Macroscopic theory of orientation transitions in the extensional flow of side-chain nematic polymers

A macroscopic continuum mechanical model for incompressible side-chain nematic polymers, under isothermal conditions is given. The model is a synthesis of a transient network model and the standard nematorheological model. Simplifications in the model yield constitutive equations that are identical to well known Theological models for polymer melts and for low molar mass nematics. A detailed analysis of four possible composite orientation modes of polymer backbone and mesogenic side groups in uniaxial extensional flow is given. It is shown that the thermal sensitivity of the viscoelastic parameters leads to thermally-induced orientation transitions. The extension rate sensitivity of the competition between elastic and flow orienting effects leads to flow-induced orientation transition. The role of smectic A fluctuations in thermally-induced transitions during uniaxial extensional nematic flow is elucidated. The model is able to predict and explain the experimentally observed orientation modes and thermally-induced orientation transitions of a side-chain nematic polymer subjected to uniaxial extensional flow.