Order in thin films of a liquid crystalline polymer

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Abstract
Ordering effects of a side group liquid crystalline polymer PMA64 have been observed by the x-ray reflectivity technique. Thin films on float glass substrate are investigated as a function of temperature and film thickness. At 100 °C, a phase transition from a smectic-A to a nematic phase is observed. The layers of the smectic-A phase are oriented parallel to the surface giving rise to a Bragg peak which is coherently superimposed on Kiessig fringes. The Kiessig fringes are caused by interference of beams reflected at the polymer surface and the polymer–glass interface, while the Bragg peak originates from the electron density modulation perpendicular to the surface. As a function of film thickness, we observe a significant deviation of the integrated intensity of the Bragg peak as compared to the integrated intensity of a Bragg peak due to perfect periodic one-dimensional density modulations. A model which includes the influence of the interfaces as well as distortions of the first and second kind is used to describe this thickness dependence of smectic order in thin films of liquid crystalline polymers. The Bragg peak is lost at the smectic–nematic phase transition where we observe a significant roughening of the free surface. This effect is discussed with respect to molecular order.