Mesoscale evolution of non-graphitizing pyrolytic carbon in aligned carbon nanotube carbon matrix nanocomposites

Polymer-derived pyrolytic carbons (PyCs) are highly desirable building blocks for high-strength low-density ceramic meta-materials, and reinforcement with nanofibers is of interest to address brittleness and tailor multi-functional properties. The properties of carbon nanotubes (CNTs) make them leading candidates for nanocomposite reinforcement, but how CNT confinement influences the structural evolution of the PyC matrix is unknown. Here, the influence of aligned CNT proximity interactions on nano- and mesoscale structural evolution of phenol-formaldehyde-derived PyCs is established as a function of pyrolysis temperature (\(T_{\mathrm {p}}\)) using X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy. Aligned CNT PyC matrix nanocomposites are found to evolve faster at the mesoscale by plateauing in crystallite size at \(T_{\mathrm {p}}\) \(\sim\)800 \(^{\circ }\hbox {C}\), which is more than \(200\,\,^{\circ }\hbox {C}\) below that of unconfined PyCs. Since the aligned CNTs used here exhibit \(\sim\)80 nm average separations and \(\sim\)8 nm diameters, confinement effects are surprisingly not found to influence PyC structure on the atomic-scale at \(T_{\mathrm {p}}\) \(\le \)1400 \(^{\circ }\hbox {C}\). Since CNT confinement could lead to anisotropic crystallite growth in PyCs synthesized below \(\sim\)1000 \(^{\circ }\hbox {C}\), and recent modeling indicates that more slender crystallites increase PyC hardness, these results inform fabrication of PyC-based meta-materials with unrivaled specific mechanical properties.