Growth of Nanoscale Carbon Structures and Their Corresponding Hydrogen Uptake Properties

Carbon nanostructures have been synthesized using the chemical vapor deposition technique (CVD) on different catalysts, using ethylene, acetylene, or methane as the hydrocarbons. Morphological characterizations obtained using a scanning electron microscope (SEM) showed that the reaction products are carbon nanofibers (CNF) with an outer diameter that depends on the reaction conditions and nature of the reactants. Hydrogen uptake measurements, performed volumetrically in a Sievert-type installation, showed the quantity of desorbed hydrogen (for pressure intervals ranging from 1 to 100 bars) depends on the synthesis conditions and the treatment preceding the hydrogen absorption process. For carbon nanotubes that were preparedaccording to literature guidelines and obtained from ethylene on a Ni:Cu catalyst, the amounts of absorbed hydrogen were less than 1% by weight. carbon nanostructures chemical vapor deposition hydrogen absorption SEM     

Effect of Ethylene Flow Rate and CVD Process Time on Diameter Distribution of MWCNTs

To date, focus of the research activities in nanoscience was to control the chemical vapor deposition (CVD) growth of carbon nanotubes (CNTs) by changing the precursor pressure and process temperature. The effect of the precursor flow rate and process time on CNTs growth parameters has been overlooked in past studies and therefore is very little known. This study was focused on the optimization of the ethylene flow rate and CVD process time for CNTs growth over Fe₂O₃/Al₂O₃ catalyst in a fluidized bed chemical vapor deposition (FBCVD) reactor, operating at atmospheric pressure. Argon and hydrogen were considered as the carrier and supporting gases, respectively. Transmission electron microscope (TEM) and Scanning Electron Microscopy (SEM) were used to investigate the surface morphology, nanostructures, purity and yield of the grown CNTs. In-depth analysis revealed an increase in tube length, yield and the carbon concentration with ethylene flow rate in the range of 50–110 sccm. However, an inverse relationship between flow rate and tube diameter distribution was predicted in the given work. The most favorable results were obtained at an ethylene flow rate of 100 sccm and a CVD process time of 60 minutes. The dense and homogeneous growth of relatively pure nanotubes of increased tube length and narrow diameter distribution, in the range of 20–25 nm, was observed at optimized flow rate and process time.     

工艺条件对氧化硅纳米结构的影响

通过金属催化化学气相沉积法,采用四氯化硅作为硅源合成了棒状氧化硅纳米结构.对产物进行了场发射扫描电镜、透射电镜及附带X射线能谱仪的表征测试.生长工艺条件包括沉积位置、反应时间、氩气冲洗次数和基板对产物纳米结构的影响进行了探讨,其中前三者分别影响气相硅源的浓度、获取硅源的量和残余氧的浓度,而基板的成分和表面粗糙度对纳米结构的生长影响显著.     

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.     

Field emission characteristics from tapered ZnO nanostructures grown onto vertically aligned carbon nanotubes

Zinc oxide (ZnO) nanostructures were grown on vertically aligned carbon nanotubes (CNTs) using thermal chemical vapor deposition (CVD) to enhance the field emission characteristics. The shape of ZnO nanostructure was tapered. Scanning electron microscopy (SEM) image showed the ZnO nanostructures were grown onto CNT surface uniformly. The field electron emission of pristine CNTs and ZnO-coated CNTs were measured. The results showed that ZnO nanostructures grown onto CNTs could improve the field emission characteristics. The ZnO-coated CNTs had a threshold electric field at about 3.1 V/μm at 1.0 mA/cm². The results demonstrated that the ZnO-coated CNT is an ideal field emitter candidate material. The stability of the field emission current was also tested.     

Synthesis of carbon nanostructures--in-situ study of carbon deposition parameters

An in-situ study of carbon deposition parameters by the method of chemical vapor deposition (CVD) from methane is used in order to estimate the time of the deactivation catalyst (Fe/Mo catalyst supported on alumina (AI2O3)). The deposition process is studied by measuring the weight change of the sample using a microbalance. The effect of the operating parameters, such as temperature, feed concentration, and catalyst composition, on the deposition rate and morphology of the deposits is investigated. Based on the initial weight of the catalyst, the relative weight gain of the sample due to carbon deposition on the catalyst is higher than 300% in a few minutes of the deposition process but the deposition rate reduces in more than 100 min. The carbon material characterized with Scanning Electron Microscopy (SEM) and Raman Spectroscopy and it is found to consist of carbon nanostructures.     

Cyclic voltammetry response of an undoped CVD diamond electrodes

The polycrystalline undoped diamond layers were deposited on tungsten wire substrates by using hot filament chemical vapor deposition (HFCVD) technique. As a working gas the mixture of methanol in excess of hydrogen was used. The morphologies and quality of as-deposited films were monitored by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy respectively. The electrochemical activity of the obtained diamond layers was monitored by using cyclic voltammetry measurements. Analysis of the ferrocyanide–ferricyanide couple at undoped diamond electrode suggests that electrochemical reaction at diamond electrode has a quasireversibile character. The ratio of the anodic and cathodic peak currents was always close to unity. In this work we showed that the amorphous carbon admixture in the CVD diamond layer has a crucial influence on its electrochemical performance.     

氢气流量对碳纳米管生长的影响

采用等离子体增强化学气相沉积技术,以C2H2、H2和N2为反应气体,制备出碳纳米管薄膜。利用扫描电镜和拉曼光谱仪对其进行表征。结果表明:氢气流量对碳纳米管薄膜的生长起着重要作用,获得分布均匀、密度适中、杂质缺陷少的碳纳米管的最佳氢气流量为30 sccm。     

Hydrogen Storage in Carbon-Based Nanostructured Materials

Carbon nanostructures represent a revolution in science and hold the potential for a large range of applications because of their interesting electrical, mechanical, and optical properties. Multiwall carbon nanotubes and carbon nanofibers of herringbone formation were grown by chemical vapor deposition on different catalysts from a number of hydrocarbon sources. After the total or particle removal of the catalyst system, the carbon nanostructures were analyzed for hydrogen uptake. Six samples of nanofibers grown on a Pd-based catalyst system (with a surface area of 425–455 m²/g) were controlled oxidized in air, such that they had different ratios of Pd/C varying from 0.05 to 0.9 mole ratio. The hydrogen uptake experiments were performed volumetrically in a Sievert-type installation and showed that the quantity of desorbed hydrogen (for pressure intervals ranging from 1 to 100 bars) by the carbon nanostructures free of any metal catalyst particles was between 0.04 and 0.33% by weight. For the samples of nanofibers that contained Pd in various Pd/C ratios, palladium revealed catalytic properties and supplied atomic hydrogen at the Pd/C interface by dissociating the H₂ molecules. The results show a direct correlation between the Pd/C ratio and the quantity of hydrogen absorbed by these samples. A saturation value of about 1.5 wt.% was reached for a high ratio of about 1:1 of Pd/C. The multiwall carbon nanotubes grown on a Fe:Co:CaCO₃ catalytic system and purified by acid cleaning and air oxidation showed a hydrogen uptake value of 0.1 to 0.2 wt.%.     

温度对BCl3-CH4-H2化学气相沉积掺硼碳沉积过程的影响

以三氯化硼、甲烷和氢气的混合气体为前驱体,利用磁悬浮天平热重系统研究了850～1200℃区间内化学气相沉积掺硼碳的原位动力学.探索了温度对沉积速率的影响,计算了该温度区间内沉积过程的表观活化能,同时借助SEM和EDS技术.测试了不同温度点(900℃、1000℃、1100℃和1200℃)沉积产物的微观结构和成分.结果表明,化学气相沉积掺硼碳属于典型的热激活反应过程;在所研究的温度区间内存在5种不同的反应控制机制;随着温度的升高,沉积产物的n(B)/n(C)和堆积密度都显著变小,说明高n(B)/n(C)和高致密度的掺硼碳涂层应在较低的温度下制备.     

Hierarchical carbon nanostructure design: ultra-long carbon nanofibers decorated with carbon nanotubes

Hierarchical carbon nanostructures based on ultra-long carbon nanofibers (CNF) decorated with carbon nanotubes (CNT) have been prepared using plasma processes. The nickel/carbon composite nanofibers, used as a support for the growth of CNT, were deposited on nanopatterned silicon substrate by a hybrid plasma process, combining magnetron sputtering and plasma-enhanced chemical vapor deposition (PECVD). Transmission electron microscopy revealed the presence of spherical nanoparticles randomly dispersed within the carbon nanofibers. The nickel nanoparticles have been used as a catalyst to initiate the growth of CNT by PECVD at 600°C. After the growth of CNT onto the ultra-long CNF, SEM imaging revealed the formation of hierarchical carbon nanostructures which consist of CNF sheathed with CNTs. Furthermore, we demonstrate that reducing the growth temperature of CNT to less than 500°C leads to the formation of carbon nanowalls on the CNF instead of CNT. This simple fabrication method allows an easy preparation of hierarchical carbon nanostructures over a large surface area, as well as a simple manipulation of such material in order to integrate it into nanodevices.     

Synthesis of multi-walled carbon nanotubes by microwave plasma-enhanced chemical vapor deposition

Microwave plasma-enhanced chemical vapor deposition (MW-PECVD) has been employed to synthesize carbon nanostructures by using Fe (or Co, Ni)/γ-Al₂O₃ as catalysts and a mixture of benzene, hydrogen, and argon as precursors. By regulating the types of catalyst, the microwave incident power, the ratio and flux of the precursors, many morphologies such as ordinary geometric, helix-shaped, and planar spiral carbon nanotubes with aspect ratios of 100–1000 have been observed. Furthermore, two novel nanostructures, which are probably the missing link between onion-like carbon particles and nanotubes, have also been obtained. The striking feature of this new approach is the low synthesis temperature (<520°C) due to the non-equilibrium characteristic of microwave plasma operated at low pressure, which is crucial for some fascinating applications.     

Formation of multi-walled carbon nanotubes with a metal-free chemical vapor deposition and their stepwise evolution

Multi-walled carbon nanotubes and one-dimensional wire-like nanostructures have been synthesized using acetylene as carbon sources with a metal-free mild chemical vapor deposition process. It shows that anisotropic carbon nanostructures can interact to form nanotubes by self-function. Furthermore, the detailed microscopic observation of the obtained nanostructures indicates that the development of fully hollow carbon nanotubes should undergo a quite complex physical and chemical transformation process, and their formation abides by the “particle-wire-tube” stepwise evolution mechanism. In this process, the one-dimensional wire-like nanostructures can be viewed as the intermediate stages of carbon nanotube formation, which record traces about nanotube evolution.     

三维炭纤维预型体上烷烃气的催化炭沉积

研究了承载镍催化剂的三维(3D)炭纤维预型体,在含氢或无氢条件下,乙烷和合成天然气在其上面化学气相沉积形成的炭沉积率和碳纳米构结物.观察了炭沉积所获石墨纳米纤维、碳纳米管和石墨碳壳,得知沉积碳的纳米结构取决于沉积温度和碳源气组成.在650℃～800℃温间,总沉积时程直至12h,研究了烃类碳源气在氢气平衡下,从体积分数100%到20%变化情况.经Ni(NO3)2-6H2O甲醇溶液浸渍的3D炭纤维预型体在炭沉积前因溶液分解可还原出Ni.采用质量变化测定法、热谱-质谱分析仪、SEM、TEM和XRD对样品进行表征.结果表明:纤维状炭与囊包炭的比率随氢气含量的增加而增加,随反应温度的增高而减少.出乎意料的是,氢气的添加并不延长催化剂的寿命.该工艺过程对炭/炭复合材料的制备展示出良好的潜力.     

Effect of deposition pressure on the morphology and structural properties of carbon nanotubes synthesized by hot-filament chemical vapor deposition

Hot-filament chemical vapor deposition has developed into an attractive method for the synthesis of various carbon nanostructures, including carbon nanotubes. This is primarily due to its versatility, low cost, repeatability, up-scalability, and ease of production. The resulting nano-material synthesized by this technique is dependent on the deposition conditions which can be easily controlled. In this paper we report on the effect of the deposition pressure on the structural properties and morphology of carbon nanotubes synthesized by hot-filament chemical vapor deposition, using Raman spectroscopy and high-resolution scanning electron microscopy, respectively. A 10 nm-thick Ni layer, deposited on a SiO2/Si substrate, was used as catalyst for carbon nanotube growth. Multi-walled carbon nanotubes with diameters ranging from 20-100 nm were synthesized at 500 degrees C with high structural perfection at deposition pressures between 150 and 200 Torr. Raman spectroscopy measurements confirm that the carbon nanotube deposit is homogeneous across the entire substrate area.     

Multi-Wall Carbon Nanotubes/Styrene Butadiene Rubber (SBR) Nanocomposite

A floating catalyst chemical vapor deposition (FC-CVD) method was designed and fabricated to produce high-quality and -quantity carbon nanotubes. The design parameters like the hydrogen flow rate; reaction time and reaction temperature were optimized to produce high yield and purity of Multi-Wall Carbon Nanotubes (MWCNTs). Multi-Walled Carbon Nanotubes (MWNTs) were used to prepare natural rubber (NR) nanocomposites. Our first efforts to achieve nanostructures in MWNTs/styrene butadiene rubber (SBR) nanocomposites were formed by incorporating carbon nanotubes in a polymer solution and subsequently evaporating the solvent. Using this technique, nanotubes can be dispersed homogeneously in the NR matrix in an attempt to increase the mechanical properties of these nanocomposites. The properties of the nanocomposites such as tensile strength, tensile modulus, elongation at break and hardness were studied. Using different percentages of carbon nanotubes from 1 wt% to 10 wt%, several nanocomposites samples were fabricated. Significant improvements in the mechanical properties of the resulting nanocomposites showed almost 10% increase in the Young's modulus for 1 wt% of CNTs and up to around 200% increase for 10 wt% of CNTs.     

High-quality single-walled carbon nanotubes synthesis by hot filament CVD on Ru nanoparticle catalyst

We investigated the single-walled carbon nanotubes (SWCNTs) growth on Ru nanoparticle catalyst via hot filament assisted chemical vapor deposition (HFCVD) with two independent W filaments for the carbon precursor (methane) and the hydrogen dissociation respectively. The Ru nanoparticles were obtained following a two-step strategy. At first the growth substrate is functionalized by silanisation, then a self assembly of a ruthenium porphyrin complex monolayer on pyridine-functionalized metal oxide substrates. We have studied the impact of the filaments power and we optimized the SWCNTs growth temperature. The as grown SWCNTs were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and Raman spectroscopy. It was found that the quality, density and the diameter of SWCNTs depends on the filament and growth temperature. Results of this study can be used to improve the understanding of the growth of SWCNTs by HFCVD.     

Comparison of chemical vapor deposition and chemical grafting for improving the mechanical properties of carbon fiber/epoxy composites with multi-wall carbon nanotubes

By engineering the fiber/matrix interface, the properties of the composite can be changed significantly. In this work, we increased the effective surface area of the fiber/matrix interface, to facilitate additional stress transfer between fibers and matrix, by grafting carbon nanotubes on to carbon fibers (in the form of carbon fabric) by two different methods: (1) chemical vapor deposition (CVD) method and (2) a purely chemical method. With the CVD process, carbon nanotubes (CNT) were directly grown on carbon fiber substrate using chemical vapors. For the chemical method, CNT with carboxyl groups were grafted on functionalized carbon fiber via a chemical reaction. The morphology of CNT/carbon fibers was examined by scanning electron microscope (SEM) which revealed uniform coverage of carbon fibers with CNT in both of CVD method and chemical grafting method. CNT-grafted woven carbon fibers were used to make carbon/epoxy composites, and their mechanical properties were measured using three-point bending and tension tests which showed that those with CNT-grafted carbon fiber reinforcements using the CVD process has 11 % higher tensile strength compared to those containing carbon fibers modified with the chemical method. Also, composites with CNT-grafted carbon fibers with chemical method showed 20 % higher tensile strength compared to composites with unmodified carbon fibers. The results of tensile test revealed that both CVD and chemical grafting could significantly improve the mechanical properties of the carbon fiber composites.     

Effects of feed gas composition and catalyst thickness on carbon nanotube and nanofiber synthesis by plasma enhanced chemical vapor deposition

Many engineering applications require carbon nanotubes with specific characteristics such as wall structure, chirality and alignment. However, precise control of nanotube properties grown to application specifications remains a significant challenge. Plasma-enhanced chemical vapor deposition (PECVD) offers a variety of advantages in the synthesis of carbon nanotubes in that several important synthesis parameters can be controlled independently. This paper reports an experimental study of the effects of reacting gas composition (percentage methane in hydrogen) and catalyst film thickness on carbon nanotube (CNT) growth and a computational study of gas-phase composition for the inlet conditions of experimentally observed carbon nanotube growth using different chemical reaction mechanisms. The simulations seek to explain the observed effects of reacting gas composition and to identify the precursors for CNT formation. The experimental results indicate that gas-phase composition significantly affects the synthesized material, which is shown to be randomly aligned nanotube and nanofiber mats for relatively methane-rich inlet gas mixtures and non-tubular carbon for methane-lean incoming mixtures. The simulation results suggest that inlet methane-hydrogen mixture coverts to an acetylene-methane-hydrogen mixture with minor amounts of ethylene, hydrogen atom, and methyl radical. Acetylene appears to be the indicator species for solid carbon formation. The simulations also show that inlet methane-hydrogen mixture does not produce enough gas-phase precursors needed to form quality CNTs below 5% CH4 concentrations in the inlet stream.     

Synthesis of carbon coated silica nanowires

Carbon coated silica nanowire hybrid structures were directly synthesized by a chemical vapor deposition method using ethanol as the precursor. The morphology and structural properties of the nanostructures were investigated. It was found that, in the sample prepared at a relative lower temperature (1185 °C), the carbon shell was composed of orderly graphitic layers, whereas the carbon shell on those fabricated at higher temperature (1236 °C) was amorphous. Moreover, the thickness of the amorphous carbon shell increased with increasing reaction temperature and reaction time.