We present a fast method to prepare hybrid materials of polyaniline (PAni) with carbon nanotubes (CNTs, both undoped and nitrogen-doped) by ball milling without solvents or strong oxidants. PAni forms nanoparticles, attached to CNTs in a nanocomposite structure, with the nanotubes well dispersed among the polymer. This is achieved with only a few minutes of ball milling. Raman spectroscopy confirms that PAni was synthesized in its conductive state and suggests a good CNT—PAni interaction, particularly with nitrogen-doped CNTs. We found that water increased polymer yield, which we optimized, together with the nanocomposite conductivity, as function of amount of water and of oxidant (FeCl3). The nanocomposite conductivity is four orders of magnitude higher than that of PAni, for both types of nanotubes. Scanning electron microscopy and X-ray diffraction both show negligible damage to the CNT during this mechanosynthesis procedure, while dry milling and milling CNT in water without aniline does damage nanotubes, indicating that the reaction absorbs most of the mechanical energy.
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Some of the initial experimental work reported here was performed when the authors worked at the Advanced Materials Department, Instituto Potosino de Investigación Científica y Tecnológica IPICYT (San Luis Potosí, S.L.P., México) and was supported by grants CB-2008-SEP-107082 (FJRM) and CB-2008-SEP-106942, (YIVC). The authors also thank Rede NANOBIOTEC-Brasil (Edital 04/CII-2008 CAPES/MEC) for support for a postdoctoral position (JCGG) and visiting professor stays (YIVC, FJRM) at UFPE. YIVC and FJRM also thank FACEPE and PROPESQ/UFPE for additional support. YIVC and FJRM also thank the Centro de Innovación en Diseño y Tecnología (CIDyT), Advanced Manufacturing and Nanotechnlogy for Device Design groups and the Department of Sciences—Chemistry and Nanotechnology of Tecnologico de Monterrey.
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García-Gallegos, J.C., Vega-Cantú, Y.I. & Rodríguez-Macías, F.J. Fast mechanochemical synthesis of carbon nanotube-polyaniline hybrid materials. Journal of Materials Research 33, 1486–1495 (2018). https://doi.org/10.1557/jmr.2018.56