Circumventing the Mechanochemical Origins of Strength Loss in the Synthesis of Hierarchical Carbon Fibers

Hierarchical carbon fibers (CFs) sheathed with radial arrays of carbon nanotubes (CNTs) are promising candidates for improving the intra- and interlaminar properties of advanced fiber-reinforced composites (e.g., graphite/epoxy) and for high-surface-area electrodes for battery and supercapacitor architectures. While CVD growth of CNTs on CFs has been previously shown to improve the apparent shear strength between fibers and polymer matrices (up to 60%), this has to date been achieved only at the expense of significant reductions in tensile strength (∼30–50%) and stiffness (∼10–20%) of the underlying fiber. Here we demonstrate two approaches for growing aligned and unaligned CNTs on CFs that enable preservation of fiber strength and stiffness. We observe that CVD-induced reduction of fiber strength and stiffness is primarily attributable to mechanochemical reorganization of the underlying fiber when heated untensioned above ∼550 °C in both hydrocarbon-containing and inert atmospheres. We show that tensioning fibers to ≥12% of tensile strength during CVD enables aligned CNT growth while simultaneously preserving fiber strength and stiffness even at growth temperatures >700 °C. We also show that CNT growth employing CO<sub>2</sub>/acetylene at 480 °C without tensioningbelow the identified critical strength-loss temperaturepreserves fiber strength. These results highlight previously unidentified mechanisms underlying synthesis of hierarchical CFs and demonstrate scalable, facile methods for doing so.