We present results of a systematic high-resolution transmission electron microscopy study of the thermal evolution of bundled single-walled carbon nanotubes (SWNTs) subjected to approximately 4-h high-temperature heat treatment (HTT) in a vacuum at successively higher temperatures up to 2200 degrees C. We have examined purified SWNT material derived from the HiPCO and ARC processes. These samples were found to thermally evolve along very different pathways that we propose depend on three factors: (1) initial diameter distribution, (2) concomitant tightness of the packing of the tubes in a bundle, and (3) the bundle size. Graphitic nanoribbons (GNR) were found to be the dominant high-temperature filament in ARC material after HTT = 2000 degrees C; they were not observed in any heat-treated HiPCO material. The first two major steps in the thermal evolution of HiPCO and ARC material agree with the literature, i.e., coalescence followed by the formation of multiwall carbon nanotubes (MWNTs). However, ARC material evolves to bundled MWNTs, while HiPCO evolves to isolated MWNTs. In ARC material, we find that the MWNTs collapse into multishell GNRs. The thermal evolution of these carbon systems is discussed in terms of the diameter distribution, nanotube coalescence pathways, C-C bond rearrangement, diffusion of carbon and subsequent island formation, as well as the nanotube collapse driven by van der Waals forces.

High temperature heat treatment (HTT) of bundled single-walled carbon nanotubes (SWNTs) in vacuum ( approximately 10(-5) Torr) has been found to lead to the formation of two types of graphitic nanoribbons (GNRs), as observed by high-resolution transmission electron microscopy. Purified SWNT bundles were first found to follow two evolutionary steps, as reported previously, that is, tube coalescence (HTT approximately 1400 degrees C) and then massive bond rearrangement (HTT approximately 1600 degrees C), leading to the formation of bundled multiwall nanotubes (MWNTs) with 3-12 shells. At HTT > 1800 degrees C, we find that these MWNTs collapse into multishell GNRs. The first type of GNR we observed is driven by the collapse of diameter-doubled single-wall nanotubes, and their production is terminated at HTT approximately 1600 degrees C when the MWNTs also start to form. We propose that the collapse is driven by van der Waals forces between adjacent tubes in the same bundle. For HTT > 2000 degrees C, the heat-treated material is found to be almost completely in the multishell GNR form.

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A systematic high-resolution transmission electron microscopy study of the thermal evolution of bundled single-walled carbon nanotubes (SWNTs) subjected to ~8 h high temperature heat treatment (HTT) in vacuum at successively higher temperatures up to 2200 °C is presented. We have examined purified SWNT material derived from the HiPCO and ARC processes (see Figure 1). These samples were found to thermally evolve along very different pathways that we propose depends on three factors: (1) initial diameter distribution, (2) concomitant tightness of the packing of the tubes in a bundle, and (3) the bundle size. Graphitic Nanoribbons (GNR) were found to be the dominant high temperature filament in ARC material after HTT=2000 °C; they were not observed in any heat-treated HiPCO material. The first two major steps in the thermal evolution of HiPCO and ARC material agree with the literature [1-3], i.e., coalescence, followed by the formation of multiwall carbon nanotubes (MWNTs). However, Arc material evolves to bundled MWNTs, while HiPCO evolves to isolated MWNTs. In ARC material, we find that the MWNTs collapse into multishell GNRs. The thermal evolution of these carbon systems is discussed in terms of the diameter distribution, nanotube coalescence pathways, CC bond rearrangement, diffusion of carbon and subsequent island formation, as well as the nanotube collapse driven by van der Waals forces. The HRTEM results were correlated with micro-Raman Scattering experiments. The thermal transformations produce changes in the radial (R) SWNT band, the G-band (and its substructure), and the relative intensity of the disorder-induced D-band scattering. The Raman spectrum of GNRs is also discussed in detail. Three relatively broad GNR Raman bands are observed: 1320, 1580, 1620, 2702 and 3250cm-1. The large GNR D-band scattering intensity is tentatively assigned to K-point modes activated by the small lateral width of the GNRs that is estimated from TEM and Raman to be ~ 6-8 nm.