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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.

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I.Y.S. was supported in part by the Department of Defense (DoD) through the National Defense Science and Engineering Graduate Fellowship (NDSEG) Program. A.L.K. and A.J.C. were supported by the CMSE Research Experience for Undergraduates Program, as part of the MRSEC Program of the National Science Foundation under Grant Number DMR-08-19762, and the MIT Materials Processing Center. This work was partially supported by Airbus, Embraer, Lockheed Martin, Saab AB, ANSYS, Hexcel, Saertex, and TohoTenax through MIT’s Nano-Engineered Composite aerospace Structures (NECST) Consortium. The authors thank P. Boisvert, T. McClure, and C. Settens for helpful discussions, and the members of necstlab at MIT for technical support and advice. This work made use of the MRSEC Shared Experimental Facilities at MIT, supported by the National Science Foundation under award number DMR-08-19762, and utilized the core facilities at the Institute for Soldier Nanotechnologies at MIT, supported in part by the U.S. Army Research Office under contracts W911NF-07-D-0004 and W911NF-13-D-0001.

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Correspondence to Itai Y. Stein or Brian L. Wardle.

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Stein, I.Y., Kaiser, A.L., Constable, A.J. et al. Mesoscale evolution of non-graphitizing pyrolytic carbon in aligned carbon nanotube carbon matrix nanocomposites. J Mater Sci 52, 13799–13811 (2017).

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  • Carbon Nanotubes (CNT)
  • Polymer Matrix Nanocomposites
  • Pyrolytic Carbon
  • Mesoscale Evolution
  • Crystallite Growth