不同催化剂表面定向生长单壁碳纳米管的研究

以不同含水量的乙醇为碳源,分别以Fe/Mo、Ag、Au为催化剂,采用化学气相沉积法制备了单壁碳纳米管.通过SEM,AFM,TEM等表征方法研究了碳纳米管的形貌和微观结构.结果表明,用Fe/Mo、Ag、Au均能长出高质量的碳管阵列,特别是Au的“Sputtering”法,可以不用繁琐地制备纳米颗粒催化剂便得到SWNT阵列...     

催化剂结构与形态对碳纳米管生长的影响

采用溶胶-凝胶超临界流体干燥技术制备了含铁、钴的纳米SiO2复合气凝胶催化剂,用于碳纳米管和纳米碳包覆磁性纳米粒子的合成。利用N2物理吸附、XRD、TEM、HRTEM、EDS、SAED等手段对催化剂在不同温度下处理后晶型的转变、形态的变化进行了分析,并考察了催化剂对碳纳米管形貌、结构和碳增重率的变化。结果表明:随着处理温度从600℃升高到1000℃,催化剂比表面积从312.4m2 g降低到79.6m2 g,催化剂粒子从非晶态向晶态转变,粒径从5nm增大至60nm左右,碳的增重率从254.8%下降41.5%。采用低温处理的催化剂,碳产物中以碳纳米管为主,而采用较高温度处理后的催化剂,碳产物中则以碳包覆粒子为主,且随处理温度的升高碳包覆粒子的含量逐渐增加。     

玄武岩纤维表面生长碳纳米管及其复合材料性能的研究

针对玄武岩纤维(CBF)表面光滑且惰性,在与树脂基体复合制备复合材料时二者结合能力较低的问题,采用化学镀镍在玄武岩纤维表面均匀加载镍催化剂,借助化学气相沉积(CVD)生长碳纳米管(CNTs)。用场发射扫描电镜(FESEM)、透射电镜(TEM)、拉曼光谱(Raman)等方法对生长的CNTs进行表征,并测试复合材料的界面剪切强度。结果表明化学镀镍工艺能在CBF表面均匀加载镍催化剂,有利于CVD生长CNTs。工艺最佳条件为施镀时间15min、500℃下生长10min,此条件下生长的CNTs整齐排列在CBF表面,结晶性较好且呈中空管状。采用生长了CNTs的CBF制备复合材料的界面强度提高了10%。     

碳纤维布表面原位生长碳纳米管的形貌和结构

利用催化化学气相沉积的方法,在碳纤维布上原位生长了碳纳米管(CNTs);并利用扫描电子显微镜、拉曼光谱和透射电子显微镜研究了沿气流方向不同位置处生长的CNTs的形貌与结构演变。结果表明:沿气流方向不同位置处生长的CNTs呈定向排列,结构和质量相近;但不同位置处生长的CNTs的长度不同,远离进气口处生长的CNTs的长度约为进气口处CNTs长度的两倍。     

碳纤维表面原位生长碳纳米管的研究

采用化学气相沉积工艺在碳纤维的表面分别制备了形貌为卷曲状和直立状的原位生长碳纳米管,利用扫描电镜和透射电镜分析了碳纤维表面原位生长碳纳米管的形貌、管径和管壁状态,借助拉曼光谱分析了原位生长碳纳米管的微观结构。结果表明,卷曲状和直立状原位生长碳纳米管都完整地包裹了碳纤维的表面。卷曲状原位生长碳纳米管主要生长在碳纤维的轴向上,呈现卷曲状形貌,其长度分布在5~20μm,管径分布在10~150nm。卷曲状碳纳米管之间互相交联,形成三维网络结构。直立状碳纳米管主要生长在碳纤维的径向上,呈现放射状形貌,其长度分布在10~30μm,直径分布在10~200nm。直立状碳纳米管在纤维表面分布均匀,碳纳米管之间形成了大量的孔隙,碳纳米管在碳纤维的表面呈现出疏松的网络结构。拉曼光谱分析发现两种碳纳米管均在1350cm-1和1580cm-1附近出现了显著的碳峰位。此外,卷曲状和直立状碳纳米管的D峰和G峰的强度比例分别为0.352和0.351,两种碳纳米管均具有较高的石墨化程度。     

理论分析辉光放电对碳纳米管生长速率的影响

利用负偏压增强热丝化学气相沉积，在沉积过渡层Ta和催化剂NiFe层的Si衬底上制备了碳纳米管，并用扫描电子显微镜研究了它们的形貌。发现辉光放电后，碳纳米管的平均长度比无辉光放电时大，并且随着负偏压的增大而增大，即辉光放电增大了它们的生长速率。结合辉光放电和扩散理论分析了辉光放电对碳纳米管生长速率的影响，结果表明在生长碳纳米管的过程中，由于辉光放电的产生，碳在催化剂中的活度得到增强，从而增大了碳纳米管的生长速率。     

定向碳纳米管薄膜的制备研究

采用化学气相沉积法制备了定向碳纳米管薄膜,研究了向反应室载入水、氨水对定向碳纳米管薄膜的影响,并用SEM、TEM、XRD对碳纳米管进行了表征。结果表明：向反应室载入水的量增大,定向碳纳米管的长度先增加后减小。载入水的氩气流量为400ml／min,定向碳纳米管的长度1750μm;向反应室载入氨水,得到疏密相间排列的定向碳纳米管薄膜,氨水量增加,定向碳纳米管薄膜的厚度减小。     

辉光放电和压强对准直碳纳米管生长的影响

利用负偏压增强热丝化学气相沉积系统在沉积有过渡层Ta和催化剂层NiFe的Si村底上制备出准直碳纳米管，并用扫描电子显微镜研完了它们的生长和结构，结果表明辉光放电和压强对其生长和结构有极大的影响。若无辉光放电产生，碳纳米管是弯曲的，有辉光放电时，碳纳米管是准直的。当压强较大时，准直碳纳米管较容易生长，并且随着压强的减小，其平均直径减小和平均长度增大。但压强为5Pa时，准直碳纳米管却不能够生长。最后，分析和讨论了辉光放电和压强对准直碳纳米管生长和结构的影响。     

以乙二胺为促进剂在碳纤维表面生长定向碳纳米管阵列

采用注射化学气相沉积(Chemical vapor deposition,CVD),以乙二胺(Ethylenediamine,EDA)为促进剂,在未涂覆无机陶瓷涂层的碳纤维表面直接生长了定向碳纳米管(Carbon nanotubers,CNTs)阵列。研究表明:碳纤维表面的定向CNTs沿纤维轴向呈对称分布,生长密度约为5×109 tubes/cm2,长度可达18μm。定向CNTs具有多壁、竹节状结构,平均直径约为37nm。EDA对CNTs的生长形貌影响显著,是CNTs在碳纤维表面定向生长的关键。     

非定向多壁碳纳米管制备过程中引入水对其生长的影响

用催化化学气相沉积法制备非定向多壁碳纳米管时,利用气体携带水进入反应区域,考察了水对碳纳米管生长的影响,并用透射电子显微镜对其形貌进行表征.结果显示,带入适量的水后,碳纳米管的产率可以得到较大提高,同时对碳纳米管形貌基本不产生影响.但水量太多或太少都会影响所得碳纳米管的产率,尤其当水过多时,还会对碳纳米管的产率产生较大影响.     

炭纸上原位生长CNF/CP复合体的氧气电催化反应性能

利用催化气相化学沉积(Catalytic chemical vapor deposition,CCVD)法在炭纸上原位生长得到CNF/CP复合体,并对这种复合体的物理化学性能和氧气电催化还原反应(Oxygen reduction reaction,ORR)性能进行了研究.结果表明:纳米炭纤维较为均匀地分散在炭纸上,其中纳米炭纤维具有窄的直径分布.所制CNF/CP复合体具有较大的比表面积和独特的中孔结构;相对于炭纸,CNF/CP复合体的端面碳原子和基面碳原子比例较高.另外,CNF/CP还具有较高的ORR反应活性,其ORR为2电子反应过程,原因可以归结于纳米炭纤维独特的微结构.同时,CNF/CP也具有较高的交换电流密度和较正的平衡电压.     

Electrochemical characterization of carbon nanotube forests grown on copper foil using transition metal catalysts

Growth of vertical, multiwalled carbon nanotubes (CNTs) on bulk copper foil substrates can be achieved by sputtering either Ni or Inconel thin films on Cu substrates followed by thermal chemical vapor deposition using a xylene and ferrocene mixture. During CVD growth, Fe nanoparticles from the ferrocene act as a vapor phase delivered catalyst in addition to the transition metal thin film, which breaks up into islands. Both the thin film and iron are needed for dense and uniform growth of CNTs on the copper substrates. The benefits of this relatively simple and cost effective method of directly integrating CNTs with highly conductive copper substrates are the resulting high density of nanotubes that do not require the use of additional binders and the potential for low contact resistance between the nanotubes and the substrate. This method is therefore of interest for charge storage applications such as double layer capacitors. Inconel thin films in conjunction with Fe from ferrocene appear to work better in comparison to Ni thin films in terms of CNT density and charge storage capability. We report here the power density and specific capacitance values of the double layer capacitors developed from the CNTs grown directly on copper substrates.     

Effect of nitrogen and hydrogen on the growth of multiwall carbon nanotubes on flexible carbon cloth using thermal chemical vapor deposition

In this study, the effect of various mixture fluxes of nitrogen (N₂) and hydrogen (H₂) on carbon nanotube (CNT) synthesis grown on flexible carbon cloth using thermal chemical vapor deposition (thermal CVD) with ethylene (C₂H₄) as the carbon source and nickel (Ni) as the catalyst was investigated. Field emission scanning electron microscopy (FE-SEM) was utilized to study the morphology of CNTs on flexible carbon cloths with various N₂ and H₂ inlet flow rates. The results indicate that average diameter of MWCNTs decreases with increasing H₂ and N₂ flow rates; however, the density of CNTs increases first and then decreases with increasing H₂ and N₂ flow rates. On the other hand, in our field emission experiments, the result indicates that the field emission is strongly dependent on the density and geometry of MWCNTs. In addition, we also found that the contact electrical conductance measurement is an easy method to predict the field emission characteristics of MWCNTs.     

Effect of fibre coating and geometry on the tensile properties of hybrid carbon nanotube coated carbon fibre reinforced composite

Hierarchically structured hybrid composites are ideal engineered materials to carry loads and stresses due to their high in-plane specific mechanical properties. Growing carbon nanotubes (CNTs) on the surface of high performance carbon fibres (CFs) provides a means to tailor the mechanical properties of the fibre–resin interface of a composite. The growth of CNT on CF was conducted via floating catalyst chemical vapor deposition (CVD). The mechanical properties of the resultant fibres, carbon nanotube (CNT) density and alignment morphology were shown to depend on the CNT growth temperature, growth time, carrier gas flow rate, catalyst amount, and atmospheric conditions within the CVD chamber. Carbon nanotube coated carbon fibre reinforced polypropylene (CNT-CF/PP) composites were fabricated and characterized. A combination of Halpin–Tsai equations, Voigt–Reuss model, rule of mixture and Krenchel approach were used in hierarchy to predict the mechanical properties of randomly oriented short fibre reinforced composite. A fractographic analysis was carried out in which the fibre orientation distribution has been analyzed on the composite fracture surfaces with Scanning Electron Microscope (SEM) and image processing software. Finally, the discrepancies between the predicted and experimental values are explained.     

Electrosorption behavior of cations with carbon nanotubes and carbon nanofibres composite film electrodes

The cost-effective, large area carbon nanotubes and carbon nanofibres (CNTs-CNFs) composite film was synthesized on graphite substrate by low pressure and low temperature thermal chemical vapor deposition. Cyclic voltammetry and ac impedance spectroscopy were employed to systematically study the electrochemical properties of CNTs-CNFs film. The electrosorption in salt solutions by CNTs-CNFs film electrodes was studied. It is found that electrosorption of CNTs-CNFs film electrodes is mainly due to Coulombic interaction on the electrical double-layer. Several experiments were conducted to study the ion removal capacity and selectivity of CNTs-CNFs film electrodes, showing that multivalent cations were preferentially adsorbed from the aqueous solution. For cations with same charge, the one with smaller hydrated radius would be more effectively removed.     

Laterally organized carbon nanotube arrays based on hot-filament chemical vapor deposition

Lateral porous anodic alumina (PAA) templates were used to organize carbon nanotubes (CNTs) grown by a hot-filament assisted chemical vapor deposition (HFCVD) process. For the CNT growth, we used a modified “home-made” HFCVD system with two independently powered filaments which are fitted respectively on the methane (CH₄) gas line, which serves as a carbon precursor and on the hydrogen (H₂) gas line, which acts as an etching agent for the parasitic amorphous carbon. Various activation powers of the hot filaments were used to directly or indirectly decompose the gas mixtures at relatively low substrate temperatures. A parametric study of the HFCVD process has been carried out for optimizing the confined CNTs growth inside the lateral PAA templates.     

Multi-walled carbon nanotube growth on oxidized silicon substrates using cyclohexane precursor by chemical vapor deposition

Randomly oriented multi-walled nanotubes (MWNTs) are grown by a thermal chemical vapor deposition (CVD) process from cyclohexane precursor on a 20% copper-80% nickel (Cu-Ni) catalyst on oxidized silicon substrates. This combination of precursor and catalyst, to our knowledge, has been employed for the first time to demonstrate growth of multi-walled carbon nanotubes. The effects of annealing, gas ambient and catalyst layer thickness on the morphology of the grown carbon layers are discussed. The low resistivity values of the MWNTs grown on oxidized silicon substrates are attractive for their potential use in photonic devices and display applications.     

炭纤维表面生长碳纳米管

采用化学气相沉积工艺在炭纤维表面生长了碳纳米管,并观察了它的微观形貌,且对其影响因素进行了初步研究.结果表明:纤维表面的纵向沟槽可以负载催化剂粒子,是生长碳纳米管的物理基础;催化剂的浓度太高,金属粒子容易团聚长大,所得碳纳米管的管径较大;而催化剂浓度太低,则不能在炭纤维整个表面均匀生长碳纳米管;最佳的催化剂溶液的浓度是0.05mol/L的硝酸钴.比较了铁、钴、镍三种过渡金属催化剂,从形成的碳纳米管的质量来看,钴催化剂最佳.     

In situ growth carbon nanotube reinforced SiCf/SiC composite

Carbon nanotube (CNT) reinforced SiC_f/SiC composite was prepared by in situ chemical vapor deposition (CVD) growth of CNTs on SiC fibers then following polymer impregnation pyrolysis (PIP) process. The nature of CNTs and the microstructure of the as prepared CNT-SiC_f/SiC composite were investigated. The mechanical properties of the as prepared CNT-SiC_f/SiC composite were measured. The results reveal that the in situ CVD growth of CNTs on SiC fibers remarkably promotes the mechanical properties of SiC_f/SiC composite. The secondly pull-out of CNTs from matrix during the pull-out of the SiC fibers from matrix consumes the deformation energies, resulting in promotion of the mechanical properties for composite.     

The effect of temperature on the growth of carbon nanotubes on copper foil using a nickel thin film as catalyst

Growth of carbon nanotubes (CNTs) on bulk copper foil substrates has been achieved by sputtering a nickel thin film on Cu substrates followed by thermal chemical vapor deposition. The characteristics of the nanotubes are strongly dependent on the Ni film thickness and reaction temperature. Specifically, a correlation between the thin film nickel catalyst thickness and the CNT diameter was found. Two hydrocarbon sources investigated were methane and acetylene to determine the best conditions for growth of CNTs on copper. These results demonstrate the effectiveness of this simple method of directly integrating CNTs with highly conductive substrates for use in applications where a conductive CNT network is desirable.