Single-walled Carbon Nanotube Bundles Research Articles

Evaluating SWCNT assembly properties from the temperature dependence of electrical resistivity

We developed a theoretical model to describe the electrical resistivity in films and fibers made of single-walled carbon nanotubes (SWCNTs). The proposed model considers the formation of randomly oriented bundles of metallic and semiconducting nanotubes and takes into account the influence of temperature, while separating contributions of SWCNTs and their junctions to the total resistivity. To verify the model, we applied a powerful experimental tool – measurements of the temperature dependence of electrical resistivity of the investigated macroscopic SWCNT assemblies (pristine and doped SWCNT fibers). This allowed us to estimate various parameters of the material, such as the average length of SWCNT bundles, the acoustic phonon scattering length, and the bundle contact resistance, which are difficult to evaluate experimentally for entangled SWCNTs. The study highlights the importance of understanding the relationship between structural characteristics and electrical properties in SWCNT assemblies. The findings provide insights into optimizing the conductivity of these materials and offer a quick estimation method of the SWCNT network properties based on varying temperature measurements for future fiber and film-based applications.

Effect of bundling on phonon transport in single-walled carbon nanotubes

Thermally conductive bulk materials composed of single-walled carbon nanotubes (SWCNTs), such as fibers and mats, are characterized by a complex network formed by entangled SWCNTs. The fundamental unit of this network is a bundle, in which SWCNTs are assembled through weak van der Waals interactions. Although the thermal conductivity of a bundle is conventionally described as the sum of the heat conduction in the constituent SWCNTs, recent experiments have demonstrated that bundling may reduce the high thermal conductivity of SWCNTs, which is counterintuitive considering the weak interactions between SWCNTs in a bundle. Herein, by performing spectral phonon transport analysis for bundles of SWCNTs with radii of approximately 3.4 Å, we explore the effect of the bundle size and chiral configuration on phonon transport in bundles. Results show that although the heat conduction properties of individual SWCNTs are maintained for bundles with a length of less than 1 μm around room temperature in both the ballistic and quasi-ballistic regimes, intertube interactions between constituent SWCNTs coupled with their structural low dimensionality may yield additional thermal resistance. In particular, the thermal conductivity of a bundle decreases when low-frequency phonons influenced by intertube interactions substantially contribute to the overall heat conduction, namely, either at low temperatures or for long bundles. Although the observed additional thermal resistance cannot fully explain the experimental results of reduced thermal conductivity, our findings on the effect of bundling can advance the understanding of thermal transport in bundles and the thermal management of SWCNT bulk materials.

Self-supporting oxygen vacancy-rich α-MnO2 nanowire/few-layer graphite/SWNT bundle composite film for high-performance flexible aqueous zinc-ion battery cathode

The increasing demand for flexible and wearable electronic devices has led to widespread interest in flexible electrochemical energy storage devices. However, the transformation of the battery structure from conventional to flexible presents a great challenge to the battery design. Herein, we developed a facile method for the preparation of a self-supporting composite film consisting of oxygen-vacancy rich MnO2 nanowires (NWs), few-layer graphite nanosheets (FLGs), and single-walled carbon nanotube (SWNT) bundles as the cathode of flexible zinc-ion batteries. This ternary interwoven interconnection 3D structure enhances the electrochemical performance of the battery and realizes fast charge transfer; oxygen vacancies in the MnO2 NWs caused by heat treatment (300 °C in Ar) allow for rapid intercalation and diffusion of Zn2+. The interwoven FLGs and SWNT bundles improve the electrical conductivity, and the robust interactions between the two carbon nanomaterials and the MnO2 NWs effectively make the composite film with excellent mechanical properties. This self-supporting flexible electrode exhibits a high specific capacity of 374 mAh/g at 0.4 A/g, maintains a Coulombic efficiency of ∼ 100 % after 1600 cycles at 2 A/g, and has a high energy density of 651.5 Wh kg−1 at 65.2 W kg−1. Moreover, the flexible zinc ion batteries assembled with the electrode demonstrate good mechanical properties and a high reversible specific capacity of 343 mAh/g after 75 bending cycles. Based on these findings, we believe that this composite film holds great promise as a cathode material in flexible energy storage applications.

Thermal Conductance between <6 nm Single-Walled Carbon Nanotube Bundle and Si Substrate

Thermal Conductance between <6 nm Single-Walled Carbon Nanotube Bundle and Si Substrate

Электрохимические сенсоры на основе сеток из однослойных углеродных нанотрубок для вольтамперометрического определения аскорбиновой кислоты

Modern highly sensitive and selective sensors are able to determine biologically active substances, which makes this direction one of the most popular areas of analytical chemistry. The study featured the electrochemical properties of new fiber materials based on single-wall carbon nanotubes with prospects of using them in the voltammetry of ascorbic acid. 
 The authors developed a new technology to synthesize films from disordered single-wall carbon nanotubes by chemical vapor deposition. Fibers were produced from a solvent by wet-pulling of single-wall carbon nanotubes networks. Thin films of randomly oriented single-wall carbon nanotube bundles were deposited downstream of a floating aerosol CVD reactor, which included a high temperature furnace with a quartz tube. The synthesis of the single-wall carbon nanotube samples was performed at 825°C. Ethanol served as carbon source while ferrocene was used as catalyst precursor. The single-wall carbon nanotubes were collected on a nitrocellulose filter in the form of films with transmittances of 10% in the middle of the visible wavelength (550 nm). The method was optimized to involve air annealing at 300–320°C and a treatment with strong inorganic acids, i.e., HCl, HNO3 + H2SO4. The voltammetric curves recording included background electrolyte, scan rate, and preconditioning. These parameters were selected experimentally to obtain the maximal sensor response to ascorbic acid content. The anodic peak of ascorbic acid in the phosphate buffer electrolyte (pH 6.86) was observed at a potential of +0.2 V. The current and peak area of ascorbic acid oxidation depended neither on the time nor on the conditioning potential of the sensor. The linear dependences of these parameters on the concentration of ascorbic acid stayed within 50–500 μmol/L (8.8–90 mg/L) at a scan rate of 0.1 mV/s. The single-wall carbon nanotube microsensor had a length of 0.5 cm and an average width of 400 μm. Its sensitivity was two times as high as that of a disk glassy carbon electrode with a diameter of 5 mm. 
 The experimental sensors proved effective in determining ascorbic acid in food products, pharmaceuticals, and biological fluids.

Effect of the reinforcement phase on the electrical and mechanical properties of Cu–SWCNTs nanocomposites

In this research a pre-treatment of single-walled carbon nanotubes (SWCNTs) was performed to obtain Cu–SWCNTs composites by powder metallurgy technique. The SWCNTs were subjected to a chemical functionalization in acidic medium followed by a copper coating to improve their incorporation into the metal matrix. The results revealed a considerable inclusion of carboxyl, carbonyl and hydroxyl groups in the nanotubes, maintaining their structural integrity which was demonstrated by characterization using X-ray photoelectronic spectroscopy (XPS), scanning electron microscopy (SEM) and Raman spectroscopy techniques. The electroless process used allowed a complete reduction of copper sulfate to a metallic copper obtaining a suitable and homogeneous carbon nanotubes incorporation into the copper matrix. Microhardness measurements of the Cu–0.01 % SWCNT composite presented an improvement of 13 % compared with pure copper. Furthermore, this composite showed the best tribological properties obtaining a wear rate of 2.1 × 10−4 mm3/Nm, 18 % better than Cu, which was associated with the improved dispersion of the SWCNTs bundles into the matrix, and with a lower amount of surface defects. The maximum electrical conductivity obtained was 96 % IACS in the samples with the least amount of reinforcement phase which confirms their homogeneity into the copper matrix.

Dynamic Performance of Hybrid Infrared Modulator Based on Single‐Walled Carbon Nanotubes and Ionic Liquid Enabling Fast Response

Herein, a new type of infrared film using single‐walled carbon nanotubes (SWNTs) is developed. The optimal sonication settings to produce SWNTs with the highest possible absorption of infrared light are discovered. A hybrid infrared modulator that combines SWNTs with ionic liquids, with a very fast response time is also developed. By carefully controlling the size of the SWNT bundles and the pore size of the filter membrane used to deposit the SWNTs, a response time of a few hundred microseconds (635 μs) at the half‐power point is achieved, which is the optical 3‐dB point. This technology has the potential to be used in a variety of innovative applications, such as smart windows and military camouflage, due to its excellent infrared optical properties.

Scattering-induced circuit modelling and performance analysis of coupled hybrid Interconnections: Sub-threshold performance evaluation

This paper presents the scattering induced circuit modelling and performance analysis in terms of crosstalk and frequency stability in the newly proposed hybrid interconnects operating in the sub-threshold domain. The electrical performances of hybrid copper carbon-nanotube (HCNT), hybrid copper graphene nanoribbon (HGNR) and hybrid Copper carbon (H Carbon) interconnects are examined and compared with that of copper (Cu), single walled carbon nanotube bundles (SWCNTs) and lithium doped multilayer graphene nanoribbon (MLGNR) interconnects in terms of dynamic and functional crosstalk results by employing the transmission line (TL) analytical model for sub-threshold applications. The impact of the grain-size on the resistivity of Cu and the various scatterings induced mean free path (MFP) on the overall resistance has been analysed in the modelling of HGNR interconnects. The comprehensive analysis of the crosstalk induced delay (dynamic crosstalk), the positive peaks and the time-duration (functional crosstalk) ensures the efficacy of hybrid interconnects, especially H Carbon interconnects in the designing of on-chip interconnects. It has also been observed from the frequency response that the maximum 3-dB bandwidth is obtained in the case of H Carbon hybrid interconnects (approx. 6.7586 × 1010 Hz) at 300 K temperature values. Further, the bandwidth values tend to decrease with the rise in temperature values.

Structural transition of single-walled carbon nanotube (6, 6) bundles under lateral shocks

Dynamic response of single-walled carbon nanotube (SWCNT) (6,6) bundles under planar shock are investigated using molecular dynamics (MD) simulations. The Hugoniot data indicate that the shock velocity (up) in the range of 0–12 km/s can generate a wide range of shock waves (0–24 km/s), and high pressure up 0–500 GPa. The SWCNT bundles undergo a radial deformation at ∼5 GPa (up=1 km/s). As pressure reaches ∼38 GPa (up=3 km/s), the bundles are activated and transform into a diamond-graphite structure, and a diamond-like mixture at ∼90 GPa (up=5 km/s) is formed, which is partly reversible upon release to atmospheric pressure. Finally, it completely liquefied into an amorphous carbon structure at pressure over 150 GPa (up=6 km/s). Meanwhile, the density functional theory calculations show that structural transition processes of SWCNT (6,6) bundles under lateral compression agree well with the MD simulations. This study provides atomistic insights into the structural transition of SWCNT bundles under shock compressions.

Phase transitions of carbon nanotube bundles under non-proportional triaxial compressions

Lateral compressions of (n, n) and (n, 0) single-walled carbon nanotube (SWCNT) bundles are simulated by density functional theory. Feasible transition pathways are verified by the body-centered tetragonal C4 (bct-C4) phase from the (4, 4) bundle and the carbon-centered orthorhombic C8 (Cco-C8) phase from (6, 6) and (8, 8) bundles. Three new phases, the sp3-hybridized phases Cco-C16 from the (4, 0) bundle and Cco-C32 from the (8, 0) bundle, the hexagonal phase Hex-C24 composed of sp2- and sp3-hybridized carbons from the (6, 0) bundle, under non-proportional triaxial loading are predicted. Measured hardness values for Cco-C16/C32 exceed 40 GPa, indicating super-hardness. Electronic band structures of Cco-C16/C32 exhibit a 3.64 eV bandgap, while Hex-C24 exhibits metallic carbon properties. Our results provide the potential phase transition pathways of SWCNT bundles under non-proportional compression.

(Invited) Engineering Single Wall Carbon Nanotubes for Sub-Cellular Drug Delivery

Single wall carbon nanotubes (SWCNTs) have been rigorously studied and engineered for a myriad of applications including drug delivery due to their unique, desirable properties. Since SWCNTs bundle in aqueous media and the bundling substantially diminishes their desirable properties along with inducing cytotoxicity, strategies to disperse individually SWCNTs with therapeutic molecules and biologic excipients have been heavily investigated. However, a handful of studies has been performed to understand the interactions between therapeutic molecules and excipients with SWCNT interface as well as the mechanism of intracellular release for therapeutic effects. Additionally, little attention has been paid to how cell type and cell metabolic activity level influence internalization of SWCNTs with different lengths. In this talk, I will discuss cell type, cell metabolic activity, and SWCNT length dependent cellular processing of SWCNTs dispersed with diverse biocompatible dispersing agents. Our results demonstrate that proper choice of dispersing agent can allow for interaction with F-actin, accumulation in the endoplasmic reticulum for eventual expulsion, or accumulation in cell nucleus. Further, macrophages with relatively high cell metabolic activity level compared to other cell types such as fibroblasts have shown to internalize significantly higher amount of SWCNTs per cell. The total mass of SWCNTs internalized per cell increases with a decrease in SWCNT length. Lastly, I will discuss our recent effort to create a ternary complex of SWCNTs, drug, and protein for intracellular delivery and release of model drugs. To overcome the limitation of the existing methods being only plausible for model drugs that are soluble in aqueous solutions, we developed a facile schema to assemble stepwise various combinations of therapeutic molecules and excipients on SWCNTs in different solvents using a preformed SWCNT network. These ternary complexes allow dialing in delivery of therapeutic molecules and excipients to achieve desired cell viability reduction. These findings allow for the development of new SWCNT-based biological applications as they establish important parameters of biomolecule adsorption on SWCNTs, SWCNT internalization and subcellular processing, which are crucial for applications ranging from drug delivery to cell type-specific modulation.

Experimental heat capacity of 1D chains of Xe atoms adsorbed in the grooves of c-SWCNTs bundles: Contributions of vibrations and spatial redistribution of atoms

In the temperature range of 2−75 K, the analysis and comparison were performed: (i) experimental CP,Xe(T) and theoretical CV,Xe(T) heat capacity of 1D chains of xenon atoms adsorbed in grooves on the outer surface of bundles of single-walled carbon nanotubes with closed ends (c-SWCNTs); (ii) the experimental heat capacity CP,Xe(T) and the experimental contribution to the radial thermal expansion of the c-SWNTs-Xe sample of Xe that adsorbed the grooves of c-SWCNTs [αXe(T)]. There is an anomaly near 60 K on the CP,Xe(T) and αXe(T) curves due to the contribution of the spatial redistribution of Xe atoms between the chains and the outer surface of c-SWNTs. It was found that the dependencies of CP,Xe(T) and αXe(T) are qualitatively similar below 60 K. The anomaly near 60 K in the CP,Xe(T) curve indicates the complete of fragmentation of 1D Xe atomic chains. The obtained result is important for understanding the kinetics of gas impurity sorption/desorption processes in c-SWNTs.

Partial dehydration-mediated selective ion-permeation through subnanometer-scale windows in highly crystalline single walled carbon nanotube walls

We propose single-atom catalytic oxidation method for production of subnanometer-scale windows on the graphene layer of single walled carbon nanotubes (SWCNTs) in this study. We used the free-standing SWCNT films which had merits for reliable measurements and applicability to electrochemical measurements for determination of the nanowindow size. Copper(II) 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine (CuPc) was adsorbed on SWCNT bundles using liquid-phase adsorption at surface coverage of 0.9. Then, nanowindows were produced by oxidation above 550 K being higher than the decomposition temperature of the bulk CuPc. The oxidation of CuPc-adsorbed SWCNT film markedly increased the surface area from N2 adsorption at 77 K due to access of N2 to the internal tube space through the nanowindows. The nanowindow size was estimated to be the molecular size of N2 through the evident low-pressure adsorption hysteresis of the N2 adsorption isotherm and TEM observation. The selective ion permeability through the nanowindows for H3O+, Li+, Na+, K+, Mg2+, Ca2+, and Ba2+ ions was determined by the inside-capacitance being the capacitance difference of SWCNT between with and without nanowindows. The selective permeation of the hydrated ions depended on the oxidation conditions for production of nanowindows, showing less than 1 nm of the nanowindow size. The relationship between the inside-capacitance and hydrated ion diameter for the selective permeation of hydrated ions indicated partial dehydration of the hydrated ions just only on their permeation through the nanowindows under the accelerated conditions.

Conductivity-based approach to estimate average bundle length in randomly oriented network of single-walled carbon nanotubes

In this paper, we report a method to estimate the average length of bundles in a randomly oriented network of single-walled carbon nanotubes (SWCNTs) by analyzing the dependence of its sheet resistance on the distance between contacts. We propose an analytical model to verify the method and find the model's limitations using Monte Carlo simulations. Then, we apply the proposed approach to experimental results acquired from 95% (at 550 nm wavelength) transparent SWCNT films. The proposed method to estimate the average SWCNT bundle length can be used in situ and does not require any specific sample preparation step that can distort the SWCNT network.

Low-temperature radiation damage studies in single-walled carbon nanotube bundles by hopping conductance

The paper shows the results of studying radiation defects in single-walled carbon nanotube bundles at low temperatures. The data were obtained in a unique experiment that inseparably combines 1 MeV electron irradiation at a temperature of ∼10 K and electrical conductivity measurements over a wide temperature range of 5–300 K. The experiment allowed us to reveal and separate the influence of stable and unstable radiation defects on the electrical properties of SWCNTs. It is shown that the 2D Mott variable range hopping conduction regime exhibits resistance to electron irradiation. The hopping conductivity is the dominant charge transfer mechanism in the temperature range of 5–50 K in both the pristine and irradiated SWCNT samples. It was found that the parameters of hopping transport demonstrate high sensitivity to the introduction and annealing of radiation defects. The low-temperature electron irradiation revealed the possibility of the emergence of an additional conduction channel in the irradiated SWCNTs. This channel demonstrates thermally activated behavior with a low activation energy of ∼0.5 meV at temperatures of 5–50 K. The obtained data indicate that unstable radiation defects create conditions for the possibility of impurity band conduction in SWCNT bundles.

More than the interface: Synergistic engineering of the interfacial and its subjacent layers followed by self-triggering for high efficient bioelectricity harvesting

The practical application of microbial fuel cell (MFC) is severely impeded by its low output power density stemming from the low bacterial loadings and the sluggish extracellular electron transfer (EET) kinetics. Thus, the current collector designed to greatly enhance the electrocatalytic performance of microbial electrodes ought to possess both high hydrophilicity and high conductivity, which are, however, often mutually incompatible. Herein, to resolve this dilemma, a composite bioelectrode consisting of the poly(ionic liquid) functionalized single-walled carbon nanotube bundles (SWCNT-PIL) layer at the biotic-electrode interface and its subjacent hydrophilic graphene oxides (GO) layer is prepared. Bacterial adhesion is significantly enhanced, resulting from the positive charges of SWCNT-PIL and the hydrophilic GO. After self-reduction of GO by attached electricigens, the as-prepared mrGSP bioelectrode exhibits a maximum output power density of 4.808 W m−2, which is more than one order of magnitude larger than that of conventional carbon-based electrode (0.319 W m−2), because the SWCNT-PIL layer is capable of not only accelerating the flavin-based mediated electron transfer (MET), but also upregulating the membrane protein expression from 14.64% to 18.01% induced by the enhanced electric field, promoting the outer membrane c-type cytochromes-based direct electron transfer (DET). This work provides a new concept of synergistic engineering the interfacial and its subjacent layers to solve the dilemma between high hydrophilicity and high conductivity of the current collector surface for microbial electrocatalysis.

Designed Production of Atomic-Scale Nanowindows in Single-Walled Carbon Nanotubes

The controlled production of nanowindows in graphene layers is desirable for the development of ultrathin membranes. Herein, we propose a single-atom catalytic oxidation method for introducing nanowindows into the graphene layers of single-walled carbon nanotubes (SWCNTs). Using liquid-phase adsorption, copper(II) 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine (CuPc) was adsorbed on SWCNT bundles at a surface coverage of 0.9. Subsequently, narrow nanowindows with a number density of 0.13 nm-2 were produced by oxidation above 550 K, which is higher than the decomposition temperature of bulk CuPc. In particular, oxidation of the CuPc-adsorbed SWCNTs at 623 K increased the surface area from 280 to 1690 m2 g-1 owing to the efficient production of nanowindows. The nanowindow size was estimated to be similar to the molecular size of N2 based on the pronounced low-pressure adsorption hysteresis in the N2 adsorption isotherm. In addition, the enthalpy change for the nanowindow-formation equilibrium decreased by 4 kJ mol-1 when CuPc was present, further evidencing the catalytic effect of the Cu atoms supplied by the adsorbed CuPc molecules.

Sb2Te3 nanoparticle-containing single-walled carbon nanotube films coated with Sb2Te3 electrodeposited layers for thermoelectric applications

Single-walled carbon nanotubes (SWCNTs) are promising thermoelectric materials owing to their flexibility and excellent durability when exposed to heat and chemicals. Thus, they are expected to be used in power supplies for various sensors. However, their thermoelectric performances are inferior to those of inorganic thermoelectric materials. To improve the thermoelectric performance while maintaining the excellent characteristics of SWCNTs, a novel approach to form inorganic thermoelectric layers on the SWCNT bundle surfaces using electrodeposition is proposed. We synthesized Sb2Te3 nanoparticle-containing SWCNT films and coated them with electrodeposited Sb2Te3 layers. The Sb2Te3 nanoparticles were synthesized via a spontaneous redox reaction, which were then added to a SWCNT dispersion solution, and films were produced via vacuum filtration. At higher nanoparticle contents in the films, the Sb2Te3 electrodeposited layers completely covered the SWCNT bundles owing to the increase in the concentration of precursor ions near the SWCNT bundle surface, which in turn was the result of melted nanoparticles. The thermoelectric performance improved, and the maximum power factor at approximately 25 °C was 59.5 µW/(m K2), which was 4.7 times higher than that of the normal SWCNT film. These findings provide valuable insights for designing and fabricating high-performance flexible thermoelectric materials.

Enhanced toughness of boron carbide by single-wall carbon nanotube bundles

Breaking the contradictory of hardness and toughness in B4C is still a challenge to fabricate robust materials. Although compositing B4C with carbon nanotubes (CNTs) is an effective way to improve the toughness, the toughness has the limitation about 6 MPa·m1/2 or hardness below 30 GPa. The limitation of toughness in B4C-CNTs composites is caused by the weak interaction between B4C and CNTs, which impair the strength of composite. So, in this work, the inner compressive stress is introduced in B4C composite with the single-walled carbon nanotube bundles (B4C-SWNTb) by high pressure and high temperature (HPHT). The optimal hardness and fracture toughness are 30 GPa and 8.27 MPa·m1/2 in B4C-2 vol% SWNTb composites, which is 3.3 times higher than that of pure B4C. The high hardness and excellent toughness of B4C-SWNTb composite come from grain refinement of B4C particles, strong combination and inner compressive stress between B4C and SWNTb. This work holds much significance for improving hardness and toughness simultaneously in robust matrix composites.

Delay analysis of mixed CNT bundles as global interconnect for nanotechnology nodes

Abstract This paper presents modeling of high current capability of mixed carbon nanotube (CNT) bundle interconnects depending upon the type of constituent CNT materials and their orientations. With different arrangements, one category of novel mixed CNT bundles formed by the combination of multi-walled/multi-shell CNT and double-shell CNT bundles (MDCB) are proposed and compared with the mixed CNT bundles (MSCB) formed with multi-shell CNT and single-walled CNT bundles. A time-domain analysis is performed for these structures to analyse the effect of delay and power dissipation. It has also been observed that MDCB structures give better performance (≈ 30%) than MSCB structures in terms of power-delay product at the global length of interconnect for nano-regime technology nodes. Also, MDCB structure formed by placing multi-walled CNTs along the periphery and double-walled CNTs in the centre of structure yields the best result against all proposed mixed CNT bundled structures and can be employed for future interconnect applications.