Quantifying alignment in carbon nanotube yarns and similar two-dimensional anisotropic systems

Abstract: The uniaxial orientational order in a macromolecular system is usually specified using the Hermans factor which is equivalent to the second moment of the system's orientation distribution function (ODF) expanded in terms of Legendre polynomials. In this work, we show that for aligned materials that are two‐dimensional (2D) or have a measurable 2D intensity distribution, such as carbon nanotube (CNT) textiles, the Hermans factor is not appropriate. The ODF must be expanded in terms of Chebyshev polynomials and therefore, its second moment is a better measure of orientation in 2D. We also demonstrate that both orientation parameters (Hermans in three dimensional (3D) and Chebyshev in 2D) depend not only on the respective full‐width‐at‐half‐maximum of the peaks in the ODF but also on the shape of the fitted functions. Most importantly, we demonstrate a method to rapidly estimate the Chebyshev orientation parameter from a sample's 2D Fourier power spectrum, using an analysis program written in Python which is available for open access. As validation examples, we use digital photographs of dry spaghetti as well as scanning electron microscopy images of direct‐spun carbon nanotube fibers, proving the technique's applicability to a wide variety of fibers and images

Mechanical properties of carbon nanotube fibres: St Venant's principle at the limit and the role of imperfections

Carbon nanotube (CNT) fibres, especially if perfect in terms of purity and alignment, are of extreme anisotropy. With their high axial strength but ready slippage between the CNTs, there is utmost difficulty in transferring the force applied uniformly. Finite element analysis is used to predict the stress distribution in CNT fibres loaded by grips attached to their surface, along with the resulting tensile stress-strain curves. This study demonstrates that in accordance with St Venant’s principle very considerable length-to-diameter ratios (~ 103) are required before the stress becomes uniform across the fibre, even at low strains. It is proposed that lack of perfect orientation and presence of carbonaceous material between bundles greatly enhances the stress transfer, thus increasing the load it can carry before failing by shear. It is suggested that a very high strength batch of fibres previously observed experimentally had an unusually high concentration of internal particles, meaning that the pressure exerted by the grips would assist stress transfer between the layers. We conclude, that the strength of CNT fibres depends on the specific testing geometries and that imperfections, whether by virtue of less-than-perfect orientation or of embedded impurities, are actually major positive contributors to the observed strength.The authors are grateful to USN ONR GLOBAL for the provision of funding under award number N62909-14-1-N200. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the Office of Naval Research.This is the accepted manuscript. The final version is available at http://www.sciencedirect.com/science/article/pii/S0008622315004728

The mechanical and electrical properties of direct-spun carbon nanotube mats

The mechanical and electrical properties of a direct-spun carbon nanotube mat are measured. The mat comprises an interlinked random network of nanotube bundles, with approximately 40 nanotubes in a bundle. A small degree of in-plane anisotropy is observed. The bundles occasionally branch, and the mesh topology resembles a 2D lattice of nodal connectivity slightly below 4. The macroscopic in-plane tensile response is elasto-plastic in nature, with significant orientation hardening. In-situ microscopy reveals that the nanotube bundles do not slide past each other at their junctions under macroscopic stain. A micromechanical model is developed to relate the macroscopic modulus and flow strength to the longitudinal shear response of the nanotube bundles. The mechanical and electrical properties of the mat are compared with those of other nanotube arrangements over a wide range of density

Chirality-independent characteristic crystal length in carbon nanotube textiles measured by Raman spectroscopy

Raman spectroscopy's D:G ratio is a well-known indicator of graphitic crystallinity in single-wall carbon nanotubes (SWCNTs) with widespread qualitative application to macroscopic CNT assemblies. Here, we show how the D:G ratio yields quantitative characteristic crystal length features that is remarkably independent of SWCNT chirality when purified SWCNTs are in a high density, heavily bundled textile form. Purified, unaligned, SWCNT films of enriched length distributions and controlled chirality responded in ways consistent with power law behaviour, where the D:G ratio is proportional to the fourth power of excitation wavelength, inversely proportional to SWCNT length, and fits to a master curve independent of electronic species concentration. This behaviour, matching the established response of graphite and graphene, unexpectedly persists despite complications from chirality-dependent resonances unique to SWCNTs. We also show that textiles comprising of aligned, long length CNTs defy these simple power laws until defective multiwall CNTs and impurities are removed post-process, and only if sample heating under the Raman laser is minimized. Adjusting the Raman laser beam diameter up to 6 mm, which is well beyond the average CNT length, we propose that the CNT textile's characteristic crystal length is the CNT length or, with point defects, the distance between point defects

Extreme stretching of high G:D ratio carbon nanotube fibers using super-acid

Few-wall carbon nanotube (CNT) textiles with unparalleled graphitic perfection and a solitary, prominent radial breathing mode (RBM) associated with metallic chirality have been mechanically stretched in chlorosulfonic acid (CSA) to a degree so far unseen in CNT textiles (150–250% of original length) with notably little tension required. This dramatically enhanced their microstructural alignment and density and, after most of the residual CSA was removed by a vacuum bake, the de-doped fiber's electrical conductivity was found to be 45% greater than single-crystal graphite – a significant milestone for CNT conductor development towards graphitic intercalation compounds (GICs) and traditional metals. Correlation tables and validated, multivariate statistical models show that conductivity is overwhelmingly linked to stretching degree, although eventually saturates near single-crystal graphite levels, implying the existence of a maximum undoped conductivity. The degree of stretching within CSA is correlated with the original mechanical properties (tenacity, elongation-to-break, and linear density); the Raman G’:G ratio and the upper-end oxidation temperature in thermogravimetric analysis also predict the best results. Less graphenically pristine CNT materials stretch to a lower degree in CSA, similar to previous reports. This study highlights the importance of post-synthesis processing to achieve superior performance in carbon nanotube textile materials

Triboluminescence flashes from high-speed ruptures in carbon nanotube Macro-Yarns

© 2017 During tensile tests of carbon nanotube (CNT) macrostructures (ribbons, ropes and tows) under dynamic strain rates (1000 s –1 ), we recorded temporally sporadic, spatially localized visible light emissions (“flashes”) of less than 1.5 µs duration. The flashes occurred at the fracture sites and were, depending on the sample morphology, either distributed randomly over time (for tows) or occurred all at once over larger areas of several pixels (for ribbons). In situ thermal camera measurements, as well as ex situ analysis by electron microscopy reveal a hierarchical mechanism of overall heating over the whole sample length during straining, and localized heating around the fracture surfaces. Temperatures around the fracture tip were calculated to be of 1800 K in average. We propose that the flashes are caused by charge separation due to CNT bond fracture and gas discharge of the surrounding gases. Triboluminescence, known for larger sugar crystals, has not been observed for carbon nanotubes previously. It results from the yarn-like morphology, the ultra-high strength and thermal conductivity of our CNT fibers, which at high strain rates concentrate the strain at CNT level and lead to CNT fracture, rather than bundle sliding

High thermal conductivities of carbon nanotube films and micro-fibres and their dependence on morphology

Thermal conductivity of carbon nanotube (CNT) films and micro-fibres synthesised by floating catalyst chemical vapour deposition was measured by the parallel thermal conductance method. CNT films showed in-plane thermal conductivities of 110 W m⁻¹ K⁻¹. Online condensation into a micro-fibre morphology – a two-dimensional reduction in the transverse plane, including some axial stretching during solvent evaporation – resulted in room-temperature thermal conductivity values as high as 770 ± 10 W m⁻¹ K⁻¹, which is the highest thermal conductivity reported for CNT bulk materials to date. In specific terms, this matches the maximum thermal conductivity of heat-treated carbon fibre, but with a higher onset temperature for Umklapp scattering processes (300 K rather than 150 K). We selected four sample types to investigate effects of alignment, purity, and single- or multi-wall character on their thermal conductivity. For both the electrical and thermal conductivity of as-spun material, i.e. without any post-synthesis treatment, we show that the density and quality of CNT bundle alignment are still the predominant factors affecting these properties, outweighing the influence of single- or multi-walled character of the nanotubes. This raises the promise that, with optimal alignment and junction points, even higher values of thermal conductivity are achievable for macroscopic CNT fibres.We also acknowledge the US Office of Naval Research (W911NF-11-1-0250) and ONR Global (N62909-15-1-2034) for funding and support. The work at Dalhousie University was supported by NSERC (RGPIN-2015-04593), as well as the Canada Foundation for Innovation, Atlantic Innovation Fund, Dalhousie University and other partners that fund the Facilities for Materials Characterisation managed by the Institute for Research in Materials

Catalyst‐mediated enhancement of carbon nanotube textiles by laser irradiation: Nanoparticle sweating and bundle alignment

The photonic post-processing of suspended carbon nanotube (CNT) ribbons made by floating catalyst chemical vapor deposition (FC-CVD) results in selective sorting of the carbon nanotubes present. Defective, thermally non-conductive or unconnected CNTs are burned away, in some cases leaving behind a highly crystalline (as indicated by the Raman G:D ratio), highly conductive network. However, the improvement in crystallinity does not always occur but is dependent on sample composition. Here, we report on fundamental features, which are observed for all samples. Pulse irradiation (not only by laser but also white light camera flashes, as well as thermal processes such as Joule heating) lead to (1) the sweating-out of catalyst nanoparticles resulting in molten catalyst beads of up to several hundreds of nanometres in diameter on the textile surface and (2) a significant improvement in CNT bundle alignment. The behavior of the catalyst beads is material dependent. Here, we show the underlying mechanisms of the photonic post-treatment by modelling the macro- and microstructural changes of the CNT network and show that it is mainly the amount of residual catalyst which determines how much energy these materials can withstand before their complete decomposition.</jats:p

Spinning of carbon nanotube fibres using the floating catalyst high temperature route: Purity issues and the critical role of sulphur

The CVD process for the spinning of carbon nanotube (CNT) fibres combines the nucleation, growth and aggregation of CNTs in the form of an aerogel with fibre spinning into a single process step. The optimisation of the process requires agility in multi-dimensional parameter space, so one tends to find parameter 'islands' where spinning is possible, while exploration tends to follow 'routes' through this space. Here, we follow two such routes, one of which drastically improves fibre purity, the other changes the nature of the nanotubes comprising the fibres from multiwall to single wall. In the first case there is only a modest enhancement of the mechanical properties, but in the second a very considerable improvement is seen. In terms of the conditions required to make fibres comprising predominately single wall CNTs, the key factor appears to be the rigorous control of the sulphur addition, in trace quantities, coupled with the availability of carbon atoms at the earliest stage after injection, typically in the range 400-500 °C. A model is presented for the role of sulphur in floating catalysts CNT synthesis