Evidence of sequential lift in growth of aligned multiwalled carbon nanotube multilayers

We synthesized aligned multiwalled carbon nanotube multilayers by aerosol-assisted catalytic chemical vapor deposition through sequential injections of aerosols containing both carbon and catalyst precursors. Each sequence was traced by a specific duration or precursor mixture, with the carbon source being possibly enriched in (13)C isotope labels. We discovered that any sequence involved the growth of a new layer on the substrate surface, under any pre-existing one by lifting it up, giving definitive evidence of a base-growth mechanism.     

Fatigue resistance of aligned carbon nanotube arrays under cyclic compression

Structural components subject to cyclic stress can succumb to fatigue, causing them to fail at stress levels much lower than if they were under static mechanical loading. However, despite extensive research into the mechanical properties of carbon nanotube structures for more than a decade, data on the fatigue behaviour of such devices have never been reported. We show that under repeated high compressive strains, long, vertically aligned multiwalled nanotubes exhibit viscoelastic behaviour similar to that observed in soft-tissue membranes. Under compressive cyclic loading, the mechanical response of the nanotube arrays shows preconditioning, characteristic viscoelasticity-induced hysteresis, nonlinear elasticity and stress relaxation, and large deformations. Furthermore, no fatigue failure is observed at high strain amplitudes up to half a million cycles. This combination of soft-tissue-like behaviour and outstanding fatigue resistance suggests that properly engineered nanotube structures could mimic artificial tissues, and that their good electrical conductivity could lead to their use as compliant electrical contacts in a variety of applications.     

碳纳米管阵列研究进展

在介绍CNT阵列性能的基础上,对国内外直接合成CNT阵列的方法进行了评述,重点阐述了各种方法的基本特点及CNT阵列的生长机理、结构控制和批量制备问题。进而探讨了CNT原生阵列、抽丝形成的CNT丝、以及CNT阵列分散后得到的CNTs在复合材料、力学增强、功能器件等方面的初步应用,展望了CNT阵列的发展趋势,指出低成本、大批量可控制备CNT阵列仍然是未来一段时间内国际研究热点。     

Effect of constructive rehybridization on transverse conductivity of aligned single-walled carbon nanotube films

Alignment of densely packed single-walled carbon nanotubes (SWNTs) largely preserves the extraordinary electronic properties of individual SWNTs in the alignment direction, while in transverse direction the films are very resistive due to large energy barriers for tunneling between adjacent SWNTs. We demonstrate that chromium atoms inserted between the sidewalls of parallel SWNTs effectively coordinate to the benzene rings of the nanotubes via hexahapto bonds that preserve the nanotube-conjugated electronic structure and serve as a conduit for electron transfer. The atomically interconnected aligned SWNTs exhibit enhanced transverse conductivity, which increases by ～2100% as a result of the photoactivated organometallic functionalization with Cr. The hexahapto mode of bonding the graphitic surfaces of carbon nanotubes with transition metal atoms offers an attractive route to the reversible chemical engineering of the transport properties of aligned carbon nanotube thin films. We demonstrate that a device fabricated with aligned SWNTs can be reversibly switched between a state of high electrical conductivity (ON) by light and low electrical conductivity (OFF) by applied potential. This study provides a route to the design of novel nanomaterials for applications in electrical atomic switches, optoelectronic and spintronic devices.     

Reproducible fabrication of robust, renewable vertically aligned multiwalled carbon nanotube/epoxy composite electrodes

We describe the reproducible fabrication of robust, vertically aligned multiwalled carbon nanotube (VACNT)/epoxy composite electrodes. The electrodes are characterized by cyclic voltammetry, impedance spectroscopy, and scanning electron and atomic force microscopies. Low background currents are obtained at the electrodes, and common redox probe molecules and NADH show excellent voltammetric behavior. When electrode performance deteriorates due to fouling, the electrode surfaces can be reproducibly renewed by mechanical polishing followed by O(2) plasma treatment. The electrochemical performance of the electrodes is maintained after more than 100 cycles of use and renewal.     

Increasing mouse embryonic fibroblast cells adhesion on superhydrophilic vertically aligned carbon nanotube films

We have analyzed the adhesion of mouse embryonic fibroblasts (MEFs) genetically modified by green fluorescence protein (GFP) gene cultured on vertically-aligned carbon nanotubes (VACNTs) after 6 days. The VACNTs films grown on Ti were obtained by microwave plasma chemical vapor deposition process using Fe catalyst and submitted to an oxygen plasma treatment, for 2 min, at 400 V and 80 mTorr, to convert them to superhydrophilic. Cellular adhesion and morphology were analyzed by scanning electron, fluorescence microscopy, and thermodynamics analysis. Characterizations of superhydrophilic VACNTs films were evaluated by contact angle and X-Ray Photoelectron Spectroscopy. Differences of crowd adhered cells, as well as their spreading on superhydrophilic VACNTs scaffolds, were evaluated using focal adhesion analysis. This study was the first to demonstrate, in real time, that the wettability of VACNTs scaffolds might have enhanced and differential adherence patterns to the MEF-GFP on VACNTs substrates.     

A polarized infrared thermal detector made from super-aligned multiwalled carbon nanotube films

Carbon nanotube (CNT) films, easily drawn from super-aligned CNT arrays with a large area and a good compatibility with semiconductor technology, have been used as light sensitive materials for infrared (IR) detection. A bolometric CNT detector made from one layer of super-aligned CNT film shows a 15.4% resistance change under 10 mW mm(-2) of IR illumination and a fast characteristic response time of 4.4 ms due to its ultra-small heat capacity per unit area in vacuum at room temperature. Besides the power intensity detection, the anisotropic property of the super-aligned CNT films makes them ideal materials to detect the polarization of IR light simultaneously, which provides great potential in infrared imaging polarimetry. Theoretical analyses have been carried out to investigate the influences of CNT film properties on the responsivity and response time of the detector.     

Patterned arrays of vertically aligned carbon nanotube microelectrodes on carbon films prepared by thermal chemical vapor deposition

A straightforward procedure is described for preparation of arrays of microdisk electrodes comprising bundles of vertically aligned carbon nanotubes (VACNTs). The arrays are fabricated by thermal chemical vapor deposition synthesis directly on a planar carbon film support. Use of standard micro- and nanolithography procedures for patterning the bilayer catalyst spots enables arrays to be grown with controlled electrode diameters and spacings. The minimum accessible VACNT bundle diameter, and hence microelectrode diameter, is 2 microm. After insulating the arrays with SU-8 epoxy and exposing the VACNT ends by polishing or treating with O2 plasma, the microdisk electrodes exhibit attractive electrochemical properties.     

树状取向碳纳米管阵列的制备

采用在Ar气氛保护下裂解FePc制备出一种树状取向碳纳米管阵列(ACNTA),这种种特殊结构是由ACNTA裂缝自组装而成.在生长过程中裂缝处能获得更多的催化剂和碳源,因此自身能够持续发展,且裂缝以60°或120°夹角再次分裂,最终形成树状结构.     

Clean carbon nanotube field emitters aligned horizontally

Horizontally aligned carbon nanotube (CNT) field emitters, which strongly adhere to the substrate and show good field emission properties, were fabricated by electrophoresis deposition and fissure formation techniques. A thin film of CNTs was deposited on a substrate, by electrophoresis, from an aqueous mixture of CNT and detergent, and then the detergent was deposited also by electropholysis. CNTs with a clean surface were exposed in the fissures produced by firing. The field emission was increased significantly due to the additional deposition of the detergent. When the CNTs were cut by increasing the firing time, the field emission increased significantly, while their stability decreased considerably. Our method does not require any further treatment for field emission.     

Morphology and electrochemical properties of amphiphilic viologen functionalized multiwalled carbon nanotube hybrids in Langmuir-Blodgett films

Amphiphilic viologens were electrostatically adsorbed on the surface of multiwalled carbon nanotubes (MWCNT) to form viologen-MWCNT hybrids, in which the content of viologens was about 5-10% in weight. Although both viologens and MWCNT hardly dispersed in the water-insoluble organic solvents, the as-prepared viologen-MWCNT hybrids were well dispersed in them with a strong long-term stability, the features of which provided a possibility to prepare their insoluble monolayers at the air-water interface. The surface pressure-area isotherms of these hybrids revealed that they could form stable monolayers, which were transferred on the substrate surfaces by the Langmuir-Blodgett (LB) method. Morphologies of the LB films were characterized by using scanning electron microscopy and atomic force microscopy, the images of which revealed the formation of network two- or three-dimensional films of the functionalized MWCNT. Cyclic voltammograms of the LB films revealed one or two couples of one electron transfer process corresponding to the viologen-MWCNT hybrids with the cathodic and anodic potentials closely related to the alkyl chains of the viologens.     

Highly oriented carbon nanotube papers made of aligned carbon nanotubes

Paper-like carbon nanotube (CNT) materials have many important applications such as in catalysts, in filtration, actuators, capacitor or battery electrodes, and so on. Up to now, the most popular way of preparing buckypapers has involved the procedures of dispersion and filtration of a suspension of CNTs. In this work, we present a simple and effective macroscopic manipulation of aligned CNT arrays called 'domino pushing' in the preparation of the aligned thick buckypapers with large areas. This simple method can efficiently ensure that most of the CNTs are well aligned tightly in the buckypaper. The initial measurements indicate that these buckypapers have better performance on thermal and electrical conductance. These buckypapers with controllable structure also have many potential applications, including supercapacitor electrodes.     

Mechanical immobilization of Hela cells on aligned carbon nanotube array

We demonstrate that an aligned multi-walled carbon nanotube array can immobilize Hela cells through insertion of the nanotube tips into the cell. The cells were immobilized by pressing onto the nanotube array with the aid of mild centrifugal force. The nanotube array fixed a much larger number of cells compared with the flat surface of a Si substrate, indicating strong binding force of the aligned nanotubes toward the cell. This is the first example of mechanical cell immobilization, which offers future applications of the nanotube array for cellular biology, tissue engineering, and biomolecular devices.     

电场诱导多壁碳纳米管有序排列对多壁碳纳米管/环氧树脂复合材料性能的影响

采用交流（AC）电场诱导法制备了多壁碳纳米管（MWCNTs）均匀分散且定向有序排列的MWCNTs/环氧树脂复合材料。采用SEM、偏振拉曼光谱等研究了电场强度、MWCNTs含量、加电时间及温度（黏度）等因素对MWCNTs定向排列的影响,讨论了MWCNTs有序排列对MWCNTs/环氧树脂复合材料电学和力学性能的影响。结果表明：MWCNTs沿电场方向有序排列;MWCNTs/环氧树脂复合材料施加AC电场后的拉曼强度明显高于未施加电场的情况;当MWCNTs含量从0wt%增加到0.025wt%时,MWCNTs/环氧树脂复合材料导电率从2.3×10^-12 S/cm增加到1.3×10^-8 S/cm,增加了约4个数量级;MWCNTs含量为2.5wt%时,MWCNTs/环氧树脂复合材料拉伸强度提高了26.3%。     

Highly elastic and transparent multiwalled carbon nanotube/polydimethylsiloxane bilayer films as electric heating materials

Highly elastic and transparent bilayer films composed of MWCNT and polydimethylsiloxane (PDMS) layers were fabricated by spin-coating of MWCNT aqueous solution on glass plates and following curing of PDMS applied on the MWCNT layer. Morphological feature, optical transparency, tensile property, electrical property, and electric heating behavior of the bilayer films with different MWCNT layer thicknesses of 65–185 nm were investigated. SEM images confirmed that pristine MWCNTs were uniformly deposited on glass substrates and the PDMS layer was combined well with the MWCNT layer, resulting in high structural stability of the bilayer films to high elongational or twisting deformations. With the increase of the thickness of the MWCNT layer, the sheet resistance of the bilayer films decreased substantially from ~ 10⁵ Ω/sq to ~ 10³ Ω/sq, in addition to the change of the optical transmittance from ~ 75% to ~ 40% at a 550 nm wavelength. The electric heating behavior of MWCNT/PDMS bilayer films was strongly dependent on the thickness of the MWCNT layer as well as the applied voltage. Even under high twisting by 540° or continuous stepwise voltage changes for long periods of time, the MWCNT/PDMS bilayer films retained stable electrical heating performance in aspects of temperature responsiveness, steady-state maximum temperature, and electric power efficiency.     

Ultralong aligned multi-walled carbon nanotube for electrochemical sensing

We have investigated electrochemical sensing properties of electrodes fabricated with ultralong aligned multi-walled carbon nanotube (MWNT) bundles synthesized using water-assisted chemical vapor deposition on aluminum (Al) and iron (Fe) coated silicon wafer with ethylene and argon/hydrogen gas as carbon source and buffer gas respectively. Cyclic voltammograms performed on these electrodes show diffusion-controlled-reversible reaction. The dominance of radial diffusion mass transport at these electrodes was also indicated by sigmoidal-shaped voltammograms obtained at various scan rates. These electrodes were able to sense very low concentration of ascorbic acid (approximately 0.7 microM) and dopamine (approximately 1.87 microM), two model species often used in electro-analysis. The excellent electrochemical properties along with good single species detection ability suggest that these MWNTs are promising electrode materials for developing very sensitive chemical and/or biological sensors.     

Super-long aligned TiO2/carbon nanotube arrays

5?mm long aligned titanium oxide/carbon nanotube (TiO(2)/CNT) coaxial nanowire arrays have been prepared by electrochemically coating the constituent CNTs with a uniform layer of highly crystalline anatase TiO(2) nanoparticles. While the presence of the TiO(2) coating was confirmed by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and x-ray diffraction, the resultant TiO(2)/CNT coaxial arrays were demonstrated to exhibit minimized recombination of photoinduced electron-hole pairs and fast electron transfer from the long TiO(2)/CNT arrays to external circuits. This, in conjunction with the aligned macrostructure, facilitates the fabrication of TiO(2)/CNT arrays for various device applications, ranging from photodetectors to photocatalytic systems. Thus, the millimeter long TiO(2)/CNT arrays represent a significant advance in the development of new macroscopic photoelectronic nanomaterials attractive for a variety of device applications beyond those demonstrated in this study.     

Electrospun aligned PLLA/PCL/functionalised multiwalled carbon nanotube composite fibrous membranes and their bio/mechanical properties

Aligned poly(L-lactide) (PLLA)/poly(ε-caprolactone) (PCL)/functionalized multiwalled carbon nanotube (F-MWNT) composite fibrous membranes were fabricated by electrospinning. Their morphology, mechanical properties, in vitro degradation and biocompatibility were studied. With a collector rotation speed of 3000 rpm, the electrospun fibers are highly aligned and the F-MWNTs are oriented along the fiber axis, reinforcing the electrospun fibrous membranes. When the F-MWNTs are incorporated, the PLLA/PCL/F-MWNT composite fibers become thinner due to the increased electrical conductivity. However, when the F-MWNTs are increased to 3.75 wt.%, the higher viscosity and aggregation of F-MWNTs have lead to the formation of beads and a wider diameter distribution in the electrospun fibers. Also, the electrospun fibers having smaller diameter, larger porosity and lower crystallinity induced by F-MWNTs have improved the bio-degradation of the PLLA/PCL/F-MWNT fibrous membranes, which have no toxic effects on the proliferation of adipose-derived stem cells.     

Strain-dependent electrical resistance of multi-walled carbon nanotube/polymer composite films

The strain-dependent electrical resistance characteristics of multi-walled carbon nanotube (MWCNT)/polymer composite films were investigated. In this research, polyethylene oxide (PEO) is used as the polymer matrix. Two representative volume fractions of MWCNT/PEO composite films were selected: 0.56?vol% (near the percolation threshold) and 1.44?vol% (away?from the percolation threshold) of MWCNT. An experimental setup which can measure electrical resistance and strain simultaneously and continuously has been developed. Unique and repeatable relationships in resistance versus strain were obtained for multiple specimens with different volume fractions of MWCNT. The overall pattern of electrical resistance change versus strain for the specimens tested consists of linear and nonlinear regions. A resistance change model to describe the combination of linear and nonlinear modes of electrical resistance change as a function of strain is suggested. The unique characteristics in electrical resistance change for different volume fractions imply that MWCNT/PEO composite films can be used as tunable strain sensors and for application into embedded sensor systems in structures.     

定向碳纳米管/炭纳米复合材料形貌和显微结构

以CVD法定向碳纳米管(ACNTs)阵列为骨架,利用化学气相渗透(CVI)工艺制备了新型定向碳纳米管/炭(ACNT/C)纳米复合材料。通过偏光金相显微镜(PLM)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、X射线衍射(XRD)和Raman光谱等分析方法对其显微结构和热解炭沉积机理进行了研究。结果表明:所制ACNT/C纳米复合材料的热解炭结构主要为类粗糙层结构,围绕碳纳米管生长的热解炭石墨层片结构清晰,并且碳纳米管和热解炭之间具有良好的界面结合;而在相同工艺条件下围绕炭纤维生长的热解炭为典型的光滑层结构。这可能是由于在热解炭沉积过程中存在碳纳米管"诱导"沉积过程,即沿着碳纳米管径向的离域化共轭π键和具有类似结构的芳香族大分子通过π-π非共价键作用相结合,并在CNTs纳米尺寸的影响下,芳香族大分子按照"软取向"(Softepitaxy)围绕碳纳米管生成环形层片状类石墨结构的热解炭。该研究结果有望为热解炭的可控沉积起到一定的借鉴作用。