Supramolecular Assembly of Oriented Spherulitic Crystals of Conjugated Polymers Surrounding Carbon Nanotube Fibers.

The directed assembly of conjugated polymers into macroscopic organization with controlled orientation and placement is pivotal in improving device performance. Here, the supramolecular assembly of oriented spherulitic crystals of poly(3-butylthiophene) surrounding a single carbon nanotube fiber under controlled solvent evaporation of solution-cast films is reported. Oriented lamellar structures nucleate on the surface of the nanotube fiber in the form of a transcrystalline interphase. The factors influencing the formation of transcrystals are investigated in terms of chemical structure, crystallization temperature, and time. Dynamic process measurements exhibit the linear growth of transcrystals with time. Microstructural analysis of transcrystals reveals individual lamellar organization and crystal polymorphism. The form II modification occurs at low temperatures, while both form I and form II modifications coexist at high temperatures. A possible model is presented to interpret transcrystallization and polymorphism.

Processing of Composite Electrodes of Carbon Nanotube Fabrics and Inorganic Matrices via Rapid Joule Heating.

Composites of nanocarbon network structures are interesting materials, combining mechanical properties and electrical conductivity superior to those of granular systems. Hence, they are envisaged to have applications as electrodes for energy storage and transfer. Here, we show a new processing route using Joule heating for a nanostructured network composite of carbon nanotube (CNT) fabrics and an inorganic phase (namely, MoS2), and then study the resulting structure and properties. To this end, first, a unidirectional fabric of conductive CNT bundles is electrochemically coated with MoS2. Afterward, the conformally coated inorganic phase is crystallized via heat generated by direct current passing through the CNT ensemble. The Joule heating process is rapid (maximum heating rate up to 31.7 °C/s), enables accurate temperature control, and takes only a few minutes. The resulting composite material combines a high electrical conductivity of up to 1.72 (±0.25) × 105 S/m, tensile modulus as high as 8.82 ± 5.5 GPa/SG, and an axial tensile strength up to 200 ± 58 MPa/SG. Both electrical and mechanical properties are orders of magnitude above those of wet-processed nanocomposites of similar composition. The extraordinary longitudinal properties stem from the network of interconnected and highly aligned CNT bundles. Conductivity and modulus follow approximately a rule of mixtures, similar to a continuous fiber composite, whereas strength scales almost quadratically with the mass fraction of the inorganic phase due to the inorganic constraining realignment of CNTs upon stretching. This processing route is applicable to a wide range of nanocarbon-based composites with inorganic phases, leading to composites with specific strength above steel and electrical conductivity beyond the threshold for electronic limitations in battery electrodes.

TEGylated Double-Walled Carbon Nanotubes as Platforms to Engineer Neuronal Networks.

In the past two decades, important results have been obtained on the application of carbon nanotubes (CNTs) as components of smart interfaces promoting neuronal growth and differentiation. Different forms of CNTs have been employed as scaffolds, including raw CNTs and functionalized CNTs, characterized by a different number of walls, mainly single-walled CNTs (SWCNTs) or multiwalled CNTs (MWCNTs). However, double-walled carbon nanotubes (DWCNTs), which present interesting electronic and transport properties, have barely been studied in the field. Apart from the electrical conductivity, the morphology, shape, porosity, and corresponding mechanical properties of the scaffold material are important parameters when dealing with neuronal cells. Thus, the presence of open porous and interconnected networks is essential for cell growth and differentiation. Here, we present an easy methodology to prepare porous self-standing and electrically conductive DWCNT-based scaffolds and study the growth of neuro/glial networks and their synaptic activity. A cross-linking approach with triethylene glycol (TEG) derivatives is applied to improve the tensile performance of the scaffolds while neuronal growth and differentiation are promoted. By testing different DWCNT-based constructs, we confirm that the manufactured structures guarantee a biocompatible scaffold, while favoring the design of artificial networks with high complexity.

Toward Self-Powered Sensing and Thermal Energy Harvesting in High-Performance Composites via Self-Folded Carbon Nanotube Honeycomb Structures.

The development of high-performance self-powered sensors in advanced composites addresses the increasing demands of various fields such as aerospace, wearable electronics, healthcare devices, and the Internet-of-Things. Among different energy sources, the thermoelectric (TE) effect which converts ambient temperature gradients to electric energy is of particular interest. However, challenges remain on how to increase the power output as well as how to harvest thermal energy at the out-of-plane direction in high-performance fiber-reinforced composite laminates, greatly limiting the pace of advance in this evolving field. Herein, we utilize a temperature-induced self-folding process together with continuous carbon nanotube veils to overcome these two challenges simultaneously, achieving a high TE output (21 mV and 812 nW at a temperature difference of 17 °C only) in structural composites with the capability to harvest the thermal energy from out-of-plane direction. Real-time self-powered deformation and damage sensing is achieved in fabricated composite laminates based on a thermal gradient of 17 °C only, without the need of any external power supply, opening up new areas of autonomous self-powered sensing in high-performance applications based on TE materials.

Gas-to-nanotextile: high-performance materials from floating 1D nanoparticles.

Suspended in the gas phase, 1D inorganic nanoparticles (nanotubes and nanowires) grow to hundreds of microns in a second and can be thus directly assembled into freestanding network materials. The corresponding process continuously transforms gas precursors into aerosols into aerogels into macroscopic nanotextiles. By enabling the assembly of very high aspect ratio nanoparticles, this processing route has translated into high-performance structural materials, transparent conductors and battery anodes, amongst other embodiments. This paper reviews progress in the application of such manufacturing process to nanotubes and nanowires. It analyses 1D nanoparticle growth through floating catalyst chemical vapour deposition (FCCVD), in terms of reaction selectivity, scalability and its inherently ultra-fast growth rates (107-108 atoms per second) up to 1000 times faster than for substrate CVD. We summarise emerging descriptions of the formation of aerogels through percolation theory and multi-scale models for the collision and aggregation of 1D nanoparticles. The paper shows that macroscopic ensembles of 1D nanoparticles resemble textiles in their porous network structure, high flexibility and damage-tolerance. Their bulk properties depend strongly on inter-particle properties and are dominated by alignment and volume fraction. Selected examples of nanotextiles that surpass granular and monolithic materials include structural fibres with polymer-like toughness, transparent conductors, and slurry-free composite electrodes for energy storage.

Ultrafast synthesis of SiC nanowire webs by floating catalysts rationalised through in situ measurements and thermodynamic calculations.

This work presents the synthesis of SiC nanowires floating in a gas stream through the vapour-liquid-solid (VLS) mechanism using an aerosol of catalyst nanoparticles. These conditions lead to ultrafast growth at 8.5 µm s-1 (maximum of 50 µm s-1), which is up to 3 orders of magnitude above conventional substrate-based chemical vapour deposition. The high aspect ratio of the nanowires (up to 2200) favours their entanglement and the formation of freestanding network materials consisting entirely of SiCNWs. The floating catalyst chemical vapour deposition growth process is rationalised through in situ sampling of reaction products and catalyst aerosol from the gas phase, and thermodynamic calculations of the bulk ternary Si-C-Fe phase diagram. The phase diagram suggests a description of the mechanistic path for the selective growth of SiCNWs, consistent with the observation that no other types of nanowires (Si or C) are grown by the catalyst. SiCNW growth occurs at 1130 °C, close to the calculated eutectic. According to the calculated phase diagram, upon addition of Si and C, the Fe-rich liquid segregates a carbon shell, and later enrichment of the liquid in Si leads to the formation of SiC. The exceptionally fast growth rate relative to substrate-based processes is attributed to the increased availability of precursors for incorporation into the catalyst due to the high collision rate inherent to this new synthesis mode.

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.

Ultrahigh strength, modulus, and conductivity of graphitic fibers by macromolecular coalescence.

Theoretical considerations suggest that the strength of carbon nanotube (CNT) fibers be exceptional; however, their mechanical performance values are much lower than the theoretical values. To achieve macroscopic fibers with ultrahigh performance, we developed a method to form multidimensional nanostructures by coalescence of individual nanotubes. The highly aligned wet-spun fibers of single- or double-walled nanotube bundles were graphitized to induce nanotube collapse and multi-inner walled structures. These advanced nanostructures formed a network of interconnected, close-packed graphitic domains. Their near-perfect alignment and high longitudinal crystallinity that increased the shear strength between CNTs while retaining notable flexibility. The resulting fibers have an exceptional combination of high tensile strength (6.57 GPa), modulus (629 GPa), thermal conductivity (482 W/m·K), and electrical conductivity (2.2 MS/m), thereby overcoming the limits associated with conventional synthetic fibers.

Tuning the mechanical properties of composites from elastomeric to rigid thermoplastic by controlled addition of carbon nanotubes.

A commercial thermoplastic polyurethane is identified for which the addition of nanotubes dramatically improves its mechanical properties. Increasing the nanotube content from 0% to 40% results in an increase in modulus, Y, (0.4-2.2 GPa) and stress at 3% strain, σ(ϵ = 3%) , (10-50 MPa), no significant change in ultimate tensile strength, σ(B) , (≈50 MPa) and decreases in strain at break, ϵ(B) , (555-3%) and toughness, T, (177-1 MJ m(-3) ). This variation in properties spans the range from compliant and ductile, like an elastomer, at low mass fractions to stiff and brittle, like a rigid thermoplastic, at high nanotube content. For mid-range nanotube contents (≈15%) the material behaves like a rigid thermoplastic with large ductility: Y = 1.5 GPa, σ(ϵ = 3%) = 36 MPa, σ(B) = 55 MPa, ϵ(B) = 100% and T = 50 MJ m(-3) . Analysis suggests that soft polyurethane segments are immobilized by adsorption onto the nanotubes, resulting in large changes in mechanical properties.

Controlling reaction paths for ultra-fast growth of inorganic nanowires floating in the gas phase.

Synthesis of inorganic nanowires/nanotubes suspended in the gas through floating catalyst chemical vapour deposition (FCCVD) produces exceptional growth rates of 5-1000 micron per second, several orders of magnitude faster than conventional substrate processes. It leads to nanowire lengths >100 microns and thus to the possibility of direct assembly into freestanding macroscopic networks as a continuous process. This work studies the different reaction paths controlling conversion and selectivity in FCCVD applied to the synthesis of silicon nanowires (SiNWs) from silane, grown through an aerosol of gold catalyst nanoparticles. There are two main competing reactions: catalysed growth of SiNWs and non-catalysed formation of amorphous Si nanoparticles. The mass fraction of the two populations can be precisely determined by XRD and Raman spectroscopy, enabling high-throughput screening of reaction parameter space. The experimental data and accompanying analytical model show that selectivity is kinetically controlled by the ratio of precursor/hydrogen carrier gas, through its inhibition of the pyrolisis of silane into silylene. In contrast, the rate of SiNW growth is largely unaffected by hydrogen and not limited by precursor availability. These results provide a framework to describe the kinetics of nanomaterials growth by FCCVD.

Origin of the electrocatalytic activity in carbon nanotube fiber counter-electrodes for solar-energy conversion.

Carbon nanotubes are a versatile platform to develop sustainable and stable electrodes for energy-related applications. However, their electrocatalytic activity is still poorly understood. This work deciphers the origin of the catalytic activity of counter-electrodes (CEs)/current collectors made of self-standing carbon nanotube fibers (CNTfs) using Co2+/Co3+ redox couple electrolytes. This is based on comprehensive electrochemical and spectroscopic characterization of fresh and used electrodes applied to symmetric electrochemical cells using platinum-based CEs as a reference. As the most relevant findings, two straight relationships were established: (i) the limiting current and stability increase rapidly with the surface concentration of oxygen-containing functional groups, and (ii) the catalytic potential is inversely related to the amount of residual metallic Fe catalyst nanoparticles interspersed in the CNTf network. Finally, the fine tuning of the metal nanoparticle content and the degree of functionalization enabled fabrication of efficient and stable dye-sensitized solar cells with cobalt electrolytes and CNTf-CEs outperforming those with reference Pt-CEs.

Electrode Effects on Flexible and Robust Polypropylene Ferroelectret Devices for Fully Integrated Energy Harvesters.

This work presents a characterization study of the electrode interface in polypropylene ferroelectret nanogenerators. An emphasis is made on the comparison of carbon nanotube fiber electrodes with traditional metallic thin film electrodes. Multiple experiments were performed on samples with the same electrode dimensions for a range of applied pressures. Results showed higher open-circuit voltage peak values for the thin film metal electrodes, regardless of the applied pressure. Interestingly, the difference in short-circuit current values between metal and carbon nanotube-based fiber electrodes was not as significant. The carbon nanotube fiber electrode was further investigated by post-treating the fiber with acetone and comparing the results with untreated carbon nanotube film electrodes and thin film metal electrodes. In an effort to enable a monolithic integration of ferroelectret energy harvesters with flexible energy storage elements, this work also presents studies on generation and leakage of induced free charge in the electrodes of flexible ferroelectret energy harvesters. It was found the current leakage through parasitic elements is a faster process than dipole relaxation in the polypropylene film. Finally, an electrode reliability study shows no significant difference in the electrical output of the devices with metallic thin film electrodes after single folding but shows a significant deterioration after crumpling; meanwhile, these processes had no effect on the performance of similar devices with carbon nanotube fiber-based electrodes.

High Ampacity Carbon Nanotube Materials.

Constant evolution of technology is leading to the improvement of electronical devices. Smaller, lighter, faster, are but a few of the properties that have been constantly improved, but these developments come hand in hand with negative downsides. In the case of miniaturization, this shortcoming is found in the inherent property of conducting materials-the limit of current density they can withstand before failure. This property, known as ampacity, is close to reaching its limits at the current scales of use, and the performances of some conductors such as gold or copper suffer severely from it. The need to find alternative conductors with higher ampacity is, therefore, an urgent need, but at the same time, one which requires simultaneous search for decreased density if it is to succeed in an ever-growing electronical world. The uses of these carbon nanotube-based materials, from airplane lightning strike protection systems to the microchip industry, will be evaluated, failure mechanisms at maximum current densities explained, limitations and difficulties in ampacity measurements with different size ranges evaluated, and future lines of research suggested. This review will therefore provide an in-depth view of the rare properties that make carbon nanotubes and their hybrids unique.

Large-Area Schottky Junctions between ZnO and Carbon Nanotube Fibres.

In this study, large-area (10 cm2 ) samples of heterojunctions between zinc oxide and carbon nanotube (CNT) fibre arrays were synthesised. A two-step hydrothermal treatment was used to grow Zn nanowires (NWs) in situ directly onto the CNT array. This resulted in a bulk heterojunction that consisted of a five-micron layer of ZnO crystals in contact with the built-in CNT fabric current collector, with preferential orientation of the ZnO c axis perpendicular to the CNT sheet. The electrical properties of the heterojunction corresponded to a Schottky junction with a barrier height of 0.26 eV and an ideality factor of 2.9. Photoconductivity measurements indicated charge transfer through the ZnO/CNT interface, thus leading to a gain factor of approximately 100 and a responsivity as high as 5000 mA w-1 under UV irradiation. The resulting ZnO/CNT fibre hybrid was both piezoresistive and piezoelectric under transverse compression with an attractive format for energy-harvesting applications.

Gas-Phase Functionalization of Macroscopic Carbon Nanotube Fiber Assemblies: Reaction Control, Electrochemical Properties, and Use for Flexible Supercapacitors.

The assembly of aligned carbon nanotubes (CNTs) into fibers (CNTFs) is a convenient approach to exploit and apply the unique physico-chemical properties of CNTs in many fields. CNT functionalization has been extensively used for its implementation into composites and devices. However, CNTF functionalization is still in its infancy because of the challenges associated with preservation of CNTF morphology. Here, we report a thorough study of the gas-phase functionalization of CNTF assemblies using ozone which was generated in situ from a UV source. In contrast with liquid-based oxidation methods, this gas-phase approach preserves CNTF morphology, while notably increasing its hydrophilicity. The functionalized material is thoroughly characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. Its newly acquired hydrophilicity enables CNTF electrochemical characterization in aqueous media, which was not possible for the pristine material. Through comparison of electrochemical measurements in aqueous electrolytes and ionic liquids, we decouple the effects of functionalization on pseudocapacitive reactions and quantum capacitance. The functionalized CNTF assembly is successfully used as an active material and a current collector in all-solid supercapacitor flexible devices with an ionic liquid-based polymer electrolyte.

Energy storage in structural composites by introducing CNT fiber/polymer electrolyte interleaves.

This work presents a method to produce structural composites capable of energy storage. They are produced by integrating thin sandwich structures of CNT fiber veils and an ionic liquid-based polymer electrolyte between carbon fiber plies, followed by infusion and curing of an epoxy resin. The resulting structure behaves simultaneously as an electric double-layer capacitor and a structural composite, with flexural modulus of 60 GPa and flexural strength of 153 MPa, combined with 88 mF/g of specific capacitance and the highest power (30 W/kg) and energy (37.5 mWh/kg) densities reported so far for structural supercapacitors. In-situ electrochemical measurements during 4-point bending show that electrochemical performance is retained up to fracture, with minor changes in equivalent series resistance for interleaves under compressive stress. En route to improving interlaminar properties we produce grid-shaped interleaves that enable mechanical interconnection of plies by the stiff epoxy. Synchrotron 3D X-ray tomography analysis of the resulting hierarchical structure confirms the formation of interlaminar epoxy joints. The manuscript discusses encapsulation role of epoxy, demonstrated by charge-discharge measurements of composites immersed in water, a deleterious agent for ionic liquids. Finally, we show different architectures free of current collector and electrical insulators, in which both CNT fiber and CF act as active electrodes.

Interfacial charge transfer in functionalized multi-walled carbon nanotube@TiO2 nanofibres.

A new insight into photoinduced charge transfer processes across carbon nanotube@TiO2 interfaces has been gained based on experimental details from transient absorption spectroscopy. We show that photoinduced, interfacial hole transfer to carboxylic acid-functionalized multiwalled carbon nanotubes (oxMWCNTs) from TiO2 results in hole-doped oxMWCNTs and reduced TiO2. The latter is inferred from femto- and nanosecond transient absorption spectroscopy performed with oxMWCNT@TiO2 dispersions and complemented with investigations using methyl viologen and N,N,N',N'-tetramethyl-p-phenylenediamine as an electron scavenger and a hole scavenger, respectively. The results of ultraviolet photoemission spectroscopy (UPS) of the compounds corroborate the findings, highlighting the strong coupling between oxMWCNTs and TiO2 in these hybrids.

Threading through Macrocycles Enhances the Performance of Carbon Nanotubes as Polymer Fillers.

In this work, we study the reinforcement of polymers by mechanically interlocked derivatives of single-walled carbon nanotubes (SWNTs). We compare the mechanical properties of fibers made of polymers and of composites with pristine SWNTs, mechanically interlocked derivatives of SWNTs (MINTs), and the corresponding supramolecular models. Improvements of both Young's modulus and tensile strength of up to 200% were observed for the polystyrene-MINT samples with an optimized loading of just 0.01 wt %, while the supramolecular models with identical chemical composition and loading showed negligible or even detrimental influence. This behavior is found for three different types of SWNTs and two types of macrocycles. Molecular dynamics simulations show that the polymer adopts an elongated conformation parallel to the SWNT when interacting with MINT fillers, irrespective of the macrocycle chemical nature, whereas a more globular structure is taken upon facing with either pristine SWNTs or supramolecular models. The MINT composite architecture thus leads to a more efficient exploitation of the axial properties of the SWNTs and of the polymer chain at the interface, in agreement with experimental results. Our findings demonstrate that the mechanical bond imparts distinctive advantageous properties to SWNT derivatives as polymer fillers.

Inherent predominance of high chiral angle metallic carbon nanotubes in continuous fibers grown from a molten catalyst.

We present evidence that high temperature CVD growth of SWNTs under conditions of continuous spinning of macroscopic fibers leads to an inherent predominance of high chiral angle CNTs, peaking at the armchair end. Raman, UV-vis-NIR absorption, and photoluminescence spectroscopy measurements show the prevalence of metallic SWNTs. The complete chiral angle distribution is obtained by electron diffraction of over 390 CNTs. It is biased towards high chiral angles and peaks at the armchair end (30°), in good agreement with the established atomistic models for SWNT growth from a liquid catalyst. Based on the Fe-C-S constituent binary and ternary phase diagrams, thermodynamic calculations of phase compositions from fast cooling and experimental evidence of a post-synthesis catalyst, the proposed thermodynamic path of the catalyst is to form a solid FCC Fe core and a liquid Fe-S shell. S in the outer liquid shell first stabilizes the edge of the nascent CNT, but once a graphitic wall forms it is rejected due to the high interfacial energy of the Fe-C-S alloy.

Strong Carbon Nanotube Fibers by Drawing Inspiration from Polymer Fiber Spinning.

We present a method to spin highly oriented continuous fibers of adjustable carbon nanotube (CNT) type, with mechanical properties in the high-performance range. By lowering the concentration of nanotubes in the gas phase, through either reduction of the precursor feed rate or increase in carrier gas flow rate, the density of entanglements is reduced and the CNT aerogel can thus be drawn (up to 18 draw ratio) and wound at fast rates (>50 m/min). This is achieved without affecting the synthesis process, as demonstrated by Raman spectroscopy, and implies that the parameters controlling composition in terms of CNT diameter and number of layers are decoupled from those fixing CNT orientation. Applying polymer fiber wet-spinning principles then, strong CNT fibers (1 GPa/SG) are produced under dilute conditions and high draw ratios, corresponding to highly aligned fibers (from wide- and small-angle X-ray scattering). This is demonstrated for fibers either made up of predominantly single-wall CNTs (SWCNTs) or predominantly multiwall CNTs (MWCNTs), which surprisingly have very similar tensile properties. Finally, we show that postspin densification has no substantial effect on either alignment or properties (mechanical and electrical). These results demonstrate a route to control CNT assembly and reinforce their potential as a high-performance fiber.