碳纳米管/碳纤维/环氧树脂复合材料研究

制备了碳纳米管(CNTs)/碳纤维(CF)/环氧树脂(EP)三元复合材料。研究了CNTs含量对复合材料层间剪切强度、弯曲强度和弯曲模量的影响,并采用场发射扫描电镜分析了CNTs在基体树脂中的分散情况。结果表明:复合材料性能的变化源自于CNTs在基体树脂中的分散状态。当CNTs含量为0.2%(wt,下同)时,复合材料剪切强度和弯曲强度达到最大值,分别为99.2MPa和1811.4MPa,但其弯曲模量下降了8.7GPa。当CNTs添加量达到1%时,其弯曲模量达到135.9GPa,较未加入CNTs时提高了11.1%,层间剪切强度和弯曲强度分别降低了5.5MPa和359.5MPa。     

碳纳米管的剪切研究

将碳纳米管放入浓硫酸和浓硝酸(3∶1)的混合溶液中,通过长时间超声处理剪切碳纳米管,TEM观测确认,碳纳米管被剪断,长度由1μm以上减小到300nm以下。     

Effects of uniaxial compressive strain on the electronic-transport properties of zigzag carbon nanotubes

Recently, substantial attention has been paid to the strain sensitivity of the carbon nanotubes’ (CNTs’) electronic properties. In this study, the relationships between the geometric structures and electronic states of zigzag CNTs under uniaxial compressive strain were investigated. We found that different factors dominate the electronic states of zigzag CNTs depending on the strain regions: the initial stage of the strain loading, which lasts until column-buckling deformation begins, and the strain regions corresponding to column- and shell-buckling deformations. Because shell-buckling deformation significantly increases the π-orbital angle, the angle between the ρ orbital axis vectors of adjacent atoms, strong localization of the density of states (LDOS) occurs in the buckled area. We also analyzed the current able to pass through deformed CNTs using a tight-binding-based Green’s function approach and determined that the current can be significantly suppressed by applying uniaxial compressive strain. Our method of predicting the electronic state of a deformed CNT based on the π-orbital angle is expected to be useful for predicting the electronic properties of CNT-based electronic devices and sensors.

Open image in new window

     

酸氧化处理对多壁碳纳米管表面基团的影响

120℃下用浓硝酸对多壁碳纳米管(MWCNTs)进行不同时间的酸氧化处理,考察处理前后碳纳米管的形貌和元素变化,分析酸氧化处理MWCNTs表面功能基团的种类和含量.结果表明:浓硝酸处理,可在MWCNTs表面产生不同数量的羧基、羟基和羰基含氧基团;在最初2h内,羧基含量增加,羟基和羰基含量先增后减,含氧基团总量迅速增加;处理时间继续增加,羧基含量逐渐减少,羟基和羰基含量发生不规则变化,含氧基团总量趋于稳定;MWC-NTs表面首先形成羟基和羰基,这些基团继续被氧化生成羧基,并且它们被氧化生成羧基的能力不同,生成的羧基可进一步氧化最终以CO2释放出来;可通过控制浓硝酸处理的时间来控制MWCNTs表面含氧基团的种类和数量.     

碳纳米管的制备和吸附特性研究

采用CVD法制备了碳纳米管,并用TEM、BET吸附和~(129)Xe NMR对碳纳米管的表面和内部结构进行了表征.通过BET吸附和~(129)Xe NMR的结果对比分析,可以推断碳纳米管并非全部是中空的,而是被许多隔膜分隔成多个锥帽形空腔,这些隔膜一般为无定形碳,五元环或七元环.经过纯化后的碳纳米管具有优异的吸附性能,有望作为新一代的储氢材料.     

Effect of patterned and aligned carbon nanotubes on field emission properties

The field emission (FE) properties of carbon nanotubes (CNTs) films with different morphologies were simulated and examined. Based on the FE mechanism of aligned CNTs’ emitter the theoretical analysis exhibited the following relations: the FE enhancement factor with the distance between the emitters, the electric field with work function, and the work function with FE enhancement factor. Using the structure-induced CNTs growing method and theoretical results the direction of aligned CNTs could be controlled and the special morphology with different aligned CNTs’ film could be fabricated. Comparing to the experimental results (the medium density and patterned CNTs’ emitters) with the theoretically calculating results the I-V curves had the same trend with only 0.05 mA deviation. Based on the better experimental methods and means the accurate of formula could be further improved by modified the FE properties (Φ, β).     

碳纳米管对中间相炭微球制备的影响

以中温煤沥青和碳纳米管为原料进行热缩聚反应,制备出含有碳纳米管的中间相炭微球,采用扫描电子显微镜(SEM)、激光粒度仪和X射线衍射(XRD)等分析手段对其形貌及结构进行了表征。研究了添加碳纳米管对中间相炭微球形貌、粒径、产率、微晶结构及热缩聚工艺的影响。结果表明添加碳纳米管能够促进小球成核,阻止小球的融并长大,使炭微球的粒径减小,分布均匀,但过多的碳纳米管会导致球形度变差及中间相沥青产率的降低;碳纳米管的存在使石墨片层尺寸减小,石墨化程度降低;碳纳米管经过酸煮处理后,可以获得球形度更好、含有更大比例碳纳米管的中间相炭微球。     

Growth of serpentine carbon nanotubes on quartz substrates and their electrical properties

A simple method for high-yield, chemical vapor deposition (CVD) synthesis of serpentine carbon nanotubes, employing quartz substrates and a molecular cluster catalyst, is described. The growth mechanism is analyzed by controlled addition of nanoscale barriers, and by mechanical analysis of the curved sections. The serpentine structures are used to study the electrical transport properties of parallel arrays of identical nanotubes, which show three-terminal conductance that scales linearly with the number of nanotube segments. This article is published with open access at Springerlink.com     

硅烷偶联剂对单壁碳纳米管的化学修饰

采用混酸体系(浓硫酸/浓硝酸体积比为3/1)对单壁碳纳米管进行了氧化处理,并通过氧化处理后在单壁碳纳米管表面生成的羟基官能团与长链硅烷偶联剂进行反应,制备了表面有机修饰的单壁碳纳米管.经过该方法修饰的碳纳米管在三氯甲烷、四氯化碳和二硫化碳等有机溶剂中有较好的溶解性.并通过红外光谱、热失重和透射电镜对其化学结构进行了表征.     

反应温度对碳纳米管的影响

本文利用化学气相沉积( CVD)法,以乙烯为碳源气体,二茂铁为催化剂,在二氧化硅上制备出一系列碳纳米管,并通过拉曼光谱和扫描电子显微镜( SEM)对其形貌、结构和组分进行表征,分析反应温度对碳纳米管的影响.研究发现:当反应温度为860℃时,有均匀的碳纳米管薄膜生成,其管径和长度分别达到104 nm和95 μm,同时结构缺陷少,非碳管杂质较少,纯度较高.     

Hybrid metal-based carbon nanotubes: Novel platform for multifunctional applications

Combining objects with diverse properties has often the advantage of giving rise to novel functionalities. In this scenario, metal-filled and decorated carbon nanotubes (m-CNTs) represent a class of hybrid carbon-based nanostructured materials with enormous interest for application in several fields, ranging from nanoelectronics and spintronics to nanomedicine and magnetic data recording. The present review will provide the reader with an overview of state-of-the-art hybrid architectures based on m-CNT systems, methods currently employed for their fabrication, the set of their unique properties and how they can be applied toward novel devices with multifunctional properties for a broad range of applications.     

环己烷浮游催化法在碳纤维表面生长碳纳米管

以环己烷为碳源、二茂铁为催化剂前躯,采用浮游催化法成功的在碳纤维表面生长了碳纳米管(CNT),制备了多尺度杂化材料CNTs/CF。实验重点考察了反应温度、二茂铁浓度、载气等参数对CNT在纤维表面生长的影响,通过扫描电镜(SEM)、投射电镜(TEM)研究了CNTs/CF的形貌及产物CNT的微观结构。当固定反应温度为820℃、二茂铁-环己烷浓度为2g/100mL时,随着氢气在载气中含量在0～100%范围内变化,产物CNT直径亦有86nm降低至39nm。通过单丝拉伸测试发现,相比初始碳纤维,不同长度的CNTs/CF单纤维强度下降幅度均在10%以内。     

Effects of oxygen on multiwall carbon nanotubes growth by PECVD

Multiwall carbon nanotubes (MWCNTs) were grown by dielectric barrier discharge (DBD)-type plasma enhanced chemical vapor deposition (PECVD) method in downstream. The temperature was 973 K and the compositions of gases were methane, hydrogen and oxygen in the total pressure of 0.05 MPa. The effect of O₂ concentration in the mixture on the configuration of carbon nanotubes (CNTs) was investigated in detail. Results from scanning electron microscope (SEM) and transmission electron microscope (TEM) showed that CNTs grown in CH₄/H₂ (38.6%/61.4%, volume) mixture have many defects and contained disordered graphitic materials. With the addition of appropriate amount of O₂ (∼0.67%), high-purity CNTs could be obtained. However, no CNT, even no carbon matrix existed under the condition of an excessive oxygen concentration (>1.0%, volume) in the mixture. In order to understand the role of O₂ during CNTs growth, optical emission spectroscopy (OES) was in-situ employed and the results predicted that the improvement of CNTs quality in O₂ addition was attributed to the effect of OH oxidation from the reaction of atomic oxygen with hydrogen in the plasma.     

碳纳米管/环氧复合材料制备与性能研究

研究了碳纳米管管径、种类、含量以及偶联-三辊研磨-超声处理等工艺条件对碳纳米管/环氧树脂复合材料拉伸强度和电性能的影响。研究结果表明:三辊研磨-超声联用是均匀分散碳纳米管简单而有效的方法。较低的碳纳米管添加量(0.8%～4%)能大幅度提高环氧树脂的剪切强度和导电性能,添加量为3%时,复合材料的综合性能最优,即剪切强度提高了55.19%,表面/体积电阻率下降了8～10个数量级。     

Preparation and properties of polyarylene ether nitrites/multi-walled carbon nanotubes composites

Polyarylene ether nitriles (PEN)/multi-walled carbon nanotube (MWNT) composites have been successfully fabricated via PEN solution mixing MWNT and then solution-casting. The cast nanocomposite films were characterized by SEM, thermal properties and mechanical properties. The Young's modulus of PEN/MWNT composites was greatly increased with the increase of MWNT concentration. The crystalline behaviors of nanocomposites increased with the increase of MWNT concentration. Thermogravimetric analysis (TGA) measurement showed that MWNT could stabilize PEN when its weight content was greater than 2.0%, and a high char yield in N₂ could be obtained for PEN/MWNT composite at 600 °C.     

化学镀镍碳纳米管的制备及其电磁学和吸波性能研究

首先对碳纳米管(CNTs)进行纯化、敏化、活化预处理,然后利用化学镀方法在其表面沉积金属镍而制备出镀镍碳纳米管(M-CNTs)。SEM、TEM、EDS、XRD和DSC等综合表征结果表明,通过化学镀工艺,在CNTs表面均匀连续的镀覆了一层厚度约为20nm的非晶态镍镀层,且碳纳米管的分散性得到了改善,更有利于用于复合材料领域。原料碳纳米管和镀镍碳纳米管的电磁学性能的对比研究结果表明,M-CNTs的电导率较CNTs有所降低,这也间接反映了镍镀层在CNTs表面的形成;在4～18GHz内,M-CNTs的ε′、ε″、μ和μ″4个电磁参数均较CNTs均有所增加。在此基础上,进一步以M-CNTs为吸波剂,聚氨酯(PU)为粘结剂,制备了PU/M-CNTs吸波涂料,对其吸波性能的研究结果表明,PU/M-CNTs吸波涂料的吸波效果明显受涂层厚度影响,在1.0～2.0mm的范围内,随着涂层厚度的逐渐增大,其吸收峰逐渐向低频移动,且低频段的吸波效果得以加强,高频段的吸波效果有所减弱。     

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）。     

Solar cells with graphene and carbon nanotubes on silicon

Graphene and carbon nanotubes (CNTs) represent attractive materials for photovoltaic (PV) devices due to their unique electronic and optical properties. Graphene and single-wall carbon nanotubes (SWNTs) layers can be directly configured as energy conversion materials to fabricate thin-film solar cells, serving as both photogeneration sites and charge carrier collecting/transport layers. SWNTs can be modified into either p-type conductor through chemical doping (like acidic purification) or n-type conductor through polymer functionalisation. The solar cells can be simply made of a semitransparent thin film of graphene (or SWNTs) deposited on a proper type of silicon substrate to create high-density Schottky (or p–n) junctions at the interface. The high aspect ratios and large surface area of these carbon nano-structured materials can benefit exciton dissociation and charge carrier transport thus improving the power conversion efficiency.     

基于碳纳米管复合物的电化学生物传感器研究进展

新型碳纳米管复合物的开发及其在电化学生物传感器中的应用是近年来材料学和分析领域的研究热点.介绍了碳纳米管复合物在电化学生物传感领域的研究发展,重点对碳纳米管与纳米颗粒、聚合物及离子液体复合材料在电化学生物传感中的应用进行了论述.     

Effects of gamma irradiation for sterilization on aqueous dispersions of length sorted carbon nanotubes

There is currently great interest in the potential use of carbon nanotubes as delivery vessels for nanotherapeutics and other medical applications. However, no data are available on the effects of sterilization methods on the properties of nanotube dispersions, the form in which most medical applications will be processed. Here we show the effects of gamma irradiation from a ⁶⁰Co source on the dispersion and optical properties of single-wall carbon nanotubes in aqueous dispersion. Samples of different length-refined populations were sealed in ampoules and exposed to a dose of approximately 28 kGy, a level sufficient to ensure sterility of the dispersions. In contrast to literature results for solid-phase nanotube samples, the effects of gamma irradiation on the dispersion and optical properties of the nanotube samples were found to be minimal. Based on these results, gamma irradiation appears sufficiently non-destructive to be industrially useful for the sterilization of nanotube dispersions.