Strong Anisotropy and Ultralow Percolation Threshold in Multiscale Composites Modified by Carbon Nanotubes Coated Hollow Glass Fiber

Inspired by biological materials, the use of combined fillers of different types and sizes has led to multiscale, hierarchical composites which are considered to be the multifunctional materials of the next generation. However, the effects of hierarchical architecture on the electrical properties and percolation behavior remain poorly understood. Here, a multiscale polymer‐based micro‐/nano‐composite with hollow glass fibers coated by carbon nanotubes (CNTs) has been produced based on a simple dip‐coating approach. Besides a significant increase in electrical performance, the composites exhibit a very strong anisotropy of electrical properties with the difference of 2–5 orders of magnitude in different directions. In the longitudinal direction of composites, an ultralow percolation threshold is found. These unique properties are shown to be related to the hierarchical morphology, which gives rise to the existence of two percolation levels with different thresholds: a local threshold in the nanoscale 2D CNT networks at the fiber‐polymer interfaces and a global threshold in 3D network formed by the fibers. This study helps to deeper understand the macroscopic electrical performance of the hierarchical composites, potentially opening up new ways for designing novel materials via flexible tailoring the orientation of fiber and the morphology of interfaces.