Mechanisms of Single-Walled Carbon Nanotube Network Formation and Its Configuration in Polymer-Based Nanocomposites

The reinforcing and conductive performance of carbon nanotube polymer-based nanocomposites depends on the established network and its configuration. Within this study, we report on the underlying mechanisms of such network formation utilizing single-walled carbon nanotubes (SWCNTs) in low- and high-density polyethylene matrices. Mechanisms were theoretically evaluated through Doi–Edwards theory and experimentally confirmed through plasma etching coupled with electron microscopy as well as rheological flow tests. Results showed that the established network is constructed from SWCNT bundles, which geometrically entangle at a critical volume fraction Φv,crit (number of rods: β ≈ 30). Below Φv,crit, the bundles behave as individual units and may align in the flow direction. Above Φv,crit, the rotation of bundles is constrained by neighboring units, leading to a random network configuration. Moreover, the theory successfully explains SWCNT bundle behavior as a Brownian entity and predicts network formation through diminishing thermo- and hydro-dynamically driven diffusion, which can be manipulated during the production to enhance reinforcing/conductive functionality of such materials.