Carbon Nanotubes Axis Research Articles

Cytotoxicity of carbon nanotube/polycitric acid hybrid nanomaterials

Polycitric acid was conjugated onto the surface of carbon nanotubes (CNTs), and hybrid nanomaterials containing CNT axis and polycitric acid branches that were highly soluble in aqueous solutions were synthesized. In this work, pristine MWCNTs were opened and functionalized through treatment with acid, then polycitric acid was covalently grafted onto their surface by the “grafting from” approach based on polycondensation of citric acid in the melting state. The chemical structure, morphology, thermal properties and size of MWCNT-g-PCA hybrid materials were investigated by IR, 13C NMR, 1H NMR, TEM, TGA, DSC and DLS. To investigate the biocompatibility of the synthesized hybrid nanomaterials and their potential applications for future nanomedicine, short-term in vitro cytotoxicity and hemocompatibility tests were conducted on HT1080 cell line (human fibrosarcoma). Based on the results of the in vitro cytotoxicity tests and hemolysis assay, no adverse effect was observed on the HT1080 cell and also on red blood cells up to 1 mg/mL concentration. It appeared that the changes in the conformation, shape and dispersity of CNTs, induced by the conjugated hyperbranched polymers, were the main factors that affected the toxicity of CNTs and also their interaction with the cell membranes. Interestingly, the results of the cytotoxicity tests were in agreement with our previous work, carbon nanotubes-graft-polyglycerol, proving that hyperbranched polymers conjugated onto the surface of CNTs dominated their physiochemical properties and therefore their interactions with the cell membranes.

Enhanced Graphitization of Carbon Around Carbon Nanotubes During the Formation of Carbon Nanotube/Graphite Composites by Pyrolysis of Carbon Nanotube/Polyaniline Composites

The carbon nanotubes (CNTs) are actively applied to the reinforcements for composite materials during last decade. One of the attempts is development of CNT/Carbon composites. Although there are some reports on the enhancement of mechanical properties by addition of CNTs in carbon or carbon fiber, it is far below the expectation. Considering the microstructure of carbon materials such as carbon fiber, the properties of them can be modified and enhanced by control of graphitization and alignment of graphene planes. In this study, enhanced graphitization of carbon has been observed the vicinity of CNTs during the pyrolysis of CNT/Polyaniline composites. As a result, novel types of composite, consisting of treading CNTs and coated graphite, can be fabricated. High-resolution transmission electron microscopy revealed a specific orientation relationship between the graphene layers and the CNTs, with an angle of 110 degrees between the layers and the CNT axis. The possibility of graphene alignment control in the carbon by the addition of CNTs is demonstrated.

Study of PE and iPP orientations on the surface of carbon nanotubes by using molecular dynamic simulations

In this study, the early stage of interfacial crystallisation behaviour of low molecular weight polyethylene (PE) and isotactic polypropylene (iPP) oligomer on the surface of carbon nanotubes (CNTs) with different diameters, chiralities and topography structures was studied using MD simulations. We started to simulate the effect of CNTs chirality and diameter on PE molecular chain orientation, and then the effect of CNTs topography structure on PE and iPP molecular chain orientation was investigated. Finally, some experiments were carried out to prove the simulated results. Our study shows that for CNTs with a diameter comparable with the radius of gyration (Rg) of a polymer chain, an easy orientation of PE chains along CNTs axis is observed for all the systems of the CNTs with different chiralities due to a geometric confinement effect. For CNTs with a much larger diameter, multiple orientation of PE chains is induced on its surface due to the lattice matching between graphite lattice and PE molecular chains. In this case, the chirality of CNTs dominates the orientation of graphite lattice, which determines the orientation of PE chains arrangement on CNTs surface. More importantly, it was found that the groove structure formed by CNT bundles is very useful for the stabilisation of polymer chain, and thus facilitates the orientation of molecular chain along the long axis of CNTs. As a result, a novel nanohybrid shish–kebab (NHSK) structure with CNTs acting as central shish while polymer lamellae as kebab can be successfully obtained for both PE with zigzag conformation and iPP with helical conformation. This simulation result was well supported by the experimental observation. Our study could provide not only a deep understanding of the origin of the polymer chain orientation on CNTs surface but also the guidance for the preparation of polymer/CNTs nanocomposites with novel NHSK structure.

Second harmonic generation in carbon nanotubes induced by transversal electrostatic field

Carbon nanotubes (CNTs) of armchair and zigzag type contain an inversion centre, and are thus intrinsically unable to generate dipole even-order nonlinearities, such as second harmonic generation (SHG). Breaking the inversion symmetry by application of an external voltage transversal to the CNT axis will, however, induce a second harmonic response. Similarly, additional non-vanishing second harmonic tensor elements will be induced in chiral tubes already displaying an intrinsic response. Many geometries realizing such a setup can be envisaged, e.g., an experimental gate setup or deposition of CNTs on, or integration in, strongly polarized host media, perhaps facilitating a tunable second harmonic response. In this work, we calculate the SHG signal from CNTs under transversally applied electric fields based on a tight-binding model.

Anisotropic Dielectric Relaxation of the Water Confined in Nanotubes for Terahertz Spectroscopy Studied by Molecular Dynamics Simulations

The dynamics and structure of the hydrogen-bond network in confined water are of importance in understanding biological and chemical processes. Recently, terahertz (THz) time domain spectroscopy was widely applied for studying the kinetics of molecules and the hydrogen-bond network in water. However, the characteristics of the THz spectroscopy varying with respect to the confinement and the mechanism underlying the variation are still unclear. Here, on the basis of molecular dynamics simulations, the relationship between the anisotropic dielectric relaxation and the structure of the water confined in a carbon nanotube (CNT) was investigated. The results show that there are two preferred hydrogen-bond orientations of the confined water in the nanotube: (1) parallel to the CNT axis and (2) perpendicular to the CNT axis, which are clearly different. Moreover, the response of the orientations to the increment of the CNT diameters is opposite, leading to the opposite variations of the dielectric relaxation times along the two directions. The anisotropy in the relaxation time can be presented by the anisotropic dielectric permittivity which is able to be observed through THz spectroscopy. The anormal behaviors above are attributed to the special structure of the water close to the nanotube wall due to the confinement and hydrophobicity of CNT. These studies contribute an important step in understanding the THz experiments of water in nanoscales, and designing a chamber for specific chemical and biological reactions by controlling the diameters and materials of the nanotube.

Anisotropy of the water–carbon interaction: molecular simulations of water in low-diameter carbon nanotubes

Effective Lennard-Jones models for the water-carbon interaction are derived from existing high-level ab initio calculations of water adsorbed on graphene models. The resulting potential energy well (εCO + 2εCH ≈ 1 kJ mol(-1)) is deeper than most of the previously used values in the literature on water in carbon nanotubes (CNTs). Moreover, a substantial anisotropy of the water-carbon interaction (εCO ≈ 2εCH) is obtained, which is neglected in most of the literature. We systematically investigate the effect of this anisotropy on structure and dynamics of TIP5P water confined in narrow, single-walled CNTs by means of molecular dynamics simulations for T = 300 K. While for isotropic models water usually forms one-dimensional, ordered chains inside (6,6) CNTs, we find frequent chain ruptures in simulations with medium to strongly anisotropic potentials. Here, the water molecules tend to form denser clusters displaying a liquid-like behaviour, allowing for self-diffusion along the CNT axis, in contrast to all previous simulations employing spherical (εCH = 0) interaction models. For (7,7) CNTs we observe structures close to trigonal, helical ice nanotubes which exhibit a non-monotonous dependence on the anisotropy of the water-carbon interaction. Both for vanishing and for large values of εCH we find increased fluctuations leading to a more liquid-like behaviour, with enhanced axial diffusion. In contrast, structure and dynamics of water inside (8,8) CNTs are found to be almost independent of the anisotropy of the underlying potential, which is attributed to the higher stability of the non-helical fivefold water prisms. We predict this situation to also prevail for larger CNTs, as the influence of the water-water interaction dominates over that of the water-carbon interaction.

High-yield Synthesis of Nanohybrid Shish-kebab Polyethylene-carbon Nanotube Structure

We report a novel method to prepare nanohybrid shish-kebab (NHSK) structure of polyethylene (PE) and carbon nanotube (CNT). Pristine CNTs without surface modification with high concentration was effectively dispersed in xylene solution by a simple shearing method, which induces the quick crystallization of PE in xylene to form a novel NHSK structure with more dense and smaller PE kebab on CNT axis. The flocculated NHSK product was transferred quickly from the xylene solution to the ethanol solution, in order to shorten the preparation time. The freeze-drying method was used in vacuum instead of high-temperature drying to avoid the aggregation of NHSK product. These improvements allow the formation of NHSK with an absolute yield of 200 mg·h−1, which is 2000 folds of that reported previously. It is favorable to apply this structured material in high performance nanocomposite, by improving the compatibility of CNTs in polymer and the interfacial force between CNTs and polymer.

Facile synthesis of a Co3O4–carbon nanotube composite and its superior performance as an anode material for Li-ion batteries

In this work, we report a facile method for the synthesis of a Co3O4–functionalized carbon nanotube (Co3O4–f-CNT) composite via the growth of Co3O4 nanoparticles on the surface of functionalized carbon nanotubes (f-CNTs) by thermal decomposition of cobalt nitrate hexahydrate in ethanol. The composite consists of 13% carbon nanotubes and 87% Co3O4 nanoparticles by weight, and all the Co3O4 particles grew compactly along the carbon nanotube axis with a highly uniform dispersion. When used as an anode material for rechargeable lithium ion batteries, the composite manifested high capacities and excellent cycling performance at high and low current rates. The discharge capacity was 719 mA h g−1 at the 2nd cycle and 776 mA h g−1 at the 100th cycle. Even at a current density of 1 A g−1, the specific capacity still remained at about 600 mA h g−1. This superior electrochemical performance was attributed to the unique nanostructure of the composite. Because almost all of the Co3O4 nanoparticles were immobilized on the surface of f-CNTs, physical aggregation of nanoparticles was avoided during the charge–discharge processes. Furthermore, the good mechanical flexibility of f-CNTs can readily alleviate the massive volume expansion/shrinkage associated with a conversion reaction electrode. Finally, f-CNTs are highly conductive matrices for electrons due to their high conductivity, which can shorten the diffusion path for electrons.

Noncovalent Interaction of Methylene Blue with Carbon Nanotubes: Theoretical and Mass Spectrometry Characterization

Noncovalent interaction of methylene blue dye cation (MB+) with single walled carbon nanotubes (CNT) is characterized by molecular dynamics (MD) simulation, quantum chemical calculations, and laser desorption/ionization (LDI) mass spectrometry. The MD simulation of the (MB+)n–CNT (n = 1–10) complexes in water demonstrates that the MB+ cations are adsorbed on the nanotube surface in the monomeric form. MD reveals both parallel and perpendicular orientations of the MB+ tricyclic plane in relation to the long axis of CNT when placed in the water environment. The interaction energy between the components of the complex in the perpendicular conformation, as determined by quantum chemical calculations at the DFT/M05-2X/6-31++G(d,p) level of theory, explains why the bending of the MB+ cation at the sulfur atom weakens the π-system of bonds and allows for the perpendicular orientation to occur. It is also found that the adsorbed MB+ induces positive electrostatic potential around the adjacent semicylindrical segm...

Growth and Characterization of Bamboo-Shaped Carbon Nanotubes Using Nanocluster-Assembled ZnO:Co Thin Films as Catalyst

Bamboo-shaped carbon nanotubes (CNTs) had been successfully fabricated by a plasma enhanced chemical vapor deposition method, in which nanocluster-assembled ZnO:Co thin film was used as catalyst. It was found that bamboo-shaped CNTs were generally grown in a direction perpendicularly to the substrate surface with the tops of CNTs dominated by the droplet-like catalyst covered by the carbon layer. The diameter of CNTs was ranged from 20-50 nm. High resolution of TEM image showed that the typical CNT had a multi-walled structure with an inner core presented. The ordered graphite layers were inclined to an axis of CNT about 18 degrees and the interlayer space of a CNT was about 0.35 nm. Two peaks in Raman spectrum at 1586 cm(-1) and 1372 cm(-1) were identified as G-band and D-band for graphite, respectively. The results showed that catalyst based on ZnO:Co thin films could be used for the growth of CNTs with bamboo-shaped structure.

Hybrid nanoparticle architecture for cellular uptake and bioimaging: direct crystallization of a polymer immobilized with magnetic nanoparticles on carbon nanotubes

We describe here the success of an innovative approach of direct immobilization of magnetic nanoparticles (MNPs) onto carbon nanotubes (CNTs). The approach involved functionalization of magnetic nanoparticles and consequent covalent linkage to a copolymer (PE-b-PEG). Next, the immobilized magnetic nanoparticles on the copolymer were directly crystallized on the long axis of CNTs, where the interfacial adhesion comes from electrostatic and van der Waals interaction. The intracellular trafficking of a hybrid nanoparticle system [(PE-b-PEG)-MNP-CNT-FITC] in HeLa cells was monitored using a fluorescent marker, FITC, conjugated to the nanoparticle system. The distribution of the nanoparticle system inside cells was studied by fluorescence microscopy in a time and dose dependent manner, and it was observed that the nanoparticles are located in the cytoplasm and no apparent cell death was observed at the concentration studied. Also, the effect of an externally applied magnetic field on actin cytoskeleton, cell morphology and intracellular uptake of iron was studied. The approach described here is promising for simultaneous imaging and monitoring intracellular uptake.

Enhanced thermoelectric properties of CNT/PANI composite nanofibers by highly orienting the arrangement of polymer chains

Carbon nanotube (CNT)/Polyaniline (PANI) thermoelectric composite nanofibers were prepared by a combination of in situ polymerization and electro-spinning processes. The obtained composite nanofibers were macroscopically aligned, while the CNTs were embedded in the nanofibers and oriented along the fiber axis. Polarized Raman spectra and X-ray diffraction (XRD) studies verified that the PANI backbone chains were orientated along the CNT axis and therefore along the fiber axis due to the strong chemical interactions between PANI and CNTs. The highly ordered arrangement of the PANI backbone chains not only reduces the π–π conjugated defects in the polymer backbone, but also increases the effective degree of electron delocalization and therefore enhances the carrier mobility in PANI, which results in the anisotropic thermoelectric properties especially with more than a doubled improvement of power factor in the orientation direction. This study not only provides an effective route to orient the conducting polymer chains at the molecular level but also demonstrates a possibility to design a conducting polymer with high thermoelectric performance through constructing a highly extended and orderly aligned backbone chain structure by chemical routes.

Deformation of Carbon Nanotubes Colliding with a Silicon Surface and Its Dependence on Temperature

Using molecular dynamics simulation, we investigated the carbon nanotubes (CNTs) colliding with a silicon surface at a speed of 600 m/s, mimicking cold spray experiments of CNTs. Depending on temperature (300-900 K), the CNT is deposited on or bounces off the surface after impact on the surface. The CNT was more deformed as its temperature rose. The deformation of CNT was maximal for the collision geometry where the long axis of CNT lies parallel to the surface plane. However, its vibrational energy was maximal when the CNT collided with its long axis perpendicular to the surface.

Tunable Nanometer‐Scale Architecture of Organic–Inorganic Hybrid Nanostructured Materials for Structural and Functional Applications

AbstractDirect crystallization of polymer crystals along the long axis of carbon nanotubes (CNTs) to produce a hybrid nanostructured material is expected to retain the properties of CNTs and has the advantage of a strong polymer/CNT interface. Three different polymer systems are selected to elucidate the fundamental principles that govern the processing of organic–inorganic hybrid nanostructured materials with nanometer‐scale architecture. The tunable character of the nanometer‐scale hybrid architecture is investigated as a function of undercooling and polymer concentration. It is observed that while polyethylene and nylon 6,6 crystallize in a periodic manner as disk‐shaped crystals along the long axis of the CNTs, the polypropylene–CNTs result in conventional spherulites. The reasons for these differences are analyzed.

Hybrid Nanoscale Architecture for Enhancement of Antimicrobial Activity: Immobilization of Silver Nanoparticles on Thiol‐Functionalized Polymer Crystallized on Carbon Nanotubes

AbstractWe describe here the synthesis and antimicrobial activity of an innovative nanohybrid system, characterized by attachment of silver nanoparticles (AgNPs) to the thiol‐functionalized polymer that was periodically crystallized on carbon nanotubes (CNTs). The synthesis of the nanohybrid architecture first involved direct crystallization of thiol‐functionalized copolymer along the long axis of CNTs, followed by attachment of AgNPs to the thiol‐group of functionalized copolymer. The antimicrobial activity was assessed in terms of interaction withEscherichia coli, where the constituents of the nanohybrid structure play a synergistic role. The antimicrobial activity was approximately four orders of magnitude greater than the ex situ precipitated bare AgNPs. Possible mechanisms underlying enhanced antimicrobial activity are discussed. The study underscores the potential of uniquely combining CNTs and biopolymers for biomedical applications, in the present case, antimicrobial activity.

Single mode phonon energy transmission in functionalized carbon nanotubes

Although the carbon nanotube (CNT) features superior thermal properties in its pristine form, the chemical functionalization often required for many applications of CNT inevitably degrades the structural integrity and affects the transport of energy carriers. In this article, the effect of the side wall functionalization on the phonon energy transmission along the symmetry axis of CNT is studied using the phonon wave packet method. Three different functional groups are studied: methyl (-CH(3)), vinyl (-C(2)H(3)), and carboxyl (-COOH). We find that, near Γ point of the Brillouin zone, acoustic phonons show ideal transmission, while the transmission of the optical phonons is strongly suppressed. A positive correlation between the energy transmission coefficient and the phonon group velocity is observed for both acoustic and optical phonon modes. On comparing the transmission due to functional groups with equivalent point mass defects on CNT, we find that the chemistry of the functional group, rather than its molecular mass, has a dominant role in determining phonon scattering, hence the transmission, at the defect sites.

Dynamic response of phenolic resin and its carbon-nanotube composites to shock wave loading

We investigate with nonreactive molecular dynamics simulations the dynamic response of phenolic resin and its carbon-nanotube (CNT) composites to shock wave compression. For phenolic resin, our simulations yield shock states in agreement with experiments on similar polymers except the “phase change” observed in experiments, indicating that such phase change is chemical in nature. The elastic–plastic transition is characterized by shear stress relaxation and atomic-level slip, and phenolic resin shows strong strain hardening. Shock loading of the CNT-resin composites is applied parallel or perpendicular to the CNT axis, and the composites demonstrate anisotropy in wave propagation, yield and CNT deformation. The CNTs induce stress concentrations in the composites and may increase the yield strength. Our simulations suggest that the bulk shock response of the composites depends on the volume fraction, length ratio, impact cross-section, and geometry of the CNT components; the short CNTs in current simulations have insignificant effect on the bulk response of resin polymer.

Control of Unidirectional Transport of Single-File Water Molecules through Carbon Nanotubes in an Electric Field

The transport of water molecules through nanopores is not only crucial to biological activities but also useful for designing novel nanofluidic devices. Despite considerable effort and progress that has been made, a controllable and unidirectional water flow is still difficult to achieve and the underlying mechanism is far from being understood. In this paper, using molecular dynamics simulations, we systematically investigate the effects of an external electric field on the transport of single-file water molecules through a carbon nanotube (CNT). We find that the orientation of water molecules inside the CNT can be well-tuned by the electric field and is strongly coupled to the water flux. This orientation-induced water flux is energetically due to the asymmetrical water-water interaction along the CNT axis. The wavelike water density profiles are disturbed under strong field strengths. The frequency of flipping for the water dipoles will decrease as the field strength is increased, and the flipping events vanish completely for the relatively large field strengths. Most importantly, a critical field strength E(c) related to the water flux is found. The water flux is increased as E is increased for E ≤ E(c), while it is almost unchanged for E > E(c). Thus, the electric field offers a level of governing for unidirectional water flow, which may have some biological applications and provides a route for designing efficient nanopumps.

Effects of Vacancy Defects on the Interfacial Shear Strength of Carbon Nanotube Reinforced Polymer Composite

We investigate the effects of the vacancy defects (i.e., missing atoms) in carbon nanotubes (CNTs) on the interfacial shear strength (ISS) of the CNT-polyethylene composite with the molecular dynamics simulation. In the simulation, the crystalline polyethylene matrix is set up in a hexagonal array with the polymer chains parallel to the CNT axis. Vacancy defects in the CNT are introduced by removing the corresponding atoms from the pristine CNT (i.e., CNT without any defect). Three patterns of vacancy defects with three different sizes are considered. Two types of interfaces, with and without cross-links between the CNT and the matrix are also considered here. Polyethylene chains are used as cross-links between the CNT and the matrix. The Brenner potential is used for the carbon-carbon interaction in the CNT, while the polymer is modeled by a united-atom potential. The nonbonded van der Waals interaction between the CNT and the polymer matrix and within the polymer matrix itself is modeled with the Lennard-Jones potential. To determine the ISS, we conduct the CNT pull-out from the polymer matrix and the ISS has been estimated with the change of total potential energy of the CNT-polymer system. The simulation results reveal that the vacancy defects significantly influence the ISS. Moreover, the simulation clarifies that CNT breakage occurs during the pull-out process for large size vacancy defect which ultimately reduces the reinforcement.

Hindered rolling and friction anisotropy in supported carbon nanotubes

Carbon nanotubes (CNTs) are well known for their exceptional thermal, mechanical and electrical properties. For many CNT applications it is of the foremost importance to know their frictional properties. However, very little is known about the frictional forces between an individual nanotube and a substrate or tip. Here, we present a combined theoretical and experimental study of the frictional forces encountered by a nanosize tip sliding on top of a supported multiwall CNT along a direction parallel or transverse to the CNT axis. Surprisingly, we find a higher friction coefficient in the transverse direction compared with the parallel direction. This behaviour is explained by a simulation showing that transverse friction elicits a soft 'hindered rolling' of the tube and a frictional dissipation that is absent, or partially absent for chiral CNTs, when the tip slides parallel to the CNT axis. Our findings can help in developing better strategies for large-scale CNT assembling and sorting on a surface.