Liquid crystal rheology

S. Sarman, Microscopic Theory of Liquid Crystal Rheology, J. Chem. Phys. 103 (1995) 393. 

Rey, A.D. Tsuji, T. Recent advances in theoretical liquid crystal rheology. Macromol. Theory Simul. 1998, 7 (6), 623-639. 

Kiss, G., Topics in liquid crystal rheology , Malvern Webinar, 51 slides, 36 minutes, http //www.malvern.com/malvern/ondemand.nsf/webcasts7opennavigatory ear=2010 or https //www.brainshark.com/malvern/vu pi=zEGzZg27lzB28zO. 

The role of various surfactant association structures such as micelles and lyotropic liquid crystals (372), adsorption-desorption kinetics at liquid-gas interfaces (373) and interfacial rheology (373) and capillary pressure (374) on foam lamellae stability has been studied. Microvisual studies in model porous media indicate... 

Among the adaptive materials currently on the forefront are liquid crystals, electro- and magneto-rheological (ER/MR) fluids, thermo- and physioreponsive gels, and shape memory alloys. In all but the last case, these systems involve... 

Different types of liquid crystals exhibit different rheological properties [16,17]. With an increase in organization of the microstructure of the liquid crystal its consistency increases and the flow behavior becomes more viscous. The coefficient of dynamic viscosity r, although a criterion for the viscosity of ideal viscous flow behavior (Newtonian systems), is high for cubic and hexagonal liquid crystals but fairly low for lamellar ones. However, the flow characteristics are not Newtonian but plastic or pseudoplastic, respectively. 

This article reviews the following solution properties of liquid-crystalline stiff-chain polymers (1) osmotic pressure and osmotic compressibility, (2) phase behavior involving liquid crystal phasefs), (3) orientational order parameter, (4) translational and rotational diffusion coefficients, (5) zero-shear viscosity, and (6) rheological behavior in the liquid crystal state. Among the related theories, the scaled particle theory is chosen to compare with experimental results for properties (1H3), the fuzzy cylinder model theory for properties (4) and (5), and Doi s theory for property (6). In most cases the agreement between experiment and theory is satisfactory, enabling one to predict solution properties from basic molecular parameters. Procedures for data analysis are described in detail. 

Liquid-crystalline polymers with stiff backbones have many static and dynamic solution properties markedly distinct from usual flexible polymers. For example, their solutions are transformed from isotropic to liquid crystal state with increasing concentration. While very high in the concentrated isotropic state, their viscosity decreases drastically as the concentration crosses the phase boundary toward the liquid crystal state. The unique rheological properties they exhibit in the liquid crystal state are also remarkable. 

Ac Klim. D. and A.A. Collyer Rheology und Processing of Liquid Crystal Polymers,... 

In a majority of works on LC polymers, the main attention was paid to the synthesis and structural studies of such polymers. Significantly less information is available on physical properties of LC polymers, especially, when compared to low-molecular liquid crystals. In this chapter some rheological and dielectric properties of polymeric liquid crystals, characteristics of their dynamic properties and intramolecular mobility, are considered. 

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. 

Even when composition is fixed, viscosity and other rheological properties may depend on the size and arrangement of aligned domains within a sample of liquid crystalline material. No studies of this matter seem to have been made, however. Such structural characteristics do influence electrical conduction and diffusion in liquid crystals, as discussed further below. 

This brief account of past investigations is concerned with work on polymer liquid crystals (PLCs), where the majority of work has considered nematic materials. Among the unique rheological responses associated with PLCs are... 

P. Moldenaers, Rheological behavior of lyoropic polymeric liquid crystals, Ph.D. thesis, Katholiecke Universiteit Leuven (1987). 

W. R. Burghardt and G. G. Fuller, Role of director tumbling in the rheology of polymer liquid crystal solutions, Macromolecules, 24, 2546 (1991). 

Understanding surfactant phase behavior is important because it controls physical properties such as rheology and freeze-thaw stability of formulations. It is also closely related to the ability to form and stabilize emulsions and microemulsions. Micelles, vesicles, mi-croemulsions and liquid crystal phases have all been used as delivery vehicles for perfumes or other active ingredients. 

In addition to the opportunities for new materials synthesis and characterization along these lines, transport properties, rheology, and processing techniques for liquid crystal polymers are essentially unexplored. Experiences with synthesis of polymer structure based on these liquid crystal templates may open up other creative avenues for template synthesis, for example, inside other crystalline structures, chlathrates, or zeolites, or on surfaces [4], Composites, alloys, or mixtures of liquid crystalline and flexible polymers may produce new materials. 

Another peculiar property of LCPs is shown in Fig. 15.47, where the transient behaviour of the shear stress after start up of steady shear flow is shown for Vectra A900 at 290 °C at two shear rates. We will come back to this behaviour in Chap. 16 for lyotropic systems where this behaviour is quite common and in contradistinction to the transient behaviour of conventional polymers, as presented in Fig. 15.9. This damped oscillatory behaviour is also found for simple rheological models as the Jeffreys model (Te Nijenhuis 2005) and according to Burghardt and Fuller, it is explicable by the classic Leslie-Ericksen theory for the flow of liquid crystals, which tumble, rather than align, in shear flow. Moreover, it is extra complicated due to the interaction between the tumbling of the molecules and the evolving defect density (polynomial structure) of the LCP, which become finer, at start up, or coarser, after cessation of flow. 

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