Direct synthesis of fullerene-intercalated porous carbon nanofibers by chemical vapor deposition

Hybrid structures combining fullerenes and carbon nanotubes have exhibited exciting properties. However, the low efficiency and complex process of such assembly restrict their practical applications. We report a single-step procedure to synthesize the fullerene-intercalated (including endohedral metallofullerene (Y@Cn)) porous carbon nanofibers (pCNFs) by chemical vapor deposition (CVD) using a Fe/Y catalyst on a copper substrate. Fullerenes were simultaneously synthesized with the pCNF growth during the CVD process. Instead of attaching them on the surface of the CNFs, the fullerenes were inserted in the graphitic interlayer spacing, inducing micro- and mesopores in CNFs. The growth mechanism of the fullerene-intercalated pCNFs was discussed.     

Mass production of aligned carbon nanotube arrays by fluidized bed catalytic chemical vapor deposition

A parametric study investigating the impacts of loading amount of active phase, growth temperature, H₂ reduction, space velocity, and apparent gas velocity on the intercalated growth of vertically aligned carbon nanotube (CNT) arrays among lamellar catalyst was performed. A series of Fe/Mo/vermiculite catalysts with Fe/vermiculite ratio of 0.0075-0.300 were tested. Metal particles were dispersed among the layers of vermiculite after H₂ reduction. Uniform catalyst particles, with a size of 10-20 nm and a density of 8.5 × 10¹⁴ m⁻², were formed among the vermiculite layers at 650 °C. CNTs with high density synchronously grew into arrays among the vermiculites. With the increasing growth temperature, the alignment of CNTs intercalated among vermiculites became worse. Moreover, intercalated CNTs were synthesized among vermiculite layers in various flow regimes. The as-grown particles were with a size of 1-2 mm when the fluidized bed reactor was operated in particulate fluidization and bubbling fluidization, while the size of the as-grown products decreased obviously when they grown in the turbulent fluidized bed. Based on the understanding of the various parameters investigated, 3.0 kg/h of CNT arrays were mass produced in a pilot plant fluidized bed reactor.     

Growth of aligned millimeter-long carbon nanotube by chemical vapor deposition

Carbon nanotubes (CNTs) of millimeters in length have been grown by an atmospherical pressure thermal Chemical Vapor Deposition (CVD). The experimental parameters controlling the growth have been systematically studied. Growth mechanism is investigated by TEM and a pulsed growth technique. Growth kinetics is revealed by studying time dependence of CNT length. We discuss that our high CNT yield is achieved by a combination of intermediate growth rate and long catalyst lifetime.     

Micromechanical testing of carbon fibers deposited by low-pressure laser-assisted chemical vapor deposition

Carbon fibers were deposited directly from ethylene by laser-assisted chemical vapor deposition. The precursor gas pressures and the incident laser powers were varied. Micro-mechanical testing was carried out using a high-precision micro-manipulator. During three-point bend testing the fibers showed an elastic response, with no residual strain upon unloading, until fracture. The fibers’ strength and Young’s modulus are reported. A model for fiber fracture is proposed based on fiber cross-section analysis. Scanning electron microscopy was used to study the fiber cross-sections and the fiber surface morphology. The mechanical properties are related to the characteristic fiber microstructure investigated by Raman spectroscopy.     

Low temperature growth mechanisms of vertically aligned carbon nanofibers and nanotubes by radio frequency-plasma enhanced chemical vapor deposition

Using radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD), carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were synthesized at low temperature. Base growth vertical turbostratic CNFs were grown using a sputtered 8 nm Ni thin film catalyst on Si substrates at 140 °C. Tip growth vertical platelet nanofibers were grown using a Ni nanocatalyst in 8 nm Ni films on TiN/Si at 180 °C. Using a Ni catalyst on glass substrate at 180 °C a transformation of the structure from CNFs to CNTs was observed. By adding hydrogen, tip growth vertical multi-walled carbon nanotubes were produced at 180 °C using FeNi nanocatalyst in 8 nm FeNi films on glass substrates. Compared to the most widely used thermal CVD method, in which the synthesis temperature was 400–850 °C, RF-PECVD had a huge advantage in low temperature growth and control of other deposition parameters. Despite significant progress in CNT synthesis by PECVD, the low temperature growth mechanisms are not clearly understood. Here, low temperature growth mechanisms of CNFs and CNTs in RF-PECVD are discussed based on plasma physics and chemistry, catalyst, substrate characteristics, temperature, and type of gas.     

化学气相催化热解法制备螺旋纳米碳纤维

采用酒石酸铜前驱体热分解得到纳米铜粒子作为催化剂,分别对250℃、280℃、310℃分解产生的纳米铜粒子进行测试分析,在3个温度下用化学气相沉积法生长螺旋纳米碳纤维并进行综合热分析。采用X-射线衍射(XRD)分析其物相组成,晶粒大小;用扫描电子显微镜(SEM)观察螺旋纳米纤维的外观形貌。结果表明,310℃生长出的螺旋纳米碳纤维纯度高、外观形貌清晰,热分析质量损失少。     

Local chemical vapor deposition of carbon nanofibers from photoresist

The addition of nanofeatures to carbon microelectromechanical system (C-MEMS) structures would greatly increase surface area and enhance their performance in miniature batteries, super-capacitors, electrochemical and biological sensors. Negative photoresist posts were patterned on a Au/Ti contact layer by photolithography. After pyrolyzing the photoresist patterns to carbon patterns, graphitic nanofibers were observed near the contact layer. The incorporation of carbon nanofibers in C-MEMS structures via a simple pyrolysis of modified photoresist was investigated. Both experimental results considered to consist of a local chemical vapor deposition mechanism. The method represents a novel, elegant and inexpensive way to equip carbon microfeatures with nanostructures, in a process that could possibly be scaled up to the mass production of many electronic and biological devices.     

Vertically aligned carbon nanotube arrays grown on a lamellar catalyst by fluidized bed catalytic chemical vapor deposition

Large amount of vertically aligned carbon nanotube (CNT) arrays were grown among the layers of vermiculite in a fluidized bed reactor. The vermiculite, which was 100-300 μm in diameter and merely 50-100 μm thick, served as catalyst carrier. The Fe/Mo active phase was randomly distributed among the layers of vermiculite. The catalyst shows good fluidization characteristics, and can easily be fluidized in the reactor within a large range of gas velocities. When ethylene is used as carbon source, CNT arrays with a relatively uniform length and CNT diameter can be synthesized. The CNTs in the arrays are with an inner diameter of 3-6 nm, an outer diameter of 7-12 nm, and a length of up to several tens of micrometers. The as-grown CNTs possess good alignment and exhibit a purity of ca. 84%. Unlike CNT arrays grown on a plane or spherical substrate, the CNT arrays grown in the fluidized bed remain their particle morphologies with a size of 50-300 μm and the good fluidization characteristics were preserved accordingly.     

Temperature gradient chemical vapor deposition of vertically aligned carbon nanotubes

We present temperature gradient chemical vapor deposition (TG CVD) for producing vertically aligned (VA-) carbon nanotubes (CNTs). Independent heaters on the gas inlet and catalyst substrate sides of a cold-wall, vertical CVD reactor can modulate the gas temperature gradient to lead to controlled thermal histories of acetylene precursor. Our growth results reveal that such a precursor thermal history can play a significant role in the growth and structural features of the resultant VA-CNTs. We find several gas thermal zones particularly important to the VA-CNT growth by evaluating the precursor dwell time in different zones. Thermal treatment of the acetylene precursor at 600–700 °C is found crucial for the synthesis of VA-CNTs. When this thermal zone is conjoined in particular with a zone >700 °C, efficient growths of single-walled and double-walled VA-CNTs can be achieved. These gas thermal zones can contribute to VA-CNT growths by mixing various secondary hydrocarbons with acetylene, corroborated by the results of our reacting flow simulation. Our findings emphasize the influence of gas-phase reactions on the VA-CNT growth and suggest that our TG CVD approach can be practically utilized to modulate complex gas-phase phenomena for the controlled growth of VA-CNTs.     

Bamboo-shaped carbon nanofibers obtained in pyrolytic carbon by thermal gradient chemical vapor deposition

Bamboo-shaped carbon nanofibers were obtained in pyrolytic carbon fabricated by thermal gradient chemical vapor deposition and their micro-and nanostructure were examined by transmission and scanning electron microscopy. The results showed that, bamboo-shaped nanofibers with diameters from a few tens to about 250 nm were distributed homogeneously in the pyrolytic carbon. The nanofibers could be pulled out of the pyrolytic carbon when they were fractured.     

Palladium catalyzed formation of carbon nanofibers by plasma enhanced chemical vapor deposition

A dc plasma enhanced chemical vapor deposition process is used to obtain vertically aligned carbon nanofibers (CNFs) from palladium catalysts using an ammonia-acetylene process gas mixture. Transmission electron microscopy is used to elucidate the microstructure of the as-grown fibers revealing different growth anomalies such as a new secondary growth phenomenon which we term hybrid tip growth. Also included in our analysis are conventional tip growth derived structures. In a few instances, the conventional tip growth derived structures possess elongated catalyst particles that impart small cone angles to the carbon nanofiber microstructure. Detailed microchemical analysis reveals that hybrid tip grown CNFs using thick Pd films are partially filled with Pd. Analysis of these growth phenomenon and implications for potential use as on-chip interconnects are discussed.     

Modeling of a continuous rotary reactor for carbon nanotube synthesis by catalytic chemical vapor deposition

The modeling of carbon nanotube production by the CCVD process in a continuous rotary reactor with mobile bed was performed according to a rigorous chemical reaction engineering approach. The geometric, hydrodynamic, physical and physicochemical factors governing the process were analyzed in order to establish the reactor equations. While the study of the hydrodynamic factor suggests a co‐current plug‐flow approximation, the physical factor mainly deals with the phenomena of transport and the transfer of mass, which can be neglected. Concerning the physicochemical factor, the modeling is based on knowledge of the expression of the initial reaction rate, and takes into account catalytic deactivation as a function of time, according to a sigmoid decreasing law. The reactor modeling allows obtaining the evolution of partial pressure, carbon nanotube production and catalytic deactivation along the reactor for given initial operating conditions. The comparison between experimental and calculated production highlights a very good fit of data. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Growth of mechanically fixed and isolated vertically aligned carbon nanotubes and nanofibers by DC plasma-enhanced hot filament chemical vapor deposition

Vertically aligned, mechanically isolated, multiwalled carbon nanotubes (MWCNTs) and nanofibers (MWCNFs) were grown using an array of catalyst nickel nanowires embedded in an anodic aluminum oxide (AAO) nanopore template using DC plasma-enhanced hot filament chemical vapor deposition (HFCVD). The nickel nanowire array, prepared by electrodeposition of nickel into the pores of a commercially available AAO membrane, acts as a template for CNT and CNF growth. It also provides both a mechanical “fixed support” boundary condition and enforces sufficient spatial separation of the CNT/CNFs from each other to enable reliable and well-controlled mechanical testing of individual vertically aligned CNT/CNFs. In contrast with other AAO-templated growth methods, no post-growth etching of the AAO is required, since the CNTs/CNFs grow out of the pores and remain vertically aligned. A mixture of hydrogen and methane was used for the growth, with hydrogen acting as a dilution and source gas for the DC plasma, and methane as the carbon source. A negative bias was applied to the sample mount to generate the DC plasma. The filaments provided the necessary heat for dissociation of molecular species, and also heat the sample itself significantly. Both of these effects assist the CNT/CNF growth. Minimal heating came from the low-power plasma. However, the associated DC field was essential for the vertical alignment of the CNTs and CNFs. Scanning electron, transmission electron, and atomic force microscopy confirm that the CNT/CNFs are composed of graphitic layers, and form a vertically aligned, relatively uniform, and dense array across the AAO template. A significant number of the structures grown are indeed high quality nanotubes, as opposed to more defective nanofibers that are often predominant in other growth methods. This method has the advantage of being scalable and consuming less power than other techniques that grow vertically aligned CNTs/CNFs.     

Fluidized bed catalytic chemical vapor deposition synthesis of carbon nanotubes—A review

Carbon nanotubes (CNTs) are pure carbon in nanostructures with unique physico-chemical properties. They have brought significant breakthroughs in different fields such as materials, electronic devices, energy storage, separation, sensors, etc. If the CNTs are ever to fulfill their promise as an engineering material, commercial production will be required. Catalytic chemical vapor deposition (CCVD) technique coupled with a suitable reactor is considered as a scalable and relatively low-cost process enabling to produce high yield CNTs. Recent advances on CCVD of CNTs have shown that fluidized-bed reactors have a great potential for commercial production of this valuable material. However, the dominating process parameters which impact upon the CNT nucleation and growth need to be understood to control product morphology, optimize process productivity and scale up the process. This paper discusses a general overview of the key parameters in the CVD formation of CNT. The focus will be then shifted to the fluidized bed reactors as an alternative for commercial production of CNTs.     

Cu-Ni composition gradient for the catalytic synthesis of vertically aligned carbon nanofibers

The influence of catalyst alloy composition on the growth of vertically aligned carbon nanofibers was studied using Cu-Ni thin films. Metals were co-sputtered onto a substrate to form a thin film alloy with a wide compositional gradient, as determined by Auger analysis. Carbon nanofibers were then grown from the gradient catalyst film by plasma enhanced chemical vapor deposition. The alloy composition produced substantial differences in the resulting nanofibers, which varied from branched structures at 81%Ni-19%Cu to high aspect ratio nanocones at 80%Cu-20%Ni. Electron microscopy and spectroscopy techniques also revealed segregation of the initial alloy catalyst particles at certain concentrations.     

Coiled carbon nanotubes growth via reduced-pressure catalytic chemical vapor deposition

Coiled carbon nanotubes were prepared by catalytic chemical vapor deposition (CCVD) on finely divided Co nano-particles supported on silica gel under reduced pressure and relatively low gas flow rates. The morphology and the graphitization of the coil tube, coil bend, and coil node of the coiled carbon nanotubes were examined by transmission electron microscope (TEM). The influence of pH value, reaction pressure, and flow rate of C₂H₂ on the growth of the coiled carbon nanotubes were also discussed. With the drastic reduction in the consumption of C₂H₂ and lower required pressure with the modified CCVD approach, the amount of amorphous carbon coated on the carbon nanotubes was shown to be greatly reduced. Most importantly, this method offers a preferable alternative for the efficient, environment-friendly and safer growth of coiled carbon nanotubes.