In situ Raman study on single- and double-walled carbon nanotubes as a function of lithium insertion

We investigated the electrochemical lithium ion (Li(+)) insertion/desertion behavior on highly pure and bundled single- and double-walled carbon nanotubes (SWNTs and DWNTs) using an in situ Raman technique. In general, two storage sites could host Li(+) in SWNT and DWNT bundles when varying an external potential: a) the outer surface sites, and b) the interstitial spaces within the bundles. The most sensitive changes in the tangential mode (TM) of the Raman spectra upon doping with Li(+) can be divided into two regions. The first region was found from 2.8 to 1.0 V (the coverage of Li(+) on the outer surface of a bundled nanotube) and was characterized by the loss of resonant conditions via partial charge transfer, where the G(+) line of the SWNT and the TM of the outer tube of DWNTs experienced a highly depressed intensity, but remained almost constant in frequency. The appearance of a Breit-Wigner-Fano (BWF) profile provided strong evidence of metallic inner tubes within DWNTs. The second region was observed when the applied potentials ranged from 0.9 to 0 V and was characterized by Li(+) diffusion into the interstitial sites of the bundled nanotube material. This phenomenon invoked a large downshift of the G(-) band in SWNTs, and a small downshift of the TM of the inner tube of DWNTs caused by expansion of the C--C bonds due to the charge transferred to the nanotubes, and the disappearance of the BWF profile through the screening effect of the interstitial Li(+) layers.     

Raman spectroscopy study of isolated double-walled carbon nanotubes with different metallic and semiconducting configurations

A double-walled carbon nanotube (DWNT) provides the simplest system to study the interaction between concentric layers in carbon nanotubes. The inner and outer walls of a DWNT can be metallic (M) or semiconducting (S), and each of the four possible configurations (M@M, M@S, S@S, S@M) has different electronic properties. Here we report, for the first time, detailed Raman spectroscopy experiments carried out on individual DWNTs, where both concentric tubes are measured under resonance conditions, in order to understand the dependence of their electronic and optical properties according to their configuration. Interestingly, for the three DWNTs that were studied, the inner-outer tube distance (e.g., 0.31-0.33 nm) was less than the interlayer spacing in graphite. We believe these results have important implications in the fabrication of electronic devices using different types of S and M tubular interconnects.     

High-pressure Raman study of debundled single-walled carbon nanotubes

We report the pressure dependence for the radial (omega R) and tangential (omega T) band frequencies in debundled single-walled carbon nanotubes (SWNTs) derived from laser-synthesized SWNT bundles. As previously described, a chemical procedure was used to prepare debundled SWNTs from as-prepared, large SWNT bundles. The normalized pressure coefficient for omega R in the debundled sample was compared with the corresponding value in the bundled sample to quantify the strength of van der Waals interactions between tubes in these nanotube materials. Furthermore, the pressure dependences for the radial (omega R) and tangential (omega T) band frequencies in debundled tubes were also compared with corresponding dependences predicted for isolated SWNTs, obtained with generalized tight binding molecular dynamic (GTBMD) simulations described in our previous work. The results presented here collectively suggest that the van der Waals interaction is still strong in the debundled sample studied here, which contained predominantly small bundles of SWNTs rather than isolated tubes.     

Coated double-walled carbon nanotubes with ceria nanoparticles

Ce(OH)₃ particles with diameters of about 3–8 nm were deposited on the double-walled carbon nanotube (DWNT) bundles evenly by the chemical reaction of CeCl₃ and KOH solution. The Ce(OH)₃/DWNT films changed into CeO₂/DWNT films by heating the samples to 450 °C for 20 min. The atomic ratio of Ce/C in the CeO₂/DWNT film was about 1:35 calculating from the XPS spectra. The deposition mechanism of Ce(OH)₃ on DWNT bundles was also discussed.     

Effect of omitting terms involving tube radii difference in shell models on buckling solutions of DWNTs

Continuum cylindrical shell models have been widely applied in the buckling analysis of carbon nanotubes. An explicit expression for the critical buckling strain of double-walled carbon nanotubes (DWNTs) may be obtained based on cylindrical shell models. The expression is usually simplified by neglecting the terms involving outer and inner tube radii difference. In this brief note, we present the critical buckling strains of DWNTs with the inclusion of these terms and investigate the quantitative effect of neglecting these terms on the critical strain. It was found that the omission of the terms related to outer and inner tube radii difference leads to an overprediction of the critical buckling strain as well as a possible change in the buckling mode shape. It is also observed that the effect of the terms is especially significant for DWNTs with small inner radius but is negligible when the inner radius is relatively large.     

Experimental-computational study of shear interactions within double-walled carbon nanotube bundles

The mechanical behavior of carbon nanotube (CNT)-based fibers and nanocomposites depends intimately on the shear interactions between adjacent tubes. We have applied an experimental-computational approach to investigate the shear interactions between adjacent CNTs within individual double-walled nanotube (DWNT) bundles. The force required to pull out an inner bundle of DWNTs from an outer shell of DWNTs was measured using in situ scanning electron microscopy methods. The normalized force per CNT-CNT interaction (1.7 ± 1.0 nN) was found to be considerably higher than molecular mechanics (MM)-based predictions for bare CNTs (0.3 nN). This MM result is similar to the force that results from exposure of newly formed CNT surfaces, indicating that the observed pullout force arises from factors beyond what arise from potential energy effects associated with bare CNTs. Through further theoretical considerations we show that the experimentally measured pullout force may include small contributions from carbonyl functional groups terminating the free ends of the CNTs, corrugation of the CNT-CNT interactions, and polygonization of the nanotubes due to their mutual interactions. In addition, surface functional groups, such as hydroxyl groups, that may exist between the nanotubes are found to play an unimportant role. All of these potential energy effects account for less than half of the ~1.7 nN force. However, partially pulled-out inner bundles are found not to pull back into the outer shell after the outer shell is broken, suggesting that dissipation is responsible for more than half of the pullout force. The sum of force contributions from potential energy and dissipation effects are found to agree with the experimental pullout force within the experimental error.     

Inner-tube chirality determination for double-walled carbon nanotubes by scanning tunneling microscopy

Evidence for modified electronic structure in double-walled carbon nanotubes with respect to their individual inner and outer constituent single-walled nanotubes is provided by scanning tunneling microscopy and spectroscopy experiments. The contribution originating from the inner tube to the local density of states of the double-walled system was identified in agreement with previous theoretical calculations. Consequently, the chiral index for the inner tube was extracted based on the additional van Hove singularities present in the experimental tunneling spectra.     

Reinforcing the bandaged joint of double-walled carbon nanotube strands by intercalation of epoxy resin

In this study, epoxy resin was used as adhesive material to strengthen the bandaged joint of double-walled carbon nanotube (DWNT) strands in a solution mixing way. As the concentration of soaking solution rises from 10 vol.% to 50 vol.%, the average tensile strength and Young's modulus of the composite joint increase and reach as high as 379 MPa and 17.1 GPa, which are improved by the factors of 1 and 1.6 compared with those of the original joint, respectively. This reinforcement of original joint can be attributed to stronger bonding and better load transfer between the DWNT bundles inside the composite joint induced by intercalated epoxy resin, which is further proved by Raman study on D′ band.     

Thermal-gradient-induced interaction energy ramp and actuation of relative axial motion in short-sleeved double-walled carbon nanotubes

We investigate the phenomenon of actuation of relative linear motion in double-walled carbon nanotubes (DWNTs) resulting from a temperature gradient. Molecular dynamics simulations of DWNTs with short outer tube reveal that the outer tube is driven towards the cold end of the long inner tube. It is also found that the terminal velocity of the sleeve roughly depends linearly on the applied thermal gradient. We calculate the inter-tube interaction energy surface which is revealed to have a gradient depending upon the applied thermal gradient. Consequently, it is proposed that the origin of the thermophoretic motion of the outer tube may be attributed partially to the existence of such an energy gradient. A simple analytical model is presented accounting for the gradient in energy profile as well as the effect of biased thermal noise. It is shown that the proposed model predicts the dynamical behaviour of the long-time performance reasonably well.     

Carbon nanotube-reinforced composites: frequency analysis theories based on the matrix stiffness

Strong and versatile carbon nanotubes are finding new applications in improving conventional polymer-based fibers and films. This paper studies the influence of matrix stiffness and the intertube radial displacements on free vibration of an individual double-walled carbon nanotube (DWNT). For this, a double elastic beam model is presented for frequency analysis in a DWNT embedded in an elastic matrix. The analysis is based on both Euler–Bernoulli and Timoshenko beam theories which considers shear deformation and rotary inertia and for both concentric and non-concentric assumptions considering intertube radial displacements and the related internal degrees of freedom. New intertube resonant frequencies and the associated non-coaxial vibrational modes are calculated. Detailed results are demonstrated for the dependence of resonant frequencies and mode shapes on the matrix stiffness. The results indicate that internal radial displacement and surrounding matrix stiffness could substantially affect resonant frequencies especially for longer double-walled carbon nanotubes of larger innermost radius at higher resonant frequencies, and thus the latter does not keep the otherwise concentric structure at ultrahigh frequencies. Therefore, depending on the matrix stiffness, for carbon nanotubes reinforced composites, different analysis techniques should be used while the aspect ratio of carbon nanotubes has a little effect on the analysis theory which should be selected.     

Sharp burnout failure observed in high current-carrying double-walled carbon nanotube fibers

We report on the current-carrying capability and the high-current-induced thermal burnout failure modes of 5-20 μm diameter double-walled carbon nanotube (DWNT) fibers made by an improved dry-spinning method. It is found that the electrical conductivity and maximum current-carrying capability for these DWNT fibers can reach up to 5.9 × 10(5) S m(-1) and over 1 × 10(5) A cm(-2) in air. In comparison, we observed that standard carbon fiber tended to be oxidized and burnt out into cheese-like morphology when the maximum current was reached, while DWNT fiber showed a much slower breakdown behavior due to the gradual burnout in individual nanotubes. The electron microscopy observations further confirmed that the failure process of DWNT fibers occurs at localized positions, and while the individual nanotubes burn they also get aligned due to local high temperature and electrostatic field. In addition a finite element model was constructed to gain better understanding of the failure behavior of DWNT fibers.     

Energy dissipation of high-speed nanobearings from double-walled carbon nanotubes

The behavior of nanobearings constructed from double-walled carbon nanotubes (DWCNTs) is investigated with molecular dynamics simulations. The results show that the (5, 5)/(10, 10) DWCNTs can work as stable and reliable nanobearings to a speed as high as ～2.65?r?ps(-1) with an inner tube as rotator. When the speed is lower than ～0.75?r?ps(-1), the nanobearings remain in an ultrasmooth state, beyond which the intertube friction increases and fluctuates sharply. The rotational friction is sensitive to many factors such as rotation speed, radial size, and flexibility of CNTs. Increase in rotation speed and the radial sizes of CNTs leads to increase of centrifugal force and decrease of intertube distance, thus, increases the intertube friction. As a result, both the critical speed for ultrasmooth rotation and the ultimate speed decrease with increasing radius of the inner tube with constant intertube distance. The centrifugal force and thermal motion of atoms will stimulate flexile deformation of CNTs, namely waving tube axis and distorting cross-section, which will lead to an increase in rotational friction. When the outer tube serves as the rotator, the DWCNT nanobearing becomes more easily damaged.     

Atomic nanotube welders: boron interstitials triggering connections in double-walled carbon nanotubes

Here we demonstrate that the incorporation of boron (B) atoms between double-walled carbon nanotubes (DWNTs) during thermal annealing (1400-1600 degrees C) results in covalent nanotube "Y" junctions, DWNT coalescence, and the formation of flattened multiwalled carbon nanotubes (MWNTs). These processes occur via the merging of adjacent tubes, which is triggered by B interstitial atoms. We observe that B atom interstitials between DWNTs are responsible for the rapid establishment of covalent connections between neighboring tubes (polymerization), thereby resulting in the fast annealing of the carbon cylinders with B atoms embedded in the newly created carbon nanotube network. Once B is in the lattice, tube faceting (polygonization) starts to occur, and the electronic properties are expected to change dramatically. Therefore, B atoms indeed act as atomic nanotube fusers (or welders), and this process could now be used in assembling novel electronic nanotube devices, nanotube networks, carbon nanofoams and heterojunctions exhibiting p-type electronic properties.     

外压成形试验装置及成形特征研究

设计制造了管材外压成形试验装置,在该装置上实现了管材外侧的高压密封和内部芯模的拆装.采用碳钢管进行了薄壁空心花键件的外压成形试验研究,利用液体介质在管坯外部建立静水压力,使坯料横截面缩小并成形到置于其内部的芯模上,从而获得了空心花键形状的试验件.试验反映了外压成形压力较低、壁厚分布较均匀的特点,所获得的成形件内表面形状与芯模的外表面形状基本一致,同时,成形中不同键位管壁失稳的随机性,对成形件壁厚分布有一定影响.     

Buckling of defective single-walled and double-walled carbon nanotubes under axial compression by molecular dynamics simulation

Buckling of defective single-walled and double-walled carbon nanotubes (SWCNTs and DWCNTs, respectively) due to axial compressive loads has been studied by molecular dynamics simulations, and results compared with those of the perfect structures. It is found that single vacancy defect greatly weakens the carrying capacity of SWCNTs and DWCNTs, though it does slight harm to the effective elastic modulus of the tubes. The influence of defects on the buckling properties of nanotubes is related to the density of the defects, and the relative position of defects also plays an important role in buckling of DWCNTs. The van der Waals force among atoms in the inner and the outer tubes of short defective DWCNTs makes the critical buckling strain of DWCNTs greater than that of the inner tube.     

Sustained smooth dynamics in short-sleeved nanobearings based on double-walled carbon nanotubes

We carry out a molecular dynamics study of nanobearings based on double-walled carbon nanotubes with a short rotating outer tube. A (4, 4)/(9, 9) bearing configuration shows peculiar stabilization of rotational motion at certain values of angular velocities. The observed trend is found at those values of initial angular velocities (in the current context, 0.8-1.5 rad ps(-1)) which denote a transitional regime between nearly frictionless operation at low initial angular speeds and decaying performance at high initial angular velocities. With the use of detailed 'principal components analysis', we find that the energy dissipation occurs mainly due to the excitation of wavy modes in the inner tube of the bearing. It is also proposed that wavy deformation is facilitated by the actuation of axial translation of the outer tube, which acts as an energy channelling mode. Hence, we find that the absence of dissipative wavy modes results in sustained smooth rotational dynamics of the nanobearing at low temperature.     

双金属复合材料固相结合数值仿真研究

基于大变形弹塑性有限元理论,采用ANSYS有限元程序,通过建立合理的有限元分析模型,对Cu/Al双金属复合材料静液挤压固相结合的非稳态过程进行了数值模拟研究,得到了变形体在挤压过程中的等效应力、应变分布及相对滑动量随摩擦系数的变化情况,揭示了组元金属在静液挤压成形过程中的流动规律,指出在一定的变形量条件下,增大内外层金属之间的摩擦系数是较好实现内外层金属固相结合的主要方法.     

Enhanced cellular activation with single walled carbon nanotube bundles presenting antibody stimuli

Efficient immunotherapy can be accomplished by expanding T cells outside the body using single walled carbon nanotube (SWNT) bundles presenting antibody stimuli. Owing to the large surface area of these bundles, which can reach 1560 m (2)/g, T cell stimulating antibodies such as anti-CD3, can be presented at high local concentrations inducing potent activation of T cells. We show that anti-CD3 adsorbed onto SWNT bundles stimulate cells more effectively than equivalent concentrations of soluble anti-CD3. Stimulation by antibody adsorbed onto SWNT is significantly higher than other high surface area materials (activated carbon, polystyrene, and C60 nanoparticles), suggesting unique properties of SWNT bundles for stimuli presentation. We demonstrate the surface area tunability of these bundles by chemical treatment and its effect on antibody adsorption and subsequent T cell activation. In addition, the T cell response varied with the concentration of SWNT in a concentration dependent manner. Antibody stimuli adsorbed onto SWNT bundles represent a novel paradigm for efficient activation of lymphocytes, useful for basic science applications and clinical immunotherapy.     

Controllable preparation and properties of single-/double-walled carbon nanotubes

In this paper, we discussed recent studies done in our laboratories with a floating catalyst chemical vapor deposition (CVD) method. We can grow single- or double-walled carbon nanotubes (SWNTs/DWNTs) with different kinds of catalysts. Single-walled carbon nanotubes without amorphous carbon coating were prepared by thermally decomposing acetylene (C₂H₂) at the temperature range of 750–1200 °C with ferrocene as catalyst. While with sulfur promoted ferrocene catalyst, double-walled carbon nanotubes were mass-produced by pyrolizing C₂H₂ at the temperature range of 900–1100 °C. Furthermore, tunable growth of DWNTs with different diameter was achieved in our experiment. It is found that DWNTs produced at lower carbon partial pressure have much smaller inner tubes, even DWNTs with the smallest inner diameter of 0.4 nm was found in here. As convenient and effective tool, radial breathing mode (RBM) of Raman scattering technique can be used to distinguish SWNTs from DWNTs. In further studies of Raman scattering with DWNTs, the possible match of the inner tubes and the outer tubes according to the RBM bands was assigned, and different chirality types were discussed according to the diameter and chirality dependence of resonant Raman vibration. We also investigated the temperature-dependent frequency shift of resonant Raman spectra of DWNTs in the range of 78–650 K. We found that different RBM peaks, which are relative to different tube diameters, have different temperature coefficient of frequency shift, and the larger diameter carbon nanotubes have more RBM frequency downshift with increasing temperature. It is ascribed to the RBM frequency variation to the temperature dependence of the stretching force constant of C–C bond. Besides, Polarized Raman spectra were preformed on well-aligned SWNTs structure fabricated through post-growth method and found that the angular dependence of Raman intensity is consistent well with the predictions of the resonance Raman theory.     

Piezoelectric tubes and tubular composites for actuator and sensor applications

Piezoelectric actuators and sensors made with a tubular structure can provide a great agility of effective response in the radial direction. For a radially poled piezoelectric tube, the effective piezoelectric constant in that direction can be tuned to be positive, zero or negative by varying the ratio of the outer radius (R _o) to the inner radius (r _o) of the tube. For a suitable ratio of R _o/r _o, this effective constant can also be changed in sign or set to zero by adjusting the d.c. bias field level for tubes made of electrostrictive materials. Therefore, one can make a piezoelectric transducer with all the effective piezoelectric tensile constants having the same sign. End-capped thin-walled tubes also exhibit an exceptionally high hydrostatic response, and the small size of the tubular structure makes it very suitable for integration into a 1–3 composite which possesses low acoustic impedance and high hydrostatic response.