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.Mexican Council for Science and Technology (CONACyT)This is the final version of the article. It first appeared from Nature Publishing Group via http://dx.doi.org/10.1038/srep2740

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

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.JT acknowledges generous financial support from: The Cambridge Commonwealth European and International Trust, CONACyT (Mexico), Dyson Ltd, and Pembroke College Cambridge. JJV acknowledges support from MINECO (Spain) and FP7-People-Marie Curie Action-CIG.This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/nn5030835

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

Highly Oriented Direct-Spun Carbon Nanotube Textiles Aligned by In Situ Radio-Frequency Fields.

Carbon nanotubes (CNTs) individually exhibit exceptional physical properties, surpassing state-of-the-art bulk materials, but are used commercially primarily as additives rather than as a standalone macroscopic product. This limited use of bulk CNT materials results from the inability to harness the superb nanoscale properties of individual CNTs into macroscopic materials. CNT alignment within a textile has been proven as a critical contributor to narrow this gap. Here, we report the development of an altered direct CNT spinning method based on the floating catalyst chemical vapor deposition process, which directly interacts with the self-assembly of the CNT bundles in the gas phase. The setup is designed to apply an AC electric field to continuously align the CNTs in situ during the formation of CNT bundles and subsequent aerogel. A mesoscale CNT model developed to simulate the alignment process has shed light on the need to employ AC rather than DC fields based on a CNT stiffening effect (z-pinch) induced by a Lorentz force. The AC-aligned synthesis enables a means to control CNT bundle diameters, which broadened from 16 to 25 nm. The resulting bulk CNT textiles demonstrated an increase in the specific electrical and tensile properties (up to 90 and 460%, respectively) without modifying the quantity or quality of the CNTs, as verified by thermogravimetric analysis and Raman spectroscopy, respectively. The enhanced properties were correlated to the degree of CNT alignment within the textile as quantified by small-angle X-ray scattering and scanning electron microscopy image analysis. Clear alignment (orientational order parameter = 0.5) was achieved relative to the pristine material (orientational order parameter = 0.19) at applied field intensities in the range of 0.5-1 kV cm-1 at a frequency of 13.56 MHz.We gratefully acknowledge funding provided through the UK government’s modern industrial strategy by Innovate UK, part of UK Research and Innovation, and from the EPSRC project “Advanced Nanotube Application and Manufacturing Initiative under Grant No. EP/M015211/1

Dataset for Catalyst-Mediated Enhancement of Carbon Nanotube Textiles by Laser Irradiation: Nanoparticle Sweating and Bundle Alignment

The folder contains Microsoft Excel files (.xlsx) of Raman spectra, Thermogravimetric Analysis data, and TEM Energy Dispersive X-ray spectroscopy (EDX) data for the samples analysed in the work, the results from the macroscale thermomechanical model and the Python code for the microscale model

Raman and TGA data supporting Kaniyoor et al. "High throughput production of single-wall carbon nanotube fibres independent of sulfur-source"

Supporting data for Raman spectra and Thermogravimetric Analysis (TGA) data given in Kaniyoor et al. "High throughput production of single-wall carbon nanotube fibres independent of sulfur-source". The folder contains Raman spectroscopy and Thermogravimetry data for the various samples analysed in the work. Raman spectra were obtained using a Bruker Raman Senterra microscope with laser lines 532 (2.33 eV, 5 mW), 633 (1.96 eV, 5 mW), and 785 nm (1.58 eV, 10 mW). For every sample at least five different locations are sampled under a x20 objective, and averaged in the Bruker OPUS software. The raw data is presented in the Raman folder, named as Date synthesised_Sample name_Microscope Objective_Laser Wavelength_Laser Power_Accumulation time_Number of additions. Each data file has two columns which are Raman shift (in cm-1) and Intensity (counts). Please refer to the excel/.csv file in this folder to link the sample names to the flow rate, sulfur source (thiophene, carbon disulphide (CS2), elemental sulfur) and molar concentration (Low = 0.76 S:Fe, high = 1.52 S:Fe) under which the samples were synthesised. To obtain graphs presented in the paper, the data must be baseline corrected by asymmetric least squares method, and all intensities must be normalized to the respective G band intensity maximum. G:D values are calculated by taking the area of the G and D peaks. These analyses can easily be performed in Origin software. Thermogravimetry was performed using a TA Instruments Q500 under a dynamic ramp rate to 1000 ∞C with synthetic air. The data presented were obtained directly from the TA instruments software. The naming protocol is as follows: Sample synthesized date_Sample number_sulfur concentration and source hydrogen flow rate. Each data file has several columns of data. The important columns are 2nd- temperature (in celcius), 3rd ñ mass of the sample at different temperatures (in mg), 6th ñ derivate mass loss data. Information such as amorphous carbon content and residual catalyst can be obtained from the mass loss curves. Integrating different peaks in the derivative curves gives the amount of species that burn at that peak

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