Rheological Properties of Liquid-Crystal Polymers

This work is an extension of our previous studies aimed at investigating miscibility characteristics of liquid crystal polymer systems. The present study has shown that it is possible to significantly modify the rheological properties of one liquid crystal polymer by blending with another liquid crystal polymer. 

In most cases, the flow properties of polymers in solution or in a molten state are Newtonian, pseudoplastic, or a combination of both. In the case of liquid crystal polymer solutions, the flow behavior is more complex. The profound difference in the rheological behavior of ordinary and liquid crystalline polymers is due to the fact that, for the flrst ones, the molecular orientation is entirely determined by the flow process. The second ones are anisotropic materials already at equilibrium (Acierno and Brostow 1996). The spontaneous molecular orientation is already in existence before the flow and is switched on, varying in space, over distances of several microns or less (polydomain). If one ignores the latter, one can discuss the linear case (slow flow) as long as the rate of deformation due to flow (the magnitude of the symmetric part of the velocity gradient) is lower than the rate at which molecules rearrange their orientational spread by thermal motions. 

Steady flow behavior is the most thoroughly investigated rheological property. Onogi and Asada (1980) assumed that the viscosity of liquid crystal polymer solutions can be described by the universal existence of three shear flow domains ... 

Rheology, or the study of deformation and flow, represents the linking stage between polymerization and application it is concerned with the manufacture of articles and their properties. Liquid crystallinity is a rheological phenomenon it is observed as a result of a flow process producing persistent anisotropy in the fluid, and that anisotropy determines the property spectrum of the product. Thus an appreciation of rheological phenomena is doubly important in the study of liquid crystal polymers. 

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. 

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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