theory. The original calculations by Doi for this model employed a preaveraging approximation that was later... 

The three elastic constants are the Frank elastic constants, called after Frank, who introduced them already in 1958. They originate from the deformation of the director field as shown in Fig. 15.52. A continuous small deformation of an oriented material can be distinguished into three basis distortions splay, twist and bend distortions They are required to describe the resistance offered by the nematic phase to orientational distortions. As an example, values for Miesowicz viscosities and Frank elastic constants are presented in Table 15.10. It should be mentioned that those material constants are not known for many LCs and LCPs. Nevertheless, they have to be substituted in specific rheological constitutive equations in order to describe the rheological peculiarities of LCPs. Accordingly, the viscosity and the dynamic moduli will be functions of the Miesowicz viscosities and/or the Frank elastic constants. Several theories have been presented that are more or less able to explain the rheological peculiarities. Well-known are the Leslie-Ericksen theory and the Larson-Doi theory. It is far beyond the scope of this book to go into detail of these theories. The reader is referred to, e.g. Aciemo and Collyer (General References, 1996). 

Figure 10.7 (a-c) The Leslie viscosities 0 3 and o 2 determine the direction and rate of rotation of the director (represented by the cylinders) in the orientations shown, For negative values of 3 and 2 (the usual signs for rod-like nematics), the rotation directions are shown by the arrows. The viscosity ua, determines the viscosity of the liquid when the director is in the vorticity direction. (Adapted from Skarp et al., reprinted with permission from Mol. Cryst. Liq. Cryst. 60 215, Copyright 1980, Gordon and Breach Publishers.)... 

Very few data exist for the viscosities or Frank constants of discotic nematics—that is, nematics composed of disc-Uke particles or molecules (Chandrasekhar 1992). One can estimate values of the Leslie viscosities from the Kuzuu-Doi equations (10-20) by setting the aspect ratio p equal to the ratio of the thickness to the diameter of the particles thus /j — 0 for highly anisotropic disks. This implies that R(p) —1, and Eq. (10-20b) implies that the viscosity o 2 is large and positive for discoidal nematics, while it is negative for ordinary nematics composed of prolate molecules or particles. If, as expected, is much smaller in magnitude than 0 2. the director (which is orthogonal to the disks) will tend... 

The viscous properties of a smectic A are characterized by the same five independent viscosities that characterize the nematic. As we shall see, however, the elastic properties of the smectic are very different from those of a nematic, and some flows permitted to the nematic are effectively blocked for the smectic. For smectic C, for which the director is tilted with respect to the layers, there are some 20 viscosities needed to characterize the viscous properties (Leslie 1993). Formulas for these, derived using a method analogous to that used for nematics by Kuzuu and Doi (1983, 1984) can be found in Osipov et al. (1995). The smectic phase for which rheological properties are most commonly measured is smectic A, however, and hereafter we will limit our discussion to it. 

Problem 10.3(a) (Worked Example) From the Leslie-Ericksen equations at high shear rate, derive Eq. (10-29) for the director angle 6 in a shearing flow of a tumbling nematic. 

When De 1 and molecular elasticity is negligible, the flow properties of polymeric nematics can, in principle, be described by the Leslie-Ericksen equations (see Section 10.2.3). However, at moderate and high De, the Leslie-Ericksen continuum theory fails, and a molecular theory is required to describe the effect of flow on the distribution of molecular orientations. 

From slow-shear-rate solutions of the Smoluchowski equation, Eq. (11-3), with the Onsager potential, Semenov (1987) and Kuzuu and Doi (1983, 1984) computed the theoretical Leslie-Ericksen viscosities. They predicted that ai/a2 < 0 (i.e., tumbling behavior) for all concentrations in the nematic state. The ratio jai is directly related to the tumbling parameter X by X = (1 -h a3/a2)/(l — aj/aa). Note the tumbling parameter X is not to be confused with the persistence length Xp.) Thus, X < I whenever ai/a2 < 0. As discussed in Section 10.2.4.1, an approximate solution of Eq. (11-3) predicts that for long, thin, stiff molecules, X is related to the second and fourth moments Sa and S4 of the molecular orientational distribution function (Stepanov 1983 Kroger and Sellers 1995 Archer and Larson 1995) ... 

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. 

Few other sets of viscosities exist for polymeric nematics. Yang and Shine (1993) obtained three of the Leslie viscosities for monodomains of poly(n-hexyl isocyanate) (PHIC) from rheological measurements in the presence of an electric field, and they obtained values reasonably consistent with the predictions of the Kuzuu-Doi expressions. From monodomains of the polyion PBZT, poly(l,4-phenylene-2,6-benzobisthiazole) in methane sulfonic acid, some of the Leslie-Ericksen parameters have been extracted via light-scattering and magnetic-field-reorientation studies (Berry 198S Srinivasarao and... 

Inspired by a mesoscopic theory for mixtures of immiscible liquids (Doi and Ohta 1991 see also Section 9.3.3), Larson and Doi (1991) have derived mesoscopic equations for polydomain nematics by multiplying the Leslie-Ericksen equation (10-13) by the director... 

The tendency of LCs to resist and recover from distortion to their orientation field bears clear analogy to the tendency of elastic solids to resist and recover from distortion of their shape (strain). Based on this idea, Oseen, Zocher, and Frank established a linear theory for the distortional elasticity of LCs. Ericksen incorporated this into hydrostatic and hydrodynamic theories for nematics, which were further augmented by Leslie with constitutive equations. The Leslie-Ericksen theory has been the most widely used LC flow theory to date. 

Zuniga, I. Leslie, F.M. Shear-flow instabilities in non-flow-aligning nematic liquid crystals. Liq. Cryst. 1989, 5, 725-734. 

Carlsson, T. Theoretical investigation of the shear flow of nematic liquid crystals with the Leslie viscosity as > 0 hydrodynamic analogue of first order phase transition. Mol. Cryst. Liq. Cryst. 1984, 104, 307-334. 

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