The electro-structural behaviour of yarn-like carbon nanotube fibres immersed in organic liquids.

Yarn-like carbon nanotube (CNT) fibres are a hierarchically-structured material with a variety of promising applications such as high performance composites, sensors and actuators, smart textiles, and energy storage and transmission. However, in order to fully realize these possibilities, a more detailed understanding of their interactions with the environment is required. In this work, we describe a simplified representation of the hierarchical structure of the fibres from which several mathematical models are constructed to explain electro-structural interactions of fibres with organic liquids. A balance between the elastic and surface energies of the CNT bundle network in different media allows the determination of the maximum lengths that open junctions can sustain before collapsing to minimize the surface energy. This characteristic length correlates well with the increase of fibre resistance upon immersion in organic liquids. We also study the effect of charge accumulation in open interbundle junctions and derive expressions to describe experimental data on the non-ohmic electrical behaviour of fibres immersed in polar liquids. Our analyses suggest that the non-ohmic behaviour is caused by progressively shorter junctions collapsing as the voltage is increased. Since our models are not based on any property unique to carbon nanotubes, they should also be useful to describe other hierarchical structures.

High throughput production of single-wall carbon nanotube fibres independent of sulfur-source.

Floating catalyst chemical vapor deposition (FC-CVD) methods offer a highly scalable strategy for single-step synthesis and assembly of carbon nanotubes (CNTs) into macroscopic textiles. However, the non-uniform axial temperature profile of a typical reactor, and differing precursor breakdown temperatures, result in a broad distribution of catalyst particle sizes. Spun CNT fibres therefore contain nanotubes with varying diameters and wall numbers. Herein, we describe a general FC-CVD approach to obtain relatively large yields of predominantly single-wall CNT fibres, irrespective of the growth promoter (usually a sulfur compound). By increasing carrier gas (hydrogen) flow rate beyond a threshold whilst maintaining a constant C : H2 mole ratio, CNTs with narrower diameters, a high degree of graphitization (G : D ratio ∼100) and a large throughput are produced, provided S : Fe ratio is sufficiently low. Analysis of the intense Raman radial breathing modes and asymmetric G bands, and a shift in the main nanotube population from thermogravimetric data, show that with increasing flow rate, the fibres are enriched with small diameter, metallic CNTs. Transmission electron microscopy corraborates our primary observation from Raman spectroscopy that with high total flow rates, the fibres produced consist of predominantly small diameter SWCNTs.

Enhanced ordering reduces electric susceptibility of liquids confined to graphene slit pores.

The behaviours of a range of polar and non-polar organic liquids (acetone, ethanol, methanol, N-methyl-2-pyrrolidone (NMP), carbon tetrachloride and water) confined to 2D graphene nanochannels with thicknesses in the range of 4.5 Å to 40 Å were studied using classical molecular dynamics and hybrid density functional theory. All liquids were found to organise spontaneously into ordered layers parallel to the confining surfaces, with those containing polar molecules having their electric dipoles aligned parallel to such surfaces. In particular, monolayers of NMP showed remarkable in-plane ordering and low molecular mobility, suggesting the existence of a previously unknown 2D solid-like phase. Calculations for polar liquids showed dramatically reduced static permittivities normal to the confining surfaces; these changes are expected to improve electron tunnelling across the liquid films, modifying the DC electrical properties of immersed assemblies of carbon nanomaterials.

Electric field-modulated non-ohmic behavior of carbon nanotube fibers in polar liquids.

We report a previously unseen non-ohmic effect in which the resistivity of carbon nanotube fibers immersed in polar liquids is modulated by the applied electric field. This behavior depends on the surface energy, dielectric constant, and viscosity of the immersion media. Supported by synchrotron SAXS and impedance spectroscopy, we propose a model in which the gap distance, and thus the conductance, of capacitive interbundle junctions is controlled by the applied field.

Liquid infiltration into carbon nanotube fibers: effect on structure and electrical properties.

Carbon nanotube (CNT) fibers consist of a network of highly oriented carbon nanotube bundles. This paper explores the ingress of liquids into the contiguous internal pores between the bundles using measurements of contact angles and changes in fiber dimensions. The resultant effects on the internal structure of the fiber have been examined by WAXS and SAXS. A series of time-resolved experiments measured the influence of the structural changes on the electrical resistivity of the fiber. All organic liquids tested rapidly wicked into the fiber to fill its internal void structure. The local regions in which the nanotube bundles are aggregated to give a bundle network were broken up by the liquid ingress. For the range of organic penetrants examined, the strength of the effects on structure and electrical resistivity was correlated, not only with the degree to which the liquid reduced the nanotube surface energy, but also with the Hansen affinity parameters. The fact that liquid environments influence the electrical performance of these fibers is of significance if they are to replace copper as power and signal conductors, with added implications regarding the possible ingress of external insulating materials, and possibly also sensing applications.