Quantitative Characterization of Vertically Aligned Multi-Walled Carbon Nanotube Arrays Using Small Angle X-Ray Scattering (original) (raw)
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2007
Films of multiwall carbon nanotubes (MWCNTs) grown by thermal chemical vapor deposition were studied using small-angle X-ray scattering (SAXS). We assessed the extent of alignment of carbon nanotubes (CNTs) by examining relative SAXS intensities as a function of azimuthal angle. We also identified features in the SAXS patterns that correspond well to CNT diameters measured through high-resolution transmission electron microscopy. For the case of thick films, corresponding to CNTs with lengths on the order of a millimeter, we were able to study the morphology of the films as a function of distance from the catalyst substrate. We examined two different films in which the morphologies of CNTs range from vertically aligned to entangled and tortuous. We determined that the alignment of CNTs as well as their average diameter can vary significantly throughout the film, demonstrating the utility of SAXS for quantitative structural analysis of CNT films, indicating the potential to reveal new information about the CNT growth process, and relating variations in morphology to evolution of the catalyst and reaction conditions.
2007
We used small-angle X-ray scattering (SAXS) to quantitatively characterize the morphological characteristics of pristine and mechanically manipulated multiwall carbon nanotube (MWCNT) films. We determined that CNT diameters measured near the edges of a film were smaller compared to those measured in the interior. Uniaxially compressed MWCNT films exhibited a buckling deformation that was observable both in scanning electron microscopy (SEM) and SAXS. CNT films were also converted into cellular foams of CNTs through capillarity-induced densification. By examining spatially-and time-resolved SAXS data for the cellular foams, we identified low angle features in the scattering curves that correspond to the average spacing between CNTs, demonstrating that SAXS is a useful method for monitoring the packing density of CNTs in a film. For all of the morphologies that were examined (aligned, disordered, compressed, and densified), SAXS data showed good correspondence with SEM images.
Anisotropy of x-ray scattering in aligned nanotube structures
2004
Effects of orientational x-ray scattering have been experimentally examined in a film of vertically aligned multiwall carbon nanotubes (CNs). Additional contribution to the x-ray fluorescence intensity was revealed at angles close to the film normal. Theoretical considerations suggest the intensity enhancement to be caused by propagation of C K$_{\alpha}$-radiation mainly along the channels of CNs.
Nanotechnologies in Russia, 2008
Arrays of multiwalled carbon nanotubes (CNTs) aligned perpendicular to the substrate surface have been produced by the pyrolysis of a mixture of hydrocarbons with ferrocene as the source of the catalyst. Based on scanning electron microscopy data, the mechanism of formation of aligned CNT arrays is proposed. The potential of angle-resolved X-ray spectroscopy for determining the degree of disorder of graphite layers in CNTs is demonstrated. Aligned CNT arrays are characterized by anisotropy of magnetic properties due to encapsulation of metallic rods in the inner cavities of nanotubes.
Physical Chemistry Chemical Physics, 2006
Probing surface order as well as the degree of structural modification in carbon nanotube systems is of fundamental importance for incorporation of these materials into practical functional devices. The current study pertains to the analysis of the surface order of vertically-aligned singlewalled and multi-walled carbon nanotube arrays of varying length and composition by means of near-edge X-ray fine structure spectroscopy (NEXAFS). Both NEXAFS and scanning electron microscopy (SEM) studies concluded that the nanotubes in these samples were oriented vertically to the plane of the surface. However, NEXAFS polarization analysis provided a more quantitative and nuanced description of the surface structure, indicative of far less localized surface order, an observation partially attributed to misalignment and bending of the tubes. Moreover, it was demonstrated by NEXAFS that the surface order of the arrays was imperfect and relatively independent of the height of the nanotube arrays. In addition, we have shown that NEXAFS can be used to correlate the extent of chemical functionalization and oxygenation with disruption of the electronic and physical structure of nanotubes embedded in array motifs.
Non-destructive characterization of structural hierarchy within aligned carbon nanotube assemblies
Journal of Applied Physics, 2011
Understanding and controlling the hierarchical self-assembly of carbon nanotubes (CNTs) is vital for designing materials such as transparent conductors, chemical sensors, high-performance composites, and microelectronic interconnects. In particular, many applications require highdensity CNT assemblies that cannot currently be made directly by low-density CNT growth, and therefore require post-processing by methods such as elastocapillary densification. We characterize the hierarchical structure of pristine and densified vertically aligned multi-wall CNT forests, by combining small-angle and ultra-small-angle x-ray scattering (USAXS) techniques. This enables the nondestructive measurement of both the individual CNT diameter and CNT bundle diameter within CNT forests, which are otherwise quantified only by delicate and often destructive microscopy techniques. Our measurements show that multi-wall CNT forests grown by chemical vapor deposition consist of isolated and bundled CNTs, with an average bundle diameter of 16 nm. After capillary densification of the CNT forest, USAXS reveals bundles with a diameter >4 lm, in addition to the small bundles observed in the as-grown forests. Combining these characterization methods with new CNT processing methods could enable the engineering of macro-scale CNT assemblies that exhibit significantly improved bulk properties.
XAS study of the orientation of oriented carbon nanotube films
Physica Scripta, 2009
We report a quantitative x-ray absorption spectroscopy (XAS) study of the orientation of carbon nanotubes (CNTs) grown on plain SiO 2 (thickness 8 nm)/Si(100) substrates by a catalytically enhanced dc hot filament chemical vapour deposition (CVD) process. The alignment and orientation of CNT films are generally provided in the literature by scanning electron microscope (SEM) and transmission electron microscope (TEM) images qualitatively. A very few other techniques have been used to more deeply study the alignment of CNTs grown by the CVD technique, such as x-ray diffraction (XRD) or grazing-incidence small-angle x-ray scattering (GISAXS). XAS recorded on the C K-edge provides information on the local environment around carbon atoms and helps us study the orientation of CNTs. We find spectral features very similar to those of HOPG, in agreement with the literature. Meanwhile, we do not observe any extinction of the π * band at grazing incidence. CNTs have an averaged direction perpendicular to the surface of the substrate.
Journal of Applied Crystallography, 2007
This work presents an analysis method for small-angle scattering data utilizing a simplified tube (hollow cylinder) form factor. The simplified form factor captures the rod-like character of a tube at long length scales (one-dimensional), the sheet-like character of the tube wall at intermediate length scales (twodimensional), and the surface characteristics of a tube at small length scales while suppressing the deep minima seen in the exact form factor. Ultra-smallangle X-ray scattering data from composites made with multi-walled carbon nanotubes and a bismaleimide resin are analyzed using the simplified form factor and compared with scanning electron micrographs. Although a hollow core is not evident via microscopy, a solid rod form factor does not fit the data. However, a tube form factor does fit the data and generates reasonable geometric parameters. At higher concentrations, evidence for aggregation is seen in the data. Aggregation is accommodated by including a fractal structure factor within the simplified approach, allowing facile analysis of data from aggregated (poorly dispersed) fillers.