碳纳米管／环氧树脂复合材料的研究

研究了碳纳米管（CNTs）／环氧树脂复合材料的分散性能及电性能。探讨了碳纳米管的含量、管径和稀释剂的用量对环氧树脂电学性能的影响，并用透射电子显微镜（TEM）和扫描电子显微镜（SEM）对其进行表征。结果表明，碳纳米管的分散和含量对环氧树脂的电性能影响很大，而加入碳纳米管能够使环氧树脂由绝缘体变为导体（电阻率〈^10mΩ·cm）。     

Compression behaviour of thick vertically aligned carbon nanotube blocks

Blocks of vertically aligned multiwall carbon nanotubes were prepared by thermal chemical vapor deposition starting from camphor and ferrocene precursors. The blocks, having a thickness of approximately 2 mm and composed of nanotubes with diameter ranging between 30 and 80 nm, were submitted to compression tests. The results were analyzed accordingly with a simple model consisting in a parallel array of nanotubes under compression and bending suffering microscopic instability and compaction. The model mostly fits the experimental stress-strain curves, with a small deviation attributed to dissipative phenomena, such as frictional forces and nanotube wall breakage.     

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.     

Mechanical compliance of photolithographically defined vertically aligned carbon nanotube turf

We describe the micro-mechanical properties of vertically aligned carbon nanotubes (VACNTs) fabricated using a photolithographically patterned iron catalyst prepared using sol–gel techniques. The carbon nanotubes (CNTs) were grown via chemical vapor deposition. The relative mechanical stiffness of the resultant structure was measured using nanoindentation based techniques and is shown to be related to the number of contact sites between tubes. Elastic deformation occurs during compression at large strains, however energy is dissipated during deformation, likely through tube–tube interactions. The effective elastic modulii are depth dependent, due to the compression of pre-buckled geometries. The effective elastic modulii range between 0.03 and 0.08 GPa for a low number of contact sites and 0.1 and 0.3 GPa for a high number of contact sites.     

Temperature effects on resistance of aligned multiwalled carbon nanotube films

Electrical transport in vertically aligned films of multiwalled carbon nanotubes has been investigated in the -150 degrees C to 300 degrees C temperature range (all the tests were conducted in air at atmospheric pressure). In all the cases, the nanotube film exhibited a semi-conducting behavior, with the film resistance decreasing with increasing temperature. Removal of amorphous carbon contamination (via plasma etching) significantly improved the nanotube film's sensitivity to temperature changes (particularly in the 20 degrees C to 200 degrees C temperature range). All the of films tested in this study showed a consistent, repeatable behavior that was independent of the nanotube film length. The temperature sensitivity of the nanotube films was also found to be independent of the heating/cooling rates and without hysteresis. Because of the excellent repeatability and stability of the results, it is conceived that miniaturized temperature sensors could be designed using such aligned multiwalled nanotube films.     

Real-time imaging of vertically aligned carbon nanotube array growth kinetics

In situ time-lapse photography and laser irradiation are applied to understand unusual coordinated growth kinetics of vertically aligned carbon nanotube arrays including pauses in growth, retraction, and local equilibration in length. A model is presented which explains the measured kinetics and determines the conditions for diffusion-limited growth. Laser irradiation of the growing nanotube arrays is first used to prove that the nanotubes grow from catalyst particles at their bases, and then increase their growth rate and terminal lengths.     

Height independent compressive modulus of vertically aligned carbon nanotube arrays

The compressive modulus of dense vertically aligned multiwalled carbon nanotube (CNT) arrays synthesized by chemical vapor deposition was investigated using an optically probed precision-loading platform. For CNT arrays with heights ranging from 15 to 500 microm, the moduli were measured to be about 0.25 MPa and were found to be independent of array height. A continuum mechanics model based on multimode buckling guided by the wavy features of CNT arrays is derived and explains well the measured compressive properties. The measured compressive modulus of the CNT arrays also satisfies the "Dahlquist tack criterion" for pressure sensitive adhesives, which was previously observed for these vertically aligned CNT arrays (Zhao, Y., et al. J. Vac. Sci. Technol., B 2006, 24, 331-335).     

宏观超长定向碳纳米管阵列的制备

采用二甲苯和二茂铁作为碳源和催化剂的化学气相沉积法连续制备定向碳纳米管阵列,在反应6h内获得长度为6mm的宏观定向碳纳米管阵列。当反应时间超过6h后,定向碳纳米管阵列的生长速度明显下降,并有停止生长的趋势,反应16h,定向碳纳米管阵列的厚度仅为6．7mm。本文研究了采用多次连续进给碳源和催化剂的方式制备定向碳纳米管阵列,成功的制备了8．9mm厚的定向碳纳米管阵列,阵列中的碳纳米管具有高的定向性和良好的界面结合。     

Mechanical properties of cross-ply and quasi-isotropic composite laminates processed using aligned multi-walled carbon nanotube/epoxy prepreg

This study examined the processing and mechanical properties of cross-ply and quasi-isotropic composite laminates processed using aligned multi-walled carbon nanotube/epoxy prepreg sheets. Three kinds of CNT/epoxy laminates, ([0°/90°]s, [60°/0°/?60°]s, [0°/45°/90°/?45°]s) were successfully fabricated using aligned CNT/epoxy prepreg sheets. The CNT volume fraction was approximately 10%. No visible void or delamination was observed in composite laminates, and the thickness of each layer was almost equal to that of the prepreg. To evaluate the elastic moduli, E₁₁, E₂₂, and G₁₂, of each ply in the laminates, on-axis and off-axis tensile tests (0°, 45°, 90°) were conducted of aligned CNT/epoxy lamina specimens. The Young’s modulus of CNT/epoxy cross-ply and quasi-isotropic laminates agreed with the theoretical values, which were calculated using classical laminate theory and elastic moduli of CNT/epoxy lamina. The respective failure strains of [0°/90°]s, [60°/0°/?60°]s, and [0°/45°/90°/?45°]s laminates are 0.65, 0.92, 0.63%, which are higher than that of 0° composite lamina (0.5%). Results suggest that the failure strain of 0° layer in composite laminates is improved because of the other layers.     

Enhanced field emission properties of vertically aligned double-walled carbon nanotube arrays

Vertically aligned double-walled carbon nanotube (VA-DWCNT) arrays were synthesized by point-arc microwave plasma chemical vapor deposition on Cr/n-Si and SiO(2)/n-Si substrates. The outer tube diameters of VA-DWCNTs are in the range of 2.5-3.8?nm, and the average interlayer spacing is approximately 0.42?nm. The field emission properties of these VA-DWCNTs were studied. It was found that a VA-DWCNT array grown on a Cr/n-Si substrate had better field emission properties as compared with a VA-DWCNT array grown on a SiO(2)/n-Si substrate and randomly oriented DWCNTs, showing a turn-on field of about 0.85?V?μm(-1) at the emission current density of 0.1?μA?cm(-2) and a threshold field of 1.67?V?μm(-1) at the emission current density of 1.0?mA?cm(-2). The better field emission performance of the VA-DWCNT array was mainly attributed to the vertical alignment of DWCNTs on the Cr/n-Si substrate and the low contact resistance between CNTs and the Cr/n-Si substrate.     

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%。     

Tritrichomonas foetus adhere to superhydrophilic vertically aligned multi-walled carbon nanotube surface

For the first time, we show that Tritrichomonas foetus can adhere on superhydrophilic vertically aligned carbon nanotubes (VACNT) films. Scanning electron microscopy shows an unusual adhesion with a higher membrane filopodium projection in all directions, directly attached to superhydrophilic VACNT tips.     

取向碳纳米管/环氧树脂复合薄膜制备及结构与性能表征

碳纳米管(Carbon nanotube, CNT)/环氧树脂(Epoxy resin, EP)纳米复合材料中树脂含量、分布、CNT取向及其与树脂间界面结合是制备高性能纳米复合材料的关键因素。为了探究树脂分布和CNT/EP复合材料性能之间的关系,采用浮动催化化学气相沉积法制备的CNT薄膜和EP为原料,通过浸渍、牵伸、清洗和热压固化工艺制备CNT/EP复合薄膜。利用聚焦离子束结合扫描电子显微镜定性表征树脂在复合膜中的分布状态。结果表明,随着树脂含量增加,树脂在复合薄膜表面富集程度增加。在最优工艺条件下制备的纳米复合材料中CNT含量为66.14wt%, 拉伸强度和拉伸模量达到1405 MPa和46.7 GPa。      

Transparent,electrically conductive,and flexible films made from multiwalled carbon nanotube/epoxy composites

Optically transparent, conductive, and mechanically flexible epoxy thin films are produced in the present study. Two types of multiwalled carbon nanotubes (MWCNTs) with different aspect ratios are dispersed in epoxy resin through an ultrasonication process. The MWCNT content is varied during the preparation of the thin films. The light transmittance and electrical conductivity of the thin films are characterized. Results show that composites containing MWCNTs with a lower aspect ratio exhibit enhanced electrical conductivity compared to those with a higher aspect ratio. A sheet resistance as low as 100 Ω/sq with nearly 60% optical transparency in 550 nm is achieved with the addition of MWCNTs in epoxy. In summary, transparent, conductive, and flexible MWCNT/epoxy thin films are successfully produced, and the properties of such films are governed by the aspect ratio and content of MWCNTs.     

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.     

Preparation of continuous carbon nanotube networks in carbon fiber/epoxy composite

In order to optimize carbon nanotube (CNT) dispersion state in fiber/epoxy composite, a novel kind of CNT organization form of continuous networks was designed. The present work mainly discussed the feasibility of preparing continuous CNT networks in composite: Fiber fabric was immersed into CNT aqueous solution (containing dispersant) followed by freeze drying and pyrolysis process, prior to epoxy infusion. The morphologies of fabric with CNTs were observed by Scanning Electron Microscope. The relationship between CNT networks and flowing epoxy resin was studied. Properties of composite, including out-of-plane electrical conductivity and interlaminar shear strength (ILSS), were measured. The results demonstrated that continuous and porous CNT networks formed by entangled CNTs could be assembled in fiber fabric. Most part of them were preserved in composite due to the robustness of network structures. The preserved CNT networks significantly improved out-of-plane electrical conductivity, and also have an effect on ILSS value.     

Synthesis of vertically aligned carbon nanotube arrays by injection method in CVD

The well aligned multiwalled carbon nanotube arrays were synthesized by injecting the acetonitrile-ferrocene solution at regular intervals of time. The carbon nanotube arrays were deposited on quartz substrate which is placed at the centre of the CVD reactor in quartz tube. The injection method in chemical vapor deposition allows-excellent control of the catalyst to carbon ratio which facilitates the better growth of aligned carbon nanotubes. The effect of various reaction parameters such as growth temperature, catalyst concentration, gas flow rate, growth time and substrate surface on growth of carbon nanotubes have been studied. It was observed that the diameter of carbon nanotubes increases with increase in catalyst concentration and temperature of the synthesis. The SEM analysis reveals that the average growth rate of carbon nanotube film synthesis was about 1.1 microm/min when the synthesis time was one hour.     

Effective growth of vertically aligned carbon nanotube turfs on flexible Al foil

Vertically aligned multi-walled carbon nanotube turfs (VACNTs) have been synthesized onto commercially available aluminum foil without the use of a pre-deposited catalyst. We used ferrocene as a precursor powder catalyst and acetylene as a carbon source to grow VACNTs using three-temperature-zone chemical vapor deposition at 550–950 °C. The greatest average height of the VACNTs was 124.5 ± 1.7 μm, attained with heating at 750 °C for 10 min. The diameters of the VACNTs were in the range of 5.25–11.85 nm with growth at temperatures of 600–850 °C. The scalable deposition method allows large area coverage on flexible metal foils, which is well suited for integration of vertically aligned carbon nanotubes into plastic electronics.     

Effects of stretching on mechanical properties of aligned multi-walled carbon nanotube/epoxy composites

Composites based on epoxy resin and differently aligned multi-walled carbon nanotube (MWCNT) sheets have been developed using hot-melt prepreg processing. Aligned MWCNT sheets were produced from MWCNT arrays using the drawing and winding technique. Wavy MWCNTs in the sheets have limited reinforcement efficiency in the composites. Therefore, mechanical stretching of the MWCNT sheets and their prepregs was conducted for this study. Mechanical stretching of the MWCNT sheets and hot stretching of the MWCNT/epoxy prepregs markedly improved the mechanical properties of the composites. The improved mechanical properties of stretched composites derived from the increased MWCNT volume fraction and the reduced MWCNT waviness caused by stretching. With a 3% stretch ratio, the MWCNT/epoxy composites achieved their best mechanical properties in this study. Although hot stretching of the prepregs increased the tensile strength and modulus of the composites considerably, its efficiency was lower than that of stretching the MWCNT sheets.