Organoclay/thermotropic liquid crystalline polymer nanocomposites. Part V: morphological and rheological studies

Abstract

Small amounts of organoclays in different sizes and concentrations were added into thermotropic liquid crystalline polymer (TLCP) by a combination method of ultrasonication, centrifugation, and solution casting (and shear-induced phase separation). Four kinds of organoclay-modified TLCP composites were obtained. TC3 UP was a kind of organoclay which displayed a marked shear-induced phase separation phenomenon at 190 °C and higher temperatures. TC3 UP could be separated into a TLCP-rich part, TC3 white, and an organoclay-rich part, TC3 dark. TC3 white was an organoclay-modified TLCP with fully exfoliated organoclay of a uniform size of 15–25 nm well dispersed in the TLCP. TC3 dark had a typical intercalated model structure with some TLCP molecules confined in organoclay galleries. TC3 FS was an organoclay-modified TLCP with organoclay of comparable size to that of the fully extended TLCP molecule, i.e., 85 nm. The organoclay layers dispersed into the polymeric matrix as a few randomly organized organoclay layers or stacks of layers in the quiescent condition in organoclay-modified TLCPs. The larger organoclay size or higher concentration of organoclay in the composites (such as, TC3 UP and TC3 dark) caused a greater proportion of the layers or stacks be hydro-dynamically impeded in the quiescent state, resulting in the filler–filler interaction becoming important and in fact dominating the long-term viscoelasticity of the composites. Additionally, the ease with which the organoclay structure could be altered by flow was considerably enhanced, primarily because of filler–filler interactions. Organoclay size has primary effect on the liquid crystallinity of TLCP. Small or comparable organoclay size with the fully extended TLCP molecule in TC3 white and TC3 FS has weak or negligible negative influence on the liquid crystallinity of TLCP, while larger organoclay size totally damages the liquid crystallinity of TLCP. The morphologies, liquid crystallinity as well as the linear and non-linear viscoelastic behaviors of organoclay-modified TLCPs have been characterized in detail.