Structure–Property Relations in Carbon Nanotube Fibers by Downscaling Solution Processing

At the microscopic scale, carbon nanotubes (CNTs) combine impressive tensile strength and electrical conductivity; however, their macroscopic counterparts have not met expectations. The reasons are variously attributed to inherent CNT sample properties (diameter and helicity polydispersity, high defect density, insufficient length) and manufacturing shortcomings (inadequate ordering and packing), which can lead to poor transmission of stress and current. To efficiently investigate the disparity between microscopic and macroscopic properties, a new method is introduced for processing microgram quantities of CNTs into highly oriented and well‐packed fibers. CNTs are dissolved into chlorosulfonic acid and processed into aligned films; each film can be peeled and twisted into multiple discrete fibers. Fibers fabricated by this method and solution‐spinning are directly compared to determine the impact of alignment, twist, packing density, and length. Surprisingly, these discrete fibers can be twice as strong as their solution‐spun counterparts despite a lower degree of alignment. Strength appears to be more sensitive to internal twist and packing density, while fiber conductivity is essentially equivalent among the two sets of samples. Importantly, this rapid fiber manufacturing method uses three orders of magnitude less material than solution spinning, expanding the experimental parameter space and enabling the exploration of unique CNT sources.     

Synthesis and characterization of vertically aligned carbon nanotube forest for solid state fiber spinning

Continuous carbon nanotubes (CNT) fibers were directly spun from a vertically aligned CNT forest grown by a plasma-enhanced chemical vapor deposition (PECVD) process. The correlation of the CNT structure with Fe catalyst coarsening, reaction time, and the CNTs bundling phenomenon was investigated. We controlled the diameters and walls of the CNTs and minimized the amorphous carbon deposition on the CNTs for favorable bundling and spinning of the CNT fibers. The CNT fibers were fabricated with an as-grown vertically aligned CNT forest by a PECVD process using nanocatalyst an Al2O3 buffer layer, followed by a dry spinning process. Well-aligned CNT fibers were successfully manufactured using a dry spinning process and a surface tension-based densification process by ethanol. The mechanical properties were characterized for the CNT fibers spun from different lengths of a vertically aligned CNT forest. Highly oriented CNT fibers from the dry spinning process were characterized with high strength, high modulus, and high electrical as well as thermal conductivities for possible application as ultralight, highly strong structural materials. Examples of structural materials include space elevator cables, artificial muscle, and armor material, while multifunctional materials include E-textile, touch panels, biosensors, and super capacitors.     

Significantly Increased Solubility of Carbon Nanotubes in Superacid by Oxidation and Their Assembly into High‐Performance Fibers

This study demonstrates that small amount of oxygen incorporated into carbon nanotubes (CNTs) during the purification process greatly increases their solubility in chlorosulfonic acid (CSA). Using as‐purchased and unpurified CNT powders, the optimal purification process is established to significantly increase the solubility of CNTs in CSA, and spin CNT fibers with high mechanical strength (0.84 N tex^?1) and electrical conductivity (1.4 MS m^?1) from the CNT liquid crystal dope with high concentration of CNTs in CSA. The knowledge obtained here may guide development of a way to dissolve extremely long CNTs at high concentration and thereby to enable production of CNT fibers with ultimate properties.     

State of the Art of Carbon Nanotube Fibers: Opportunities and Challenges

The superb mechanical and physical properties of individual carbon nanotubes (CNTs) have provided the impetus for researchers in developing high‐performance continuous fibers based upon CNTs. The reported high specific strength, specific stiffness and electrical conductivity of CNT fibers demonstrate the potential of their wide application in many fields. In this review paper, we assess the state of the art advances in CNT‐based continuous fibers in terms of their fabrication methods, characterization and modeling of mechanical and physical properties, and applications. The opportunities and challenges in CNT fiber research are also discussed.     

Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

From Molecular Reconstruction of Mesoscopic Functional Conductive Silk Fibrous Materials to Remote Respiration Monitoring

Turning insulating silk fibroin materials into conductive ones turns out to be the essential step toward achieving active silk flexible electronics. This work aims to acquire electrically conductive biocompatible fibers of regenerated Bombyx mori silk fibroin (SF) materials based on carbon nanotubes (CNTs) templated nucleation reconstruction of silk fibroin networks. The electronical conductivity of the reconstructed mesoscopic functional fibers can be tuned by the density of the incorporated CNTs. It follows that the hybrid fibers experience an abrupt increase in conductivity when exceeding the percolation threshold of CNTs >35 wt%, which leads to the highest conductivity of 638.9 S m^?1 among organic‐carbon‐based hybrid fibers, and 8 times higher than the best available materials of the similar types. In addition, the silk‐CNT mesoscopic hybrid materials achieve some new functionalities, i.e., humidity‐responsive conductivity, which is attributed to the coupling of the humidity inducing cyclic contraction of SFs and the conductivity of CNTs. The silk‐CNT materials, as a type of biocompatible electronic functional fibrous material for pressure and electric response humidity sensing, are further fabricated into a smart facial mask to implement respiration condition monitoring for remote diagnosis and medication.     

Evaluation and visualization of the percolating networks in multi-wall carbon nanotube/epoxy composites

In this study, epoxy-based nanocomposites containing multi-wall carbon nanotubes (CNTs) were produced by a calendering approach. The electrical conductivities of these composites were investigated as a function of CNT content. The conductivity was found to obey a percolation-like power law with a percolation threshold below 0.05 vol.%. The electrical conductivity of the neat epoxy resin could be enhanced by nine orders of magnitude, with the addition of only 0.6 vol.% CNTs, suggesting the formation of a well-conducting network by the CNTs throughout the insulating polymer matrix. To characterize the dispersion and the morphology of CNTs in epoxy matrix, different microscopic techniques were applied to characterize the dispersion and the morphology of CNTs in epoxy matrix, such as atomic force microscopy, transmission electron microscopy, and scanning electron microscopy (SEM). In particular, the charge contrast imaging in SEM allows a visualization of the overall distribution of CNTs at a micro-scale, as well as the identification of CNT bundles at a nano-scale. On the basis of microscopic investigation, the electrical conduction mechanism of CNT/epoxy composites is discussed.     

Micromechanics modeling of the electrical conductivity of carbon nanotube (CNT)–polymer nanocomposites

A mixed micromechanics model was developed to predict the overall electrical conductivity of carbon nanotube (CNT)–polymer nanocomposites. Two electrical conductivity mechanisms, electron hopping and conductive networks, were incorporated into the model by introducing an interphase layer and considering the effective aspect ratio of CNTs. It was found that the modeling results agree well with the experimental data for both single-wall carbon nanotube and multi-wall carbon nanotube based nanocomposites. Simulation results suggest that both electron hopping and conductive networks contribute to the electrical conductivity of the nanocomposites, while conductive networks become dominant as CNT volume fraction increases. It was also indicated that the sizes of CNTs have significant effects on the percolation threshold and the overall electrical conductivity of the nanocomposites. This developed model is expected to provide a more accurate prediction on the electrical conductivity of CNT–polymer nanocomposites and useful guidelines for the design and optimization of conductive polymer nanocomposites.     

Fabrication and Electrical Characterization of Densified Carbon Nanotube Micropillars for IC Interconnection

Closely packed carbon nanotube (CNT) bundles are expected to have higher conductivity than copper and could potentially replace copper for electrical and thermal conductors in IC chips. However, it is extremely difficult, if not impossible, to controllably grow closely packed CNT bundles. We report on a novel postgrowth capillary densification method, which results in dramatic increase of CNT site density. Bare CNT pillars are densified approximately 15 times. High-density CNT micropillars and micrologs with round cross sections were fabricated from CNTs coated with parylene prior to densification. These CNT micropillars and micrologs could be used as basic building blocks for future IC interconnection. Electrical characterization results show that the densification process does not mitigate the electrical conducting performance of CNTs.      

Composite Yarns of Multiwalled Carbon Nanotubes with Metallic Electrical Conductivity

Unique macrostructures known as spun carbon‐nanotube fibers (CNT yarns) can be manufactured from vertically aligned forests of multiwalled carbon nanotubes (MWCNTs). These yarns behave as semiconductors with room‐temperature conductivities of about 5 × 10² S cm^?1. Their potential use as, for example, microelectrodes in medical implants, wires in microelectronics, or lightweight conductors in the aviation industry has hitherto been hampered by their insufficient electrical conductivity. In this Full Paper, the synthesis of metal–CNT composite yarns, which combine the unique properties of CNT yarns and nanocrystalline metals to obtain a new class of materials with enhanced electrical conductivity, is presented. The synthesis is achieved using a new technique, self‐fuelled electrodeposition (SFED), which combines a metal reducing agent and an external circuit for transfer of electrons to the CNT surface, where the deposition of metal nanoparticles takes place. In particular, the Cu–CNT and Au–CNT composite yarns prepared by this method have metal‐like electrical conductivities (2–3 × 10⁵ S cm^?1) and are mechanically robust against stringent tape tests. However, the tensile strengths of the composite yarns are 30–50% smaller than that of the unmodified CNT yarn. The SFED technique described here can also be used as a convenient means for the deposition of metal nanoparticles on solid electrode supports, such as conducting glass or carbon black, for catalytic applications.     

Optimized network of multi-walled carbon nanotubes for chemical sensing

This work reports the design of a resistive gas sensor based on 2D mats of multi-walled carbon nanotubes (MWCNTs) grown by aerosol-assisted chemical vapour deposition. The sensor sensitivity was optimized using chlorine as analyte by tuning both CNT network morphology and CNT electronic properties. Optimized devices, operating at room temperature, have been calibrated over a large range of concentration and are shown to be sensitive down to 27 ppb of chlorine. The as-grown MWCNT response is compared with responses of 2000?°C annealed CNTs, as well as of nitrogen-doped CNTs and CNTs functionalized with polyethyleneimine (PEI). Under chlorine exposure, the resistance decrease of as-grown and annealed CNTs is attributed to charge transfer from chlorine to CNTs and demonstrates their p-type semiconductor behaviour. XPS analysis of CNTs exposed to chlorine shows the presence of chloride species that confirms electron charge transfer from chlorine to CNTs. By contrast, the resistance of nitrogen-doped and PEI functionalized CNTs exposed to chlorine increases, in agreement with their n-type semiconductor nature. The best response is obtained using annealed CNTs and is attributed to their higher degree of crystallinity.     

Preparation of carbon nanotube/epoxy composite films with high tensile strength and electrical conductivity by impregnation under pressure

Based on the production of a carbon nanotube (CNT) assembly, a new technique is developed for preparing CNT/epoxy (EP) composite films with high tensile strength and electrical conductivity. CNTs are synthesized by floating catalyst spray pyrolysis. After self-assembling into a hollow cylindrical assembly, CNTs are drawn and wound on a rotating drum to form a uniform CNT film. EP resin solutions of different concentrations are used to fill into the pores within the film under different pressures and form composite films after hot-press curing. The permeability of the EP resin and thus the interfacial bonding between the CNT and the EP resin are studied by varying the concentration of the EP resin solution and the pressure used for impregnation. Under optimal preparation conditions, the composite film contains CNTs of a high content of 59 wt.%, and shows a high tensile strength of 1.4 GPa and a high electrical conductivity of 1.4x10^5 S·m^-1, 159% and 309% higher than those of the neat CNT film, respectively.     

Electrical conductive CNT-PVA/PC nanocomposites with high tensile elongation

Electrically conductive CNT reinforced polycarbonate matrix nanocomposites with high strain-to-failure were fabricated by inserting polyvinylalcohol as a surface modifier through a melt blending process. The addition of PVA by coating the CNT through a simple ball milling process before melt blending with a polycarbonate matrix resulted in an increased percolation limit as compared to that prepared using uncoated CNTs, while the electrical conductivity was maintained at a similar level of 2 x 10(-2) S/cm. However, tensile elongation was considerably improved by the addition of PVA and remained at 81% even though 5 wt% of the CNTs were added for electrical conductivity, while elongation dropped to 25% when the CNTs were not coated with PVA. The addition of PVA induces homogeneous dispersion of CNTs during the melt blending process and can enhance both electrical conductivity and mechanical durability.     

Preparation of continuous carbon nanotube networks in carbon fiber/epoxy composite

In order to optimize carbon nanotube (CNT) dispersion state in fiber/epoxy composite, a novel kind of CNT organization form of continuous networks was designed. The present work mainly discussed the feasibility of preparing continuous CNT networks in composite: Fiber fabric was immersed into CNT aqueous solution (containing dispersant) followed by freeze drying and pyrolysis process, prior to epoxy infusion. The morphologies of fabric with CNTs were observed by Scanning Electron Microscope. The relationship between CNT networks and flowing epoxy resin was studied. Properties of composite, including out-of-plane electrical conductivity and interlaminar shear strength (ILSS), were measured. The results demonstrated that continuous and porous CNT networks formed by entangled CNTs could be assembled in fiber fabric. Most part of them were preserved in composite due to the robustness of network structures. The preserved CNT networks significantly improved out-of-plane electrical conductivity, and also have an effect on ILSS value.     

Influence of the concentration of carbon nanotubes on electrical conductivity of magnetically aligned MWCNT–polypyrrole composites

The goal of this work is to study the effect of high magnetic pulses on electrical property of carbon nanotube–polypyrrole (CNT–PPy) composites with different CNT concentrations. CNT–PPy composites are produced in fractions of 1, 5 and 9 wt%. During the polymerization process, the CNTs are homogeneously dispersed throughout the polymer matrix in an ultrasonic bath. Nanocomposite rods are prepared. After exposure to 30 magnetic pulses, the resistivity of the rods is measured. The surface conductivity of thin tablets of composites is studied by 4-probe technique. The magnitude of the pulsed magnetic field is 10 Tesla with time duration of 1.5 ms. The results show that after applying 30 magnetic pulses, the electrical resistivity of the composites decreases depending on the concentration of CNTs in the composites. The orientation of CNTs is probed by atomic force microscopy (AFM) technique. AFM images approved alignment of CNT–polymer fibres in the magnetic field. We found that the enhancement in the electrical properties of CNT–PPy composites is due to rearrangement and alignment of CNTs in a high magnetic field. The stability of nano-composites is studied by Fourier transform infrared spectroscopy.     

Wide‐Range Tunable Dynamic Property of Carbon‐Nanotube‐Based Fibers

A carbon nanotube (CNT) fiber is formed by assembling millions of individual tubes. The assembly feature provides the fiber with rich interface structures and thus various ways of energy dissipation, as reflected by the nonzero loss tangent (>0.028–0.045) at low vibration frequencies. A fiber containing entangled CNTs possesses higher loss tangents than a fiber spun from aligned CNTs. Liquid densification and polymer infiltration, the two common ways to increase the interfacial friction and thus the fiber's tensile strength and modulus, are found to efficiently reduce the damping coefficient. This is because the sliding tendency between CNT bundles can also be well suppressed by a high packing density and the formation of covalent polymer cross‐links within the fiber. The CNT/bismaleimide composite fiber exhibits the smallest loss tangent, nearly the same as that of carbon fibers. At a higher level of the assembly structure, namely a multi‐ply CNT yarn, the interfiber friction and sliding tendency obviously influence the yarn's damping performance, and the loss tangent can be tuned within a wide range, similar to carbon fibers, nylon yarns, or cotton yarns. The wide‐range tunable dynamic properties allow new applications ranging from high quality factor materials to dissipative systems.     

Solid-state spun fibers and yarns from 1-mm long carbon nanotube forests synthesized by water-assisted chemical vapor deposition

We report continuous carbon nanotube (CNT) fibers and yarns dry-drawn directly from water-assisted chemical vapor deposition (CVD) grown forests with about 1-mm height. As-drawn CNT fibers exist as aerogel and can be transformed into more compact fibers through twisting or densification with a volatile organic liquid. CNT fibers are characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Raman microscopy, and wide-angle X-ray diffraction. Mechanical properties and electrical conductivity of the post-treated CNT fibers are investigated. The resulting fibers show the work of rupture of 30 J/g and DC electrical conductivity of 5.0 × 10⁴ S/m.     

The effect of geometric factor of carbon nanofillers on the electrical conductivity and electromagnetic interference shielding properties of poly(trimethylene terephthalate) composites: a comparative study

In this study, the effects of filler geometry on the electrical conductivity and electromagnetic interference (EMI) shielding properties of poly(trimethylene terephthalate) (PTT) composites filled with graphene nanosheets (GNSs), carbon nanotubes (CNTs), and GNS–CNT hybrid nanofillers have been investigated. The GNSs, CNTs, and hybrid GNS–CNT were well dispersed in the PTT matrix using a simple coagulation process. GNSs were prepared from graphene oxide (GO) through hydrazine reduction, and thermal reduction of GO at two different temperatures of 1050 and 1500 °C. PTT filled with different aspect ratios and oxygen functional groups of GNS were also prepared in order to compare the electrical conductivity and EMI shielding properties. The aspect ratios of GNSs and CNTs were estimated by using an ellipsoid model. Percolation scaling laws were applied to the magnitudes of conductivity to reveal the percolation network and filler dispersion. The percolation exponent of the PTT/GNS composites was larger than that of the PTT/CNT composites. The percolated filler–filler network at which the percolation exponent changed was correlated with the filler geometric structure. GNS–CNT hybrid nanofillers formed a complex double brush structure in the PTT/GNS–CNT composites. The geometric structure, aspect ratio, and intrinsic conductivity of carbon nanofillers affected the electrical percolation threshold and EMI shielding efficiency of the composites.     

Macroscopic carbon nanotube assemblies: preparation, properties, and potential applications

As classical 1D nanoscale structures, carbon nanotubes (CNTs) possess remarkable mechanical, electrical, thermal, and optical properties. In the past several years, considerable attention has been paid to the use of CNTs as building blocks for novel high-performance materials. In this way, the production of macroscopic architectures based on assembled CNTs with controlled orientation and configurations is an important step towards their application. So far, various forms of macroscale CNT assemblies have been produced, such as 1D CNT fibers, 2D CNT films/sheets, and 3D aligned CNT arrays or foams. These macroarchitectures, depending on the manner in which they are assembled, display a variety of fascinating features that cannot be achieved using conventional materials. This review provides an overview of various macroscopic CNT assemblies, with a focus on their preparation and mechanical properties as well as their potential applications in practical fields.     

Temperature dependence of electrical conductivity in double-wall and multi-wall carbon nanotube/polyester nanocomposites

The aim of this study is to investigate temperature dependence of electrical conductivity of carbon nanotube (CNT)/polyester nanocomposites from room temperature to 77 K using four-point probe test method. To produce nanocomposites, various types and amounts of CNTs (0.1, 0.3 and 0.5 wt.%) were dispersed via 3-roll mill technique within a specially formulized resin blend of thermoset polyesters. CNTs used in the study include multi walled carbon nanotubes (MWCNT) and double-walled carbon nanotubes (DWCNT) with and without amine functional groups (–NH₂). It was observed that the incorporation of carbon nanotubes into resin blend yields electrically percolating networks and electrical conductivity of the resulting nanocomposites increases with increasing amount of nanotubes. However, nanocomposites containing amino functionalized carbon nanotubes exhibit relatively lower electrical conductivity compared to those with non-functionalized carbon nanotubes. To get better interpretation of the mechanism leading to conductive network via CNTs with and without amine functional groups, the experimental results were fitted to fluctuation-induced tunneling through the barriers between the metallic regions model. It was found that the results are in good agreement with prediction of proposed model.