Intermediate Polymer Relaxation Explains the Anomalous Rheology of Nanocomposites with Ultrasmall Attractive POSS Nanoparticles

The rheological properties of entangled polymers loaded with very small, strongly attractive polyhedral oligomeric silsesquioxane (POSS) fillers differ from that of nanocomposites with larger fillers by (1) the shorter breadth of the entanglement plateau and (2) the relatively unchanged terminal viscosity with increasing POSS loading. Although such anomalous rheological properties can rewrite the property–processing map of materials (e.g., high glass transition temperature and low viscosity), their mechanism remains unclear. In this study, we report that polymer relaxations on intermediate time scales between α and entire-chain relaxation, so-called “slower processes”, are responsible for this unusual rheological behavior of poly(2-vinylpyridine)/octa(aminophenyl)silsesquioxane (P2VP/OAPS) nanocomposites. To uncover the effects of entanglements on the nanocomposite dynamics, rheometry is used for variable matrix molecular weights. Results show a systematic change in the rheological response, which is independent of the molecular weight, and in turn, the presence of entanglements. This supports a physical interpretation that a slower process dominates the rheological response of the material at intermediate frequencies on length scales larger than the segment length or the OAPS diameter, while the underlying physical time scales associated with the entanglement relaxation remain unchanged. Such insights are anticipated to assist the future rational design of other highly attractive and ultrasmall nanoparticles that enable a fine-tuned rheological response of nanocomposites across multiple length scales.