化学气相沉积工艺制备绳状纳米碳管的研究

用硝酸铁作催化剂,乙炔作碳源气体,高纯氮气作稀释气体,在750℃下化学气相沉积生长了绳状纳米碳管,用高分辨扫描电镜观察了所得绳状纳米碳管的形貌.纳米碳管的直径为100～200nm,长度为10～20 μm.文中还提出了绳状纳米碳管的生长机理.     

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.     

Temperature and time dependence study of single-walled carbon nanotube growth by catalytic chemical vapor deposition

The temperature and time dependence of single-walled carbon nanotube (SWCNT) growth by chemical vapor deposition of ethanol on Fe₂O₃/MgO catalyst are compared at both low (∼27 Pa) and atmospheric pressure limits. SWCNTs are synthesized in two reactors with different geometries and operating pressures and are characterized by Raman spectroscopy. Both reactors show SWCNT growth within a relatively narrow temperature window of 700-850 °C, with an optimum growth time of 35 min for the cold wall reactor and 75 min for the quartz tube reactor. A kinetic model comprising of ethanol decomposition, SWCNT formation, and water etching is developed to better understand the growth mechanism. The existence of a temperature window and an optimum growth time in both reactors can be well described by the kinetic model. Simulation results suggest that the temperature and time dependence can be explained by the competition between the growth of SWCNTs and that of amorphous carbon.     

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.     

Selective area synthesis of aligned carbon nanofibers by laser-assisted catalytic chemical vapor deposition

Arrays of freestanding bamboo-type carbon nanofibers were grown on the surface of a porous alumina substrate by laser-assisted catalytic chemical vapor deposition. A continuous wave argon ion laser operated at a wavelength of 488 nm was used to thermally decompose pure ethylene over nickel catalysts. Two different catalyst preparation methods were used and are compared with respect to the synthesis of aligned nanofibers. First, a thin nickel film (50 nm) was evaporated on the substrate and was subsequently laser annealed into nanoparticles. This preparation produced non-aligned nanofiber films. Second, a 50 nm thick catalyst layer was electrochemically deposited within the pores of an alumina substrate. This preparation produced an array of vertically aligned nanofibers. A growth rate dependence on radial position within the irradiated area was observed. Average linear growth rates ranging from 554 nm/s to 25 μm/s are reported. The nanofibers were examined by scanning electron microscopy and Raman spectroscopy. Fiber texture and nanotexture were determined by lattice fringe analysis from high resolution transmission electron microscopy images. The alignment mechanism is also discussed.     

Parametric study for the growth of carbon nanotubes by catalytic chemical vapor deposition in a fluidized bed reactor

Multiwalled carbon nanotubes have been produced from H₂-C₂H₄ mixtures on Fe-SiO₂ catalysts by a fluidized bed catalytic chemical vapor deposition process. Various parameters such as the catalyst preparation, the residence time, the run duration, the temperature, the H₂:C₂H₄ ratio, the amount of metal deposited on the support have been examined. The influence of these parameters on the deposited carbon yield is reported, together with observations of the produced material. This process allows an homogeneously distributed deposition of nanotubes (10-20 nm diameter), that remain anchored to the support.     

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.     

Effect of catalyst particle interspacing on the growth of millimeter-scale carbon nanotube arrays by catalytic chemical vapor deposition

Vertically aligned millimeter-scale carbon nanotube (CNT) arrays have been successfully deposited on both Fe(3 nm)/Al₂O₃ and Fe(1 nm)/Al₂O₃ catalyst films under different optimum pretreatment conditions by catalytic chemical vapor deposition. By investigating the catalyst particles before CNT array growth, it has been found that inter-particle spacing plays a significant role in influencing CNT array height, CNT diameter and wall number in the present study. The growth kinetics of CNT arrays grown from the two catalyst films with different pretreatment conditions demonstrates a competitive lengthening-thickening process. Based on the kinetics studies, it has been proved that inter-particle spacing affects the CNT array height by affecting their lengthening time, and accordingly affects the diameter and wall number of CNTs because of the concurrent change in the thickening time.     

Dynamics of catalyst particle formation and multi-walled carbon nanotube growth in aerosol-assisted catalytic chemical vapor deposition

In aerosol-assisted catalytic chemical vapor deposition (CCVD), the catalyst and carbon precursors are introduced simultaneously in the reactor. Catalyst particles are formed in situ and aligned multi-walled CNTs grow at a high rate. To scale-up the process, it is crucial to understand the chemical transformation of the precursors along the thermal gradient of the reactor, and to correlate nanotube growth with catalyst nanoparticle formation. The products synthesized along a cylindrical CVD reactor from an aerosol composed of ferrocene and toluene, as catalyst and carbon precursor, respectively, were studied. The product surface density and iron content are determined as a function of the location and the iron vapor pressure in the reactor. Samples are analyzed by electron microscopy, X-ray diffraction and Raman spectroscopy. We show the strong influence of the thermal gradient on location and rate of formation of both iron particles and CNTs, and demonstrate that catalyst particles are formed by gas phase homogeneous nucleation with a size which correlates with iron vapor pressure. They are gradually deposited on the reactor walls where nanotubes grow with an efficiency which is varying linearly with catalyst particle density. CNT crystallinity appears very high for a large range of temperature and iron content.     

Continuous synthesis of carbon spheres by a non-catalyst vertical chemical vapor deposition

High-purity carbon spheres were continuously produced by pyrolysis of acetylene at 1000 °C under a nitrogen atmosphere in a vertical chemical vapor deposition reactor. The produced carbon spheres had diameters in the range of 200–500 nm and were perfectly spherical in shape with rough surfaces. High resolution transmission electron microscopy analysis revealed that the carbon spheres were constructed of heavily distorted graphene layers. The results of the X-ray diffraction pattern and Raman spectra also confirmed that the presence of disordered graphene layers was due to a low graphitization degree. In addition, thermal stability and thermal oxidation of carbon spheres were studied. The results found that the surface of the carbon spheres could be modified and the amount of oxygen-containing functional groups increased after oxidation. In summary, the method provided a catalyst-free, substrate-free, hydrogen-free, and cost-effective synthesis for continuous production of carbon spheres.     

Chemical kinetics of catalytic chemical vapor deposition of an acetylene/xylene mixture for improved carbon nanotube production

Carbon nanotubes (CNTs) are synthesized by catalytic chemical vapor deposition (CCVD) from xylene, acetylene and their mixture. The addition of acetylene significantly increases the decomposition rate of xylene and decreases the benzene concentration in the effluent gas, as well as improving the quality of the CNTs obtained. There is a strong interaction between acetylene and xylene during the CCVD process. Various chemical components at different positions of the CVD reactor are classified and identified by mass spectrometry. Reaction kinetics constants are determined numerically based on the in situ measurement. Chemical kinetics of CCVD process is analyzed based on a detailed mechanism (88 species and 322 reactions), which successfully demonstrates the decomposition of the used carbon sources, and the synergistic effect of the addition of acetylene. The generation of hexagonal carbon rings from the dehydrogenation of benzene rings is described and discussed combined with the formation of CNT structures.     

One-step growth of graphene–carbon nanotube hybrid materials by chemical vapor deposition

Graphene–carbon nanotube (CNT) hybrid materials were synthesized by simple one-step chemical vapor deposition (CVD) using ethanol as precursor. On a copper foil decorated with silicon nanparticles (Si NPs), a graphene film grows uniformly on the substrate while CNTs sprout out from Si NPs to form a network on top. The density of CNTs can be controlled by the CVD growth temperature. As measured by scanning and transmission electron microscopy, the obtained CNTs exhibit bamboo-like multiple-wall structures. Electrical characterization shows that the graphene–CNT hybrids exhibit p-type field-effect characteristics and a significantly higher conductivity compared to a CVD grown pure graphene film.     

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.     

The effect of substrate positions in chemical vapor deposition reactor on the growth of carbon nanotube arrays

The effect of substrate positions inside the chemical vapor deposition reactor on the length and quality of the grown carbon nanotube (CNT) arrays is reported. It was found that longer CNT arrays are grown when located downstream on the platform in the reactor. This effect becomes more pronounced for increased growth time. Related factors such as temperature of the gas mixture and its flow velocity seem to be responsible for the behavior. The quality of the CNTs is not affected by the position of the substrates inside the reactor.     

A CFD study on a vertical chemical vapor deposition reactor for growing carbon nanofibers

A computational fluid dynamic (CFD) study has been carried out to simulate velocity, temperature, and concentration profiles in a vertical chemical vapor deposition (CVD) reactor used for growing carbon nanofibers (CNFs). CNFs were grown over activated carbon fibers (ACFs) wrapped over an especially designed perforated tube which was vertically mounted in the reactor. The numerical model analysis incorporated the conservation equations of momentum, energy, and species. Natural convection effects on the heat-transfer and the exothermic heat generation due to the decomposition of benzene were included. The model simulation results revealed that approximately uniform temperature and concentration profiles existed in the ACF-packed bed. In addition, multiple combinations of the heating length and the wall temperature of the reactor were possible to achieve the prescribed CVD temperature. Under the simulated CVD conditions, the present model predicted an average carbon deposition rate of 5 × 10⁻¹³ kg/m² s, which corresponded to the yield of ∼0.005 g of CNFs per g of ACFs. The simulation results of this study are important for the optimization of the CVD operating conditions to achieve a high and uniform CNF growth in the vertical reactor.     

Synthesis of oriented nanotube films by chemical vapor deposition

Oriented nanotube films (20-35 μm thick) were synthesised on flat silicon substrates by chemical vapor deposition (CVD) of a gas mixture of acetylene and nitrogen. For the CVD we used metal oxide clusters formed by spin coating an iron(III) nitrate ethanol solution onto a silicon substrate and subsequent heating. The cluster density and its effects on the nanotube density were investigated as a function of the iron(III) nitrate concentration and the synthesis temperature. A high nanotube density was achieved with a high density of iron oxide clusters as nucleation centres for the growth of nanotubes. The cluster density was controlled by the iron(III) concentration of the ethanolic coating solution and by the synthesis temperature. The perpendicular orientation of the nanotubes with respect to the substrate surface is attributed to a high density of nanotubes.