The Morphology of Liquid-Crystalline Polymers and the Possible Consequences for their Rheological Behaviour

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Abstract
Polymer liquid crystals can occur as polydomain materials where the domain size may be tens of microns. While the material within each domain may be characterized by a common order parameter, the directors of the domains can be more or less randomly distributed. Since the transition from polydomain to monodomain material only involves the removal of grain boundaries and the alignment of directors, the free energy change must necessarily be small. Such a transition can readily be achieved, therefore, by the action of any external field: electrical, magnetic, stress or surface. In this work optical photomicrographs of polymeric liquid crystals with widely varying and in some cases well controlled morphologies are presented. Probable dependence of rheological behaviour on morphology is also discussed. Such dependence is expected to be considerable under certain conditions. Due to experimental and sample limitations, however, direct correlations of rheology and morphology are sparse. Morphological consequences for the rheology of liquid-crystalline materials can be exemplified by the following possibilities. In contrast to the case of isotropic melts, wall effects can be non-negligible. Zero shear rate rheological parameters are not expected to be uniquely defined quantities since the domain sizes are large and the director may not be effectively averaged over typical sample dimensions. Non-zero shear-rate measurements of rheological parameters is effected by the propensity of: (1) individual domain directors to align under the influence of a stress field and (2) flow alignment to dominate surface-induced alignment above some critical shear rate. The effects might be manifested by a non-newtonian regime as well as yield stress behaviour and thixotropy. The kinetics of relaxation from mono- to poly-domain material has implications for the dynamic response and rheological hysterises of the material.