Micro-drawing of glassy polybenzoxazole rigid rods and the molecular interactions with carbon nanotubes

The high-temperature (Tg > 650°) wholly aromatic polybenzoxazoles (PBO) polymer chains in thin films underwent elastic energy release via local deformation of crazing when stretched beyond a critical strain around 0.5%. The strain localization in the ultra-rigid polymer was quickly superseded by craze fibril breakdown, triggering catastrophic fracture at low extensions below ∼3%. Although the drawing stress of craze fibrillation, determined to be ∼3 GPa, was insufficient to separate chains in PBO crystallites, it forced the chains in the amorphous regions to flow into large molecular deformations (∼300% strain) at room temperature. The poor craze fibril stability of the rigid-rod chains was enhanced dramatically when surface-functionalized single-walled carbon nanotubes (SWCNTs) were dispersed into the polymer. No toughening effects were observed, however, for multi-walled carbon nanotubes (MWCNTs) although the elastic enhancement leading to increase of strain delocalization was still operative. The toughening selectivity was attributed to the PBO/CNT load transfer coupling during nanoplastic flows in which only the CNTs of compatible bending moments permitting fibril drawing were allowed to participate.