Carbon Nanotube Films Research Articles

Carbon Nanotube Films with Fewer Impurities and Higher Conductivity from Aqueously Mono-Dispersed Solution via Two-Step Filtration for Electric Heating.

With the intensification of global climate problems, electric heating has recently attracted much attention as a clean and low-carbon heating method. Carbon nanotubes (CNTs) are an ideal medium for electric heating applications due to their excellent mechanical, electrical, and thermal properties. The preparation of electrothermal films based on an aqueous CNT dispersion as a raw material is environmentally friendly. However, in the traditional one-step filtration method, the residual excess dispersant and the small aspect ratio of the CNTs in the preparation process limit the performance of electrothermal CNT films. In this paper, we report a two-step filtration method that removes the free dispersant and small CNTs in the first filtration step and obtains denser CNT films by controlling the pores of the filter membrane in the second filtration step. The results suggest that, compared to the CNT1 film obtained from one-step filtration, the CNT1-0.22 film, obtained from two-step filtration using 1 and 0.22 μm membranes, has a smoother and flatter surface, and the surface resistance is 80.0 Ω sq-1, which is 29.4% lower. The convective radiation conversion efficiency of the CNT1-0.22 film is 3.36 mW/°C, which is 36.1% lower. We anticipate that such CNT films could be widely applied in building thermal insulation and underfloor heating.

High performance THz metasurface sensor based on modified-SWCNTs film for femtomolar protein detection

Terahertz (THz) metasurface sensor plays an important role in environmental monitoring, biomedical diagnostics, and materials science. However, most traditional THz metasurfaces for trace biological substance detection either suffer from high ohmic loss, or cannot achieve ultra-low concentration detection at the femtomolar level, which limits the application range of THz metasurfaces. Here, we propose a novel metasurface based on modified single-walled carbon nanotubes (SWCNTs) film for specific detection of SAA protein in femtomolar concentration. By modifying the SWCNTs film with concentrated sulfuric acid and introducing functionalized gold nanoparticles (Au-NPs), not only the non-resonant loss of the SWCNTs film was greatly reduced, but also the specific selection of trace SAA proteins was achieved. We experimentally demonstrated that the sensitivity of this THz metasurface sensor for SAA protein detection is 37.5 GHz/fM. In contrast to conventional metal or dielectric metasurfaces, because the unique mesh-like structure of the SWCNTs film can greatly increase the interaction between trace substances and the sensor, this new modifiable metasurface can achieve the lowest detection limit of 0.1 fM, which has increased by an order of magnitude. Our results provide a new and promising method for THz metasurfaces to realize high-performance biosensors.

Field-Emission Energy Distribution of Carbon Nanotube Film and Single Tube under High Current.

A narrow energy distribution is a prominent characteristic of field-emission cold cathodes. When applied in a vacuum electronic device, the cold cathode is fabricated over a large area and works under a high current and current density. It is interesting to see the energy distribution of the field emitter under such a working situation. In this work, the energy distribution spectra of a single carbon nanotube (CNT) and a CNT film were investigated across a range of currents, spanning from low to high. A consistent result indicated that, at low current emission, the CNT film (area: 0.585 mm2) exhibited a narrow electron energy distribution as small as 0.5 eV, similar to that of a single CNT, while the energy distribution broadened with increased current and voltage, accompanied by a peak position shift. The influencing factors related to the electric field, Joule heating, Coulomb interaction, and emission site over a large area were discussed to elucidate the underlying mechanism. The results provide guidance for the electron source application of nano-materials in cold cathode devices.

Aerosol Doping System for Microscale Seamless p-n Patterning of Carbon Nanotube Films.

Carbon nanotube (CNT) films are extensively researched as a promising material for wearable thermoelectric generators (TEGs) owing to their good flexibility and high thermoelectric conversion ability. Miniaturizing a pair of p- and n-type thermocouples and increasing the number of repeating elements can effectively increase the power of TEGs. However, conventional p-n patterning methods, such as dipping and printing, have a coarse resolution at the submillimeter level, thereby limiting the miniaturization rate. This study developed an aerosol doping system as a fine n-doping method. A dopant aerosol with a <3 μm diameter was formed through ultrasonic nebulization and air separation, while n-doping was achieved by exposing the CNT film to the dopant aerosol. Microscale p-n patterning of 1 μm was achieved through exposure using small-sized aerosols at an exceptionally slow rate of 3 Å/min. This resolution is 100 times higher than those of conventional p-n patterning methods. The developed aerosol doping system for CNTs can also be used on organic semiconductor materials, such as PEDOT/PSS and perovskite materials. Therefore, it has the potential to significantly impact the realization of Internet of Things (IoT) terminals, such as flexible TEGs, transistors, and solar cells.

Carbon nanotube films with ultrahigh thermal-shock and thermal-shock-fatigue resistance characterized by ultra-fast ascending shock testing

Carbon nanotube films with ultrahigh thermal-shock and thermal-shock-fatigue resistance characterized by ultra-fast ascending shock testing

Study on transverse high-velocity impact resistance of carbon nanotube films and their based composites

This paper investigates the resistance of Carbon nanotube (CNT) films and their based composites to transverse high-speed impact and explores the effect of resin content on the impact properties. The study utilizes light gas gun experiments and employs numerical simulation to determine the critical penetration velocities for pure CNT films and those films impregnated with 20 %, 50 %, and 80 % epoxy resin solutions. The results demonstrate that including epoxy resin can enhance CNT films' impact-resisting ability, with a noticeable improvement as the resin content increases The observed strengthening mechanism in CNT resin composite films subjected to high-speed impacts primarily is energy absorption. Based on the above results, CNT films were added to the interlayer of composite laminates. It was found that CNTs could help materials resist impact and ensure the integrity of the laminate structure.

Oxygenated moiety enhanced thermal stabilization, mechanical, and thermomechanical performance of polyacrylonitrile/single wall carbon nanotubes films

AbstractThermo‐oxidative stabilization of polyacrylonitrile (PAN)‐copolymer and PAN/single‐walled carbon nanotube (SWCNT) composite films were studied in the presence of oxygenated entities which may act as an internal oxygen supplier. The oxygenated moiety exhibited dual behavior, enhancing the stabilization efficiency of PAN while also improving the dispersion of SWCNT. The addition of oxygenated moiety treated SWCNT to PAN resulted in a significant reduction in activation energy from 118 kJ/mol to 99 kJ/mol, owing to a more stable oxidation reaction. Thermogravimetric analysis showed weight loss due to stabilization, and polymer chain degradation was lower in treated SWCNT composite films, resulting in an approximate 6% increase in residual weight. Mechanical testing showed a significant increase in tensile strength to 54.15 MPa and tensile modulus to 2.53 GPa with elongation at break of 13.2%, which is attributed to the enhanced interfacial shear strength resulting from the improved dispersion of oxygenated moiety‐treated nanotubes. Furthermore, thermomechanical analysis studies showed improvement in dimension stability with oxygenated moiety treated SWCNT composite films, attributed to better dispersion and increased interfacial strength between the polymer and filler.Highlights Oxygenated entities stabilize PAN and improve SWCNT dispersion. Activation energy was reduced from 118 to 99 kJ/mol with Tween‐80. Residual weight increased by 6% with treated SWCNT in TGA. Improved tensile strength (54.14 MPa), modulus (2.53 GPa) with modified SWCNT. Dimension stability is enhanced by interfacial strength with modified SWCNT.

Wide temperature range, air stable, transparent, and self-powered photodetectors enabled by a hybrid film of graphene and single-walled carbon nanotubes

Wide temperature range, air stable, transparent, and self-powered photodetectors enabled by a hybrid film of graphene and single-walled carbon nanotubes

Transparent Cellulose/Multi-Walled Carbon Nanotube Hybrids with Improved Ultraviolet-Shielding Properties Prepared from Cotton Textile Waste.

Plastics offer many advantages and are widely used in various fields. Nevertheless, most plastics derived from petroleum are slow to degrade due to their stable polymer structure, posing serious threats to organisms and ecosystems. Thus, developing environmentally friendly and biodegradable plastics is imperative. In this study, biodegradable cellulose/multi-walled carbon nanotube (MCNT) hybrid gels and films with improved ultraviolet-shielding properties were successfully prepared using cotton textile waste as a resource. It was proven that MCNTs can be dispersed evenly in cellulose without any chemical or physical pretreatment. It was found that the contents of MCNTs had obvious effects on the structures and properties of hybrid films. Particularly, the averaged transmittance of cellulose/MCNT composite films in the range of 320-400 nm (T320-400) and 290-320 nm (T290-320) can be as low as 19.91% and 16.09%, when the content of MCNTs was 4.0%, much lower than those of pure cellulose films (T320-400: 84.12% and T290-320: 80.03%). Meanwhile, the water contact angles of the cellulose/MCNT films were increased by increasing the content of MCNTs. Most importantly, the mechanical performance of cellulose/MCNT films could be controlled by the additives of glycerol and MCNTs. The tensile strength of the cellulose/MCNT films was able to reach as high as 20.58 MPa, while the elongation at break was about 31.35%. To summarize, transparent cellulose/MCNT composites with enhanced ultraviolet-shielding properties can be manufactured successfully from low-cost cotton textile waste, which is beneficial not only in terms of environmental protection, but also the utilization of natural resources.

Micro-Pirani Pressure Sensor With Operation Range Beyond Atmospheric Pressure Based on Aligned Carbon Nanotube Films

Micro-Pirani Pressure Sensor With Operation Range Beyond Atmospheric Pressure Based on Aligned Carbon Nanotube Films

Expanding THz Vortex Generation Functionality with Advanced Spiral Zone Plates Based on Single‐Walled Carbon Nanotube Films

AbstractOptical elements based on nanomaterials are becoming major avenues to satisfy the technological requirements of compact, lightweight, and tunable elements of the emerging terahertz (THz) field. A new generation of diffractive components integrating specific geometry with additional features (flexibility, stretchability, rotation, and other approaches for tuning properties) extends the functionality of wavefront control. Here, an innovative approach is demonstrated to control the THz wavefront via a layered composition of spiral zone plates (SZPs) with tunable mutual orientation and scaling. As a proof of concept, the SZP is designed using Laguerre‐Gauss mode analysis with further fabrication and experimental characterization of the resultant vortex beams. For each single SZP, a flexible element is proposed based on a thin film of single‐walled carbon nanotubes deposited on a stretchable substrate. Thus, this diffraction element can be tuned not only by rotation (along the azimuthal direction), but also by its stretching (in the radial direction). The spatial tuning of the developed SZPs (spiral zone plates) opens up an efficient, convenient, and highly customizable approach for the manipulation of vortex beams.

Microheater Chips with Carbon Nanotube Resistors.

The specific and excellent properties of the low-dimensional nanomaterials have made them promising building blocks to be integrated into microelectromechanical systems with high performances. Here, we present a new microheater chip for in situ TEM, in which a cross-stacked superaligned carbon nanotube (CNT) film resistor is located on a suspended SiNx membrane via van der Waals (vdW) interactions. The CNT microheater has a fast high-temperature response and low power consumption, thanks to the micro/nanostructure of the CNT materials. Moreover, the membrane bulging amplitude is significantly reduced to only ∼100 nm at 800 °C for the vdW interaction between the CNTs and the SiNx membrane. An in situ observation of the Sn melting process is successfully conducted with the assistance of a customized flexible temperature control system. The uniform wafer-scaled CNT films enable a high level of consistency and cost-effective mass production of such chips. The as-developed in situ chips, as well as the related techniques, hold great promise in nanoscience, materials science, and electrochemistry.

Mechanistic study of highly effective phosphate removal from aqueous solutions over a new lanthanum carbonate fabricated carbon nanotube film

The effective purification of phosphate-containing wastewater is considered as increasingly important. In this study, a highly effective LC-CNT film was developed for efficient phosphate removal. Kinetic results showed that the adsorbent exhibited an improved mass transfer efficiency and a fast adsorption rate during adsorption (reaching 80% and 100% equilibrium adsorption capacity within 175 and 270 min, respectively). Kinetic model analysis suggested that the adsorption was a combined chemical physical process. Isotherm study revealed that the LC-CNT film showed a superior adsorption capacity (178.6 mg/g, estimated from the Langmuir model) with multiple adsorption mechanisms. pH study suggested that surface complexation and ligand exchange played important roles during adsorption, and the adsorbent worked well within the pH range of 3–7 with little La leakage. The ionic strength and competing anions showed little influence on the adsorbent effectiveness except for the carbonate and sulfate ions. The characterization and mechanism study revealed that the phosphate adsorption of the LC-CNT film was controlled by inner-sphere complexation, outer-sphere complexation and surface precipitation. The LC-CNT film also showed excellent regenerability and stability in cycling runs, further demonstrating its potential in industrial applications.

High-efficiency thermal reduction of CO2 to high-valued carbon nanotubes

To reduce the amount of carbon dioxide (CO2) already emitted into the atmosphere, various carbon capture, utilization, and storage (CCUS) technologies have been developed for climate and economic reasons in recent years. However, the state of art CCUS techniques suffer from deficiencies such as high cost, low yield, and harsh and discontinuous production conditions. In this work, we report a new thermal reduction method for continuously conversing CO2 to methane (CH4) by introducing sodium borohydride (NaBH4) as a reductant under catalyst-free conditions. Experimental results show that CO2 can be fully captured and converted to CH4 and carbon monoxide (CO) and the selectivity efficiency of CO2 to CH4 can be achieved to be as high as 90% with the optimization of experimental conditions. Such a result originates from the high activity of NaBH4 and high selectivity of the thermal reduction of CO2. To demonstrate one of the potential usages of the reduction products, we integrated the thermal reduction of CO2 with the production of carbon nanotubes (CNTs). As long as CO2 is supplied at the source end, the reduction products can undergo catalytic decomposition to produce a CNT fiber or film continuously at the final end. The present technique is featured with simple equipment setup, low cost, and continuous thermal reduction, thus providing a new pathway for the large-scale conversion of CO2 into high-valued products for wide applications.

Hydrogels and Carbon Nanotubes: Composite Electrode Materials for Long-Term Electrocardiography Monitoring.

This paper presents methods for developing high-performance interface electrode materials designed to enhance signal collection efficacy during long-term (over 24 h) electrocardiography (ECG) monitoring. The electrode materials are fabricated by integrating commercial ECG liquid hydrogels with carbon nanotubes (CNTs), which are widely utilized in dry-electrode technologies and extensively discussed in the current scientific literature. The composite materials are either prepared by dispersing CNTs within the commercial liquid hydrogel matrix or by encasing the hydrogels in macroscopic CNT films. Both approaches ensure the optimal wetting of the epidermis via the hydrogels, while the CNTs reduce material impedance and stabilize the drying process. The resulting electrode materials maintain their softness, allowing for micro-conformal skin attachment, and are biocompatible. Empirical testing confirms that the ECG electrodes employing these hybrid hydrogels adhere to relevant standards for durations exceeding 24 h. These innovative hybrid solutions merge the benefits of both wet and dry ECG electrode technologies, potentially facilitating the extended monitoring of ECG signals and thus advancing the diagnosis and treatment of various cardiac conditions.

Facile Lithium Densification Kinetics by Hyperporous/Hybrid Conductor for High-Energy-Density Lithium Metal Batteries.

Lithium metal anode (LMA) emerges as a promising candidate for lithium (Li)-based battery chemistries with high-energy-density. However, inhomogeneous charge distribution from the unbalanced ion/electron transport causes dendritic Li deposition, leading to "dead Li" and parasitic reactions, particularly at high Li utilization ratios (low negative/positive ratios in full cells). Herein, an innovative LMA structural model deploying a hyperporous/hybrid conductive architecture is proposed on single-walled carbon nanotube film (HCA/C), fabricated through a nonsolvent induced phase separation process. This design integrates ionic polymers with conductive carbon, offering a substantial improvement over traditional metal current collectors by reducing the weight of LMA and enabling high-energy-density batteries. The HCA/C promotes uniform lithium deposition even under rapid charging (up to 5mA cm-2) owing to its efficient mixed ion/electron conduction pathways. Thus, the HCA/C demonstrates stable cycling for 200 cycles with a low negative/positive ratio of 1.0 when paired with a LiNi0.8Co0.1Mn0.1O2 cathode (areal capacity of 5.0mAhcm-2). Furthermore, a stacked pouch-type full cell using HCA/C realizes a high energy density of 344Whkg-1 cell/951WhL-1 cell based on the total mass of the cell, exceeding previously reported pouch-type full cells. This work paves the way for LMA development in high-energy-density Li metal batteries.

Aerosol-Synthesized Surfactant-Free Single-Walled Carbon Nanotube-Based NO2 Sensors: Unprecedentedly High Sensitivity and Fast Recovery.

This study pioneers a chemical sensor based on surfactant-free aerosol-synthesized single-walled carbon nanotube (SWCNT) films for detecting nitrogen dioxide (NO2). Unlike conventional CNTs, the SWCNTs used in this study exhibit one of the highest surface-to-volume ratios. They show minimal bundling without the need for surfactants and have the lowest number of defects among reported CNTs. Furthermore, the dry-transferrable and facile one-step lamination resultsin promising industrial viability. When applied to devices, the sensor shows excellent sensitivity (41.6% at 500ppb), rapid response/recovery time (14.2/120.8s), a remarkably low limit of detection (below ≈0.161ppb), minimal noise, repeatability for more than 50 cycles without fluctuation, and long-term stability for longer than 6months. This is the best performance reported for a pure CNT-based sensor. In addition, the aerosol SWCNTs demonstrate consistent gas-sensing performance even after 5000 bending cycles, indicating their suitability for wearable applications. Based on experimental and theoretical analyses, the proposed aerosol CNTs are expected to overcome the limitations associated with conventional CNT-based sensors, thereby offering a promising avenue for various sensor applications.

Robust ultrahigh electromagnetic interference shielding effectiveness based on engineered structures of carbon nanotube films

High-performance electromagnetic interference (EMI) shielding materials with ultrathin, flexible, and pliable mechanical properties are highly desired for high-end equipments, yet there remain large challenges in the manufacture of these materials. Here, carbon nanotube film (CNTF)/copper (Cu) nanoparticle (NP) composite films are fabricated via a facile electrodeposition method to achieve high electromagnetic shielding efficiency. Notably, a CNTF/Cu NP composite film with 15μm thickness can achieve excellent EMI shielding efficiency of ∼248 dB and absolute EMI shielding effectiveness as high as 2.17×105 dB cm2 g-1, which are the best values for composite EMI shielding materials with similar or greater thicknesses. These engineered composite films exhibit excellent deformation tolerance, which ensures the robust reliability of EMI shielding efficiency after 20,000 cycles of repeated bending. Our results represent a critical breakthrough in the preparation of ultrathin, flexible, and pliable shielding films for applications in smart, portable and wearable electronic devices, and 5G communication.

Biomimetic Electronic Skin Based on a Stretchable Ionogel Mechanoreceptor Composed of Crumpled Conductive Rubber Electrodes for Synchronous Strain, Pressure, and Temperature Detection.

Electronic skin (e-skin) is showing a huge potential in human-computer interaction, intelligent robots, human health, motion monitoring, etc. However, it is still challenging for e-skin to realize distinguishable detection of stretching strain, vertical pressure, and temperature through a simple noncoupling structure design. Here, a stretchable multimodal biomimetic e-skin was fabricated by integrating layer-by-layer self-assembled crumpled reduced graphene oxide/multiwalled carbon nanotubes film on natural rubber (RGO/MWCNTs@NR) as stretchable conductive electrodes and polyacrylamide/NaCl ionogel as a dielectric layer into an ionotropic capacitive mechanoreceptor. Unlike natural skin receptors, the sandwich-like stretchable ionogel mechanoreceptor possessed a distinct ionotropic capacitive behavior for strain and pressure detection. The results showed that the biomimetic e-skin displayed a negative capacitance change with superior stretchability (0-300%) and a high gauge factor of 0.27 in 180-300% strain, while exhibiting a normal positive piezo-capacitance behavior in vertical pressure range of 0-15 kPa with a maximal sensitivity of 1.759 kPa-1. Based on this feature, the biomimetic e-skin showed an excellent synchronous detection capability of planar strain and vertical pressure in practical wearable applications such as gesture recognition and grasping movement detection without a complicated mathematical or signal decoupling process. In addition, the biomimetic e-skin exhibited a quantifiable linear responsiveness to temperature from 20-90 °C with a temperature coefficient of 0.55%/°C. These intriguing properties gave the biomimetic e-skin the ability to perform a complete function similar to natural skin but beyond its performance for future wearable devices and artificial intelligence devices.

Evaluating the Efficiency of Boron Nitride Coating in Single-Walled Carbon-Nanotube-Based 1D Heterostructure Films by Optical Spectroscopy.

Single-walled carbon nanotube (SWCNT) films exhibit exceptional optical and electrical properties, making them highly promising for scalable integrated devices. Previously, we employed SWCNT films as templates for the chemical vapor deposition (CVD) synthesis of one-dimensional heterostructure films where boron nitride nanotubes (BNNTs) and molybdenum disulfide nanotubes (MoS2NTs) were coaxially nested over the SWCNT networks. In this work, we have further refined the synthesis method to achieve precise control over the BNNT coating in SWCNT@BNNT heterostructure films. The resulting structure of the SWCNT@BNNT films was thoroughly characterized using a combination of electron microscopy, UV-vis-NIR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and Raman spectroscopy. Specifically, we investigated the pressure effect induced by BNNT wrapping on the SWCNTs in the SWCNT@BNNT heterostructure film and demonstrated that the shifts of the SWCNT's G and 2D (G') modes in Raman spectra can be used as a probe of the efficiency of BNNT coating. In addition, we studied the impact of vacuum annealing on the removal of the initial doping in SWCNTs, arising from exposure to ambient atmosphere, and examined the effect of MoO3 doping in SWCNT films by using UV-vis-NIR spectroscopy and Raman spectroscopy. We show that through correlation analysis of the G and 2D (G') modes in Raman spectra, it is possible to discern distinct types of doping effects as well as the influence of applied pressure on the SWCNTs within SWCNT@BNNT heterostructure films. This work contributes to a deeper understanding of the strain and doping effect in both SWCNTs and SWCNT@BNNTs, thereby providing valuable insights for future applications of carbon-nanotube-based one-dimensional heterostructures.