A chemical kinetic model for chemical vapor deposition of carbon nanotubes

Carbon nanotubes (CNTs) are classified among the most promising novel materials due to their exceptional physical properties. Still, optimal fabrication of carbon nanotubes involves a number of challenges. Whatever be the fabrication method, a process optimization can be evolved only on the basis of a good theoretical model to predict the parametric influences on the final product. The work reported here investigates the dependence of the deposition parameters on the controllable parameters for carbon nanotube growth during Chemical vapor deposition (CVD), through a chemical kinetic model. The theoretical model consisted of the design equations and the energy balance equations, based on the reaction kinetics, for the plug flow and the batch reactor, which simulate the CVD system. The numerical simulation code was developed in-house in a g++ environment. The results predicted the growth conditions for CNT: the deposition temperature, pressure and number of atoms, which were found to be influenced substantially by the initial controllable parameters namely the temperature, volumetric flow rate of the carbon precursor, and the reaction time. An experimental study was also conducted on a CVD system developed in the laboratory, to benchmark the computational results. The experimental results were found to agree well with the theoretical predictions obtained from the model.     

Preparation of carbon nanosheets deposited on carbon nanotubes by microwave plasma-enhanced chemical vapor deposition method

Carbon nanosheets were synthesized by microwave plasma-enhanced chemical vapor deposition method on carbon nanotubes substrate which was treated by hydrogen plasma. The results showed that the diameters of carbon nanotubes first got thick and then “petal-like” carbon nanosheets were grown on the outer wall of carbon nanotubes. The diameters of carbon nanotubes without and with carbon nanosheets were 100-150 and 300-500 nm, respectively. Raman spectrum indicated the graphite structure of carbon nanotubes/carbon nanosheets. The hydrogen plasma treatment and reaction time greatly affected the growth and density of carbon nanosheets. Based on above results, carbon nanosheets/carbon nanotubes probably have important applications as cold cathode materials and electrode materials.     

Individuals, grasses, and forests of single- and multi-walled carbon nanotubes grown by supported Co catalysts of different nominal thicknesses

The relationships among the nominal thickness of Co catalyst, the structure of the catalyst particles, and the structure of carbon nanotubes (CNTs) growing from the catalyst during chemical vapor deposition were investigated. Various morphologies of CNTs such as individuals, random networks parallel to the surface of the substrate (‘grasses’), and vertically aligned forests of single- and multi-walled carbon nanotubes were grown by only varying the nominal thickness of catalyst under the same reaction condition. These different morphologies at the same growth time were due to the different areal density rather than to the length of CNTs. With increasing nominal thickness of catalyst, the catalyst particles changed in diameter while their areal density remained relatively almost constant. The change in diameter possibly affected the number ratio of active catalyst particles to the whole particles, which in turn affected the areal density of CNTs and yielded the various morphologies. Longer growth time increased the CNT length, which caused further change in CNT morphologies from individuals to grasses and grasses to forests.     

Synthesis of multi-wall carbon nanotubes by the pyrolysis of ethanol on Fe/MCM-41 mesoporous molecular sieves

Ordered hexagonal arrangement MCM-41 mesoporous molecular sieves were synthesized by the traditional hydrothermal method, and Fe-loaded MCM-41 mesoporous molecular sieves (Fe/MCM-41) were prepared by the wet impregnation method. Their mesoporous structures were testified by X-ray diffraction (XRD) and the N₂ physical adsorption technique. Carbon nanotubes (CNTs) were synthesized by the chemical vapor deposition (CVD) method via the pyrolysis of ethanol at atmospheric pressure using Fe/MCM-41 as a catalytic template. The effect of different reaction temperatures ranging from 600 to 800 ^°C on the formation of CNTs was investigated. The resulting carbon materials were characterized by various physicochemical techniques such as transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The results show that multi-wall carbon nanotubes (MWCNTs) with an internal diameter of ca. 7.7 nm and an external diameter of ca. 16.9 nm were successfully obtained by the pyrolysis of ethanol at 800 ^°C utilizing Fe/MCM-41 as a catalytic template.     

Growth of single wall carbon nanotubes using PECVD technique: An efficient chemiresistor gas sensor

In this work, the uniform and vertically aligned single wall carbon nanotubes (SWCNTs) have been grown on Iron (Fe) deposited Silicon (Si) substrate by plasma enhanced chemical vapor deposition (PECVD) technique at very low temperature of 550 °C. The as-grown samples of SWCNTS were characterized by field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM) and Raman spectrometer. SWCNT based chemiresistor gas sensing device was fabricated by making the proper gold contacts on the as-grown SWCNTs. The electrical conductance and sensor response of grown SWCNTs have been investigated. The fabricated SWCNT sensor was exposed to ammonia (NH₃) gas at 200 ppm in a self assembled apparatus. The sensor response was measured at room temperature which was discussed in terms of adsorption of NH₃ gas molecules on the surface of SWCNTs. The achieved results are used to develope a miniaturized gas sensor device for monitoring and control of environment pollutants.     

The influence of treatment duration on multi-walled carbon nanotubes functionalized by H2SO4/HNO3 oxidation

Variation in the nature of multi-walled carbon nanotubes (MWCNTs) subjected to different degrees of oxidation was investigated. The microstructure was determined by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) methods, and the surface chemistry was evaluated in terms of the functional groups determined by X-ray photoelectron spectroscopy (XPS) and thermal analysis-mass spectroscopy (TA-MS). In addition, TGA was used to indicate the thermal stability of the nanotubes. Results demonstrate that the graphitic structure of nanotubes oxidized with a mild mixture of H₂SO₄/HNO₃ was preserved. Decrease in the degree of crystallinity started with widening of the C(0 0 2) XRD diffraction peak, followed by this peak shifting towards lower angles. The oxygen content increased with increasing treatment time. A defect peak incorporated in deconvolution of XPS C1s spectra was helpful for detecting the generation of defect sites. The predominant surface functionalities of the nanotubes have been changed from basic to acidic groups after treatment for one day. The samples oxidized for two days had the most abundant surface -COOH and the highest oxidation resistance. The oxidation mechanism of MWCNTs in mild H₂SO₄/HNO₃ mixture was proposed, which was a successive and iterative process, including the initial attack on active sites, and next the hexagon electrophilic attack generating new defects and introducing more oxygen, and then the tubes becoming thinner and shorter.     

Nitrogen-doped carbon nanotubes with tunable structure and high yield produced by ultrasonic spray pyrolysis

Nitrogen-doped carbon nanotubes (CN_x) were prepared by ultrasonic spray pyrolysis from mixtures of imidazole and acetonitrile. Imidazole, as an additive, was used to control the structure and nitrogen doping in CN_x by adjusting its concentration in the mixtures. Scanning electron microscopy observation showed that the addition of imidazole increased the nanotube growth rate and yield, while decreased the nanotube diameter. Transmission electron microscopy study indicated that the addition of imidazole promoted the formation of a dense bamboo-like structure in CN_x. X-ray photoelectron spectroscopy analysis demonstrated that the nitrogen content varied from 3.2 to 5.2 at.% in CN_x obtained with different imidazole concentrations. Raman spectra study showed that the intensity ratio of D to G bands gradually increased, while that of 2D to G bands decreased, due to increasing imidazole concentration. The yield of CN_x made from mixtures of imidazole and acetonitrile can reach 192 mg in 24 min, which is 15 times that of CN_x prepared from only acetonitrile. The aligned CN_x, with controlled nitrogen doping, tunable structure and high yield, may find applications in developing non-noble catalysts and novel catalyst supports for fuel cells.     

Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

The Co Mg O and Co Mn Mg O catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes（CNTs） through the catalytic chemical vapor deposition（CCVD）. The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction（TPR） and X-ray diffraction（XRD） techniques, and the synthesized carbon materials are characterized by transmission electron microscopy（TEM） and thermo gravimetric analysis（TG）. TEM measurement indicates that the catalyst Co Mg O enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the Co Mn Mg O catalyst has a higher selectivity for CNTs than Co Mg O. Meanwhile, different diameters of CNTs are synthesized by Co Mn Mg O catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution.The Co Mn Mg O catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.     

Surface modification of multi-walled carbon nanotubes by O2 plasma

The surface modification of multi-walled carbon nanotubes (MWCNTs) by O₂ plasma was carried out in this study. In order to achieve a relatively homogeneous treatment of MWCNTs powder, a rotating barrel fixed between the two discharge electrodes was used. The effect of plasma treatment parameters, such as power, time, and positions of samples (inside and outside the barrel), on the morphology and structure of MWCNTs surface was systematically analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The results showed that the direct discharge (outside the barrel) could result in not only a quick grafting of polar functional groups but also an easy damage of MWCNTs after longer time, particularly under intensive power. It was found that the surface of MWCNTs powder might be changed in three steps—expansion (loosed structure formed), peel off and oxidization with increasing of treatment time during the irradiation. In this way, a complete purification of MWCNTs powder could be finished within 30 min via plasma treatment. Our work suggested that plasma treatment could be a simple and nonpolluting method for a large scale purification of MWCNTs.     

Hydrogen-free spray pyrolysis chemical vapor deposition method for the carbon nanotube growth: Parametric studies

Spray pyrolysis chemical vapor deposition (CVD) in the absence of hydrogen at low carrier gas flow rates has been used for the growth of carbon nanotubes (CNTs). A parametric study of the carbon nanotube growth has been conducted by optimizing various parameters such as temperature, injection speed, precursor volume, and catalyst concentration. Experimental observations and characterizations reveal that the growth rate, size and quality of the carbon nanotubes are significantly dependent on the reaction parameters. Scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy techniques were employed to characterize the morphology, structure and crystallinity of the carbon nanotubes. The synthesis process can be applied to both semiconducting silicon wafer and conducting substrates such as carbon microfibers and stainless steel plates. This approach promises great potential in building various nanodevices with different electron conducting requirements. In addition, the absence of hydrogen as a carrier gas and the relatively low synthesis temperature (typically 750 °C) qualify the spray pyrolysis CVD method as a safe and easy way to scale up the CNT growth, which is applicable in industrial production.     

Synthesis of superconductor MgCNi3 with carbon nanotubes

MgCNi3, an intermetallic compound superconductor with a cubic perovskite crystal structure, has been synthesized using fine Mg and Ni powders and carbon nanotubes （CNTs） as starting materials by the conventional powder metallurgy method. The composition, microstructure and superconductivity are characterized using x-ray diffraction （XRD）, energy dispersive x-ray （EDX） analysis, scanning electron microscopy （SEM）, and superconducting quantum interference device （SQUID） magnetometer. The results indicate that the phases of the synthesized samples are MgCNi3 （major phase） and traces of C and MgO. The MgCNi3 particle sizes range from several hundreds of nanometres to several micrometres. The onset superconducting transition temperature Tc of the MgCNi3 sample is about 7.2 K. The critical current density Jc is about 3.44 × 10^4 A/cm^2 calculated according to the Bean model from the magnetization hysteresis loop of the slab MgCNi3 sample at 5 K and zero applied field.     

Preparation and characterization of amphiphilic multi-walled carbon nanotubes

Multiwalled carbon nanotubes (MWCNTs, average diameter 8 nm) functionalized by N-vinyl pyrrolidone (NVP) were synthesized by radical polymerization and characterized by Fourier transform infrared and Raman spectroscopies, thermogravimetric analysis and transmission electron microscopy. These NVP–MWCNTs exhibit remarkable solubility in water, ethanol and dimethyl formamide. The polyvinyl pyrrolidone can be attached onto the surface of the MWCNTs and the degree of functionalization is affected by NVP content. The functionalization causes possible grafting reaction and solid physical coating between MWCNTs and PVP.     

Impact of Mo and Ce on growth of single-walled carbon nanotubes by chemical vapour deposition using MgO-supported Fe catalysts

A series of nine catalysts containing Ce/Fe and Mo/Fe at various loadings on MgO supports have been studied as catalysts for chemical vapour deposition (CVD) of single-walled carbon nanotubes (SWCNTs) using a methane carbon source. Our results show that the Ce/Fe system is very suitable as a catalyst that favours SWCNT growth, and we question the special importance that has been attributed to Mo as an additive to Fe-based catalysts for SWCNT growth, as it appears that Ce is equally effective. Our results indicate that dehydroaromatization (DHA) is not a defining step for the growth mechanism, as has been suggested for Mo/Fe systems previously, and show that Ce and Mo do not seriously perturb the well-known Fe/MgO system for growth of high quality SWCNT. Using Raman spectroscopy, we have shown that the Ce/Fe/MgO catalyst system favours growth of SWCNTs with a different distribution of chiralities compared to the analogous Mo/Fe/MgO system.     

Growth of carbon nanotubes by Fe-catalyzed chemical vapor processes on silicon-based substrates

In this paper, a site-selective catalytic chemical vapor deposition synthesis of carbon nanotubes on silicon-based substrates has been developed in order to get horizontally oriented nanotubes for field effect transistors and other electronic devices. Properly micro-fabricated silicon oxide and polysilicon structures have been used as substrates. Iron nanoparticles have been obtained both from a thin Fe film evaporated by e-gun and from iron nitrate solutions accurately dispersed on the substrates. Single-walled nanotubes with diameters as small as 1 nm, bridging polysilicon and silicon dioxide “pillars”, have been grown. The morphology and structure of CNTs have been characterized by SEM, AFM and Raman spectroscopy.     

Influence of DC electric field on the Lennard-Jones potential and phonon vibrations of carbon nanotube on catalyst

Influence of DC electric field on carbon nanotube (CNT) growth in chemical vapor deposition is studied. Investigation of electric field effect in van der Waals interaction shows that increase in DC electric field raises the magnitude of attractive term of the Lennard-Jones potential. By using a theoretical model based on phonon vibrations of CNT on catalyst, it is shown that there is an optimum field for growth. Also it is observed that CNT under optimum electric field is longer than CNT in the absence of field. Finally, the relation between optimum DC electric field and type of catalyst is investigated and for some intervals of electric field, the best catalyst is introduced, which is very useful for experimental researches.     

Surface modification of pitch-based spherical activated carbon by CVD of NH3 to improve its adsorption to uric acid

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH₃ (NH₃-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N₂ adsorption, pH_PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH₃-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH₃-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH_PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.     

Electron diffraction on graphite nanocrystals in the walls of carbon nanotubes

The structure and defects in the walls and cavities of carbon nanotubes were examined by electron diffraction, transmission electron microscopy, energy dispersive X-ray analysis and Raman spectroscopy. The predominating defects in the walls of the nanotubes are graphite nanocrystals having a preferential orientation in the direction of the nanotube axis, and another significant type of defects are particles of the catalyst in the nanotube cavities. In the cavities, also the presence of molybdenum was proved having its origin in the catalyst.     

Controllable growth of individual, uniform carbon nanotubes by thermal chemical vapor deposition

We report on the controllable growth of individual, uniform carbon nanotubes using thermal chemical vapor deposition (CVD). We performed a detailed study of the various factors influencing the growth of single nanotubes. In particular, we investigated the role played by catalyst layer thickness, catalyst dot size, deposition temperature, and gas source pressure on the growth process of straight, single nanotubes. Straight, individual nanotubes with uniform diameter can be obtained by decomposition of 0.1 mbar of acetylene at a temperature of 800 °C over a 5 nm thick nickel film that is patterned into square dots with dimensions below 500 nm. We compare the performance of thermal CVD and of plasma enhanced CVD for growing individual nanotubes.     

A novel carbon nanotubes/Fe3O4 inorganic hybrid material: Synthesis, characterization and microwave electromagnetic properties

Magnetite particles with nanoscale sizes were self-assembled along multiwalled carbon nanotubes through a simple, effective and reproducible solvothermal method. The morphology, composition and phase structure of as-prepared hybrid materials were characterized by scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The results showed that denseness, size and crystallinity of magnetite can be altered by controlling the reaction parameters. Magnetization measurement indicated that both coercivity and saturation magnetization increased linearly with increasing magnetite concentration in the hybrid materials. Electromagnetic properties of the carbon nanotubes/magnetite inorganic hybrid materials were measured at 1∼18 GHz. The magnetic loss was caused mainly by ferromagnetic natural resonance, which is in agreement with the Kittel equation. The as-prepared inorganic hybrid materials are believed to have potential applications in the microwave absorbing area.