Studies on mechanism of single-walled carbon nanotube formation

We presented detailed studies of the formation of single-walled carbon nanotubes by an aerosol method based on the introduction of pre-formed catalyst particles into conditions leading to carbon nanotube synthesis. Carbon monoxide and iron nanoparticles were used as a carbon source and a catalyst, respectively. The vital role of etching agents such as CO2 and H2O in CNT formation was demonstrated on the basis of on-line Fourier-transform infrared spectroscopy measurements. Hydrogen was shown to participate in the reaction of carbon release and to prevent the oxidation of the catalyst particles and the hot wire. The addition of H2 and small amounts of CO2 and H2O led to an increase in the carbon nanotube lengths. The catalyst particle evaporation process inside the reactor was found to become significant at temperatures higher than 1100 degrees C. The carbon nanotube growth was found to occur at a temperature of around 900 degrees C in the heating section of the reactor by in situ sampling and the growth rate was calculated to exceed 1.1 microm/s. A detailed analysis of possible processes during carbon nanotube formation revealed heptagon transformation as a limiting stage. A mechanism for carbon nanotube formation was proposed.     

High-aligned carbon nanotube film with netlike bulges

High-aligned carbon nanotubes film with netlike bulges made of catalyst particles has been synthesized on a silica wafer by pyrolyzing ferrocene/melamine mixtures. The structure and composition of carbon nanotubes are investigated by scanning electron microscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electron energy-loss spectroscopy (EELS). It is found that these nanotubes have uniform outer diameters of about 25 nm and lengths of about 40 μm. High-resolution TEM images show that each carbon nanotube is composed of graphite-like layers arranged in a stacked-cup-like structure. XPS spectrum shows that the crust covering the tops of the aligned carbon nanotube film consists of carbon, iron and ferric oxide. The EELS spectrum shows that these nanotubes are pure-carbon tubes. The formation mechanism of the netlike bulges has been provided.     

堇青石载镍催化剂对燃烧合成碳纳米管的影响

借助于硝酸镍溶液, 利用浸渍法在堇青石表面均匀负载镍催化剂颗粒, 在甲烷扩散火焰中活化并催化生成碳纳米 管. 实验结果表明, 生成的多壁碳纳米管直径为30～50nm, 长度约为十几微米, 空腔比较小, 管壁石墨结晶结构良好.提高浸渍液浓度, 催化剂颗粒尺寸明显变大, 但对碳纳米管的形态影响比较小. 延长浸渍时间, 可使催化剂颗粒密度提高, 碳纳米管出现成束生长现象. 结合碳管成核生长过程和火焰燃烧的特点, 探讨了催化剂对于碳纳米管生长的影响机制.     

等离子体射流辅助双催化剂原位催化法合成碳纳米管

以甲烷为碳源，Fe2O3／Ni为固定相催化剂，在常压条件下利用等离子体射流的高温将甲烷裂解生成碳自由基和氢气。同时联合原位催化法将碳自由基在Fe2O3／Ni双催化剂的共同作用下生长出碳纳米管。运用TEM和元素分析等测试手段对所得碳纳米管进行形貌、含量、结构的表征分析。结果表明，在一定反应条件下，可获得外径为10nm-30nm，管长约数百纳米、产率为75％左右的碳纳米管。与单催化剂相比，双催化剂的联合催化作用更有利于碳管的生长。     

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.     

The effect of substrate morphology on the diameter distribution of carbon nanotubes grown on silica and ceramic substrates

Large-scale well-aligned carbon nanotube film and carbon nanotube bundles have been fabricated on smooth silica and rough polycrystalline ceramic substrates by pyrolysis of ferrocene/melamine mixtures. The images of transmission electron microscopy (TEM) and scanning electron microscope (SEM) show that carbon nanotubes grown on the silica substrate have uniform outer diameters of about ∼ 25 nm and lengths of about 40 μm, while those on the ceramic substrate have outer diameters from 10 to 90 nm and lengths up to 100 μm. Electron energy-loss spectroscopy (EELS) spectra show that nanotubes grown on the two different substrates are pure carbon tubes. The effects of substrate micro-morphologies on the diameters of carbon nanotubes have been discussed.     

Synthesis and electromagnetic wave absorption properties of multi-walled carbon nanotubes decorated by BaTiO3 nanoparticles

A hybrid composite material, consisting of BaTiO3 and multi-walled carbon nanotubes, was synthesized by an efficient solvent-thermal route. Transmission electron microscopy images clearly indicate that the surfaces of the multi-walled carbon nanotubes were uniformly decorated by well-crystallized BaTiO3 particles, with diameters of 15-30 nm. Electromagnetic wave absorption properties analysis, determined by the electromagnetic parameters measured by a vector network analyzer, shows that the reflection loss in the BaTiO3/multi-walled carbon nanotube composite was higher than that occurring in pure multi-walled carbon nanotubes or BaTiO3 and that was resulted from a better matched characteristic impedance and an enhanced complex permeability in the high frequency, which was improved by the decrease of eddy currents owing to the finite increase in resistivity. The maximum reflection loss of -37.5 dB in the BaTiO3/multi-walled carbon nanotube composite was obtained at a frequency of 10.4 GHz and the absorption range under -10 dB was from 9.6-13.1 GHz range as the absorber thickness was 2 mm.     

Nanocrystallized steel surface by micro-shot peening for catalyst-free carbon nanotube growth

Nanocrystallized steel surface by micro-shot peening (MSP) were applied to carbon nanotube growth in this study. Micro-shot peening treatment severely deformed steel surface and nanocrystallized surface layer was formed by the plastic deformation. The grain sizes of the nanocrystallized layer were 10-30 nm after 300 s of MSP treatment. On the nanocrystallized surface, carbon nanotubes were formed with thermal chemical vapour deposition without catalysts. Before carbon nanotube growth, the nanocrystallized steel surface was reduced with H₂/N₂ gas at 600 °C. The carbon nanotube growth was performed at 600 °C with C₂H₂ gas carried by H₂/N₂ gas. The carbon nanotubes formed on the nano-structured surface was multi-walled carbon nanotube and the diameter was 10-20 nm. The reduction process before carbon nanotube growth was essential to form carbon nanotubes on the nanocrystallized surface with MSP.     

Synthesis of carbon nanotube films by thermal CVD in the presence of supported catalyst particles. Part I: The silicon substrate/nanotube film interface

The interface between the silicon substrate and a carbon nanotube film grown by thermal CVD with acetylene (C₂H₂) and hydrogen at 750 or 900 °C has been characterized by high resolution and analytical transmission electron microscopy, including electron spectroscopic imaging. Silicon (0 0 2) substrates coated with a thin (2.8 nm) iron film were heat treated in the CVD furnace at the deposition temperature in a mixture of flowing argon and hydrogen whereby nanosized particles of (Fe,Si)₃O₄ formed. These particles were reduced to catalytic iron silicides with the –(Fe, Si), ₂–Fe₂Si and ₁–Fe₂Si structures during CVD at 900 °C, and multi-wall carbon nanotubes grew from supported particles via a base-growth mechanism. A limited number of intermediate iron carbides, hexagonal and orthorhombic Fe₇C₃, were also present on the substrate surface after CVD at 900 °C. The reduction of the preformed (Fe, Si)₃O₄ particles during thermal CVD at 750 °C was accompanied by disintegration leading to the formation of a number of smaller (<5 and up to 10 nm) iron and silicon containing particles. It is believed that the formation of these small particles is a prerequisite for the growth of aligned multi-wall carbon nanotube films.     

In situ nucleation of carbon nanotubes by the injection of carbon atoms into metal particles

The synthesis of carbon nanotubes (CNTs) of desired chiralities and diameters is one of the most important challenges in nanotube science and achieving such selectivity may require a detailed understanding of their growth mechanism. We report the formation of CNTs in an entirely condensed phase process that allows us, for the first time, to monitor the nucleation of a nanotube on the spherical surface of a metal particle. When multiwalled CNTs containing metal particle cores are irradiated with an electron beam, carbon from graphitic shells surrounding the metal particles is ingested into the body of the particle and subsequently emerges as single-walled nanotubes (SWNTs) or multiwalled nanotubes (MWNTs) inside the host nanotubes. These observations, at atomic resolution in an electron microscope, show that there is direct bonding between the tubes and the metal surface from which the tubes sprout and can be readily explained by bulk diffusion of carbon through the body of catalytic particles, with no evidence of surface diffusion.     

流动催化法连续制备碳纳米管及其形态和结构的研究

以二茂铁作为催化剂来源、以苯作为碳源、氢气和氩气分别作为载气和稀释气体,在１１００℃连续地合成了碳纳米管．碳纳米管的生成分二个过程：催化生长和表面无定形碳的生成．所得到的碳纳米管的内径为３～６ｎｍ,而外径约为２０～７０ｎｍ碳纳米管的外径随气体流速的增加而变细,在较细的碳纳米管中观察到了由催化生长而成的具有光滑薄壁的原始碳纳米管．生成的碳纳米管的长度达数十微米、直径较均匀,其端部大多为圆形,但也观察到其他的形状的端部．     

Synthesis of carbon nanotubes using Ni95Ti5 nanocrystalline film as a catalyst

Carbon nanotubes (CNTs) were synthesized by low-pressure chemical vapour deposition (LPCVD) using N2:C2H2:H2 gas mixtures on nanocrystalline Ni95Ti5 film. This nanocrystalline film was deposited on silicon substrate using vapour condensation method. The growth temperature and growth time was kept at 800 degrees C and 30 mins, respectively and the pressure was maintained at 10 Torr. The growth mechanism of CNTs was investigated using FESEM, TEM, HRTEM, and Raman Spectroscopy. From FESEM image of Ni95Ti5 nanocrystalline film, it is clear that the particle size varies from 5-10 nm. EDX analysis suggests that Ni95Ti5 alloy contains Ni and Ti both. It is clear from TEM images that CNTs are multiwalled with the diameter varying from 10-30 nm and length of several micrometers. HRTEM image shows that the structure of these multi-walled nanotube (MWNTs) is bamboo-shaped and the catalyst exists at the tip of MWNTs. Fourier Transform Raman Spectroscopy confirmed that graphitic structure of as-prepared CNTs. Field emission measurements reveal that the carbon nanotubes grown for 30 mins showed a turn-on field of 7.2 V/microm, when the current density achieves 10 microA/cm2. The field enhancement factor was calculated to be 708.50 for carbon nanotubes grown for 30 mins.     

An efficient fabrication of vertically aligned carbon nanotubes on flexible aluminum foils by catalyst-supported chemical vapor deposition

An efficient and versatile growth of thin-layer carbon nanotubes on a flexible aluminum foil (for kitchen use) by catalyst-supported chemical vapor deposition is reported. The aluminum foil used in the present experiment is commercially available for kitchen use. The electron-beam vapor deposition and dip-coating have been used for preparing catalysts on the aluminum foil. Vertically aligned thin-layer CNTs with typical diameters of 2.5-6.0?nm and lengths up to 90?μm are obtained when ethanol is used in combination with Fe and Co catalyst particles at a growth temperature of around 650?°C under an Ar/H(2) gas flow. Thermo-gravimetric analyses together with HR-TEM observations indicate that the purity of the CNTs synthesized by the current technique is very high.     

Arc process parameters for single-walled carbon nanotube growth and production: experiments and modeling

Collarets rich in single-walled carbon nanotubes (SWCNTs) have been grown using a direct current arc method. Arc process parameters such as current, pressure, and anode to cathode distance were varied experimentally and by modeling to provide an optimal working window. The best collaret yields were obtained when helium was used as a buffer gas. Mixing helium with argon in the buffer permits controlling nanotube diameters. In addition to an experimental study, a modeling approach was developed assuming local thermal equilibrium and homogenous and heterogeneous neutral chemistry. The gas-phase chemical model involves 81 neutral carbon species (C1, C2, . . ., C79, C60F, C70F) and 554 reactions with rates taken from data of Krestinin and Moravsky. Axial profiles of temperature, C atom, C2 radical, and fullerene distributions in the reactor are predicted as a function of process parameters. Carbon nanotube growth is considered by a set of surface reactions simulating open nanotube growth. Because nanotube surface chemistry is controlled by the local terminated bond and not by the bulk nanotube bond, a mechanistic approach based on the formal resemblance between the bonding and the structure of open nanotube and other carbon surfaces is proposed to explain nanotube growth. Predicted growth rates are in the range of 100 to 1000 microm/min.     

Effect of ammonia on the growth of carbon nanotubes

Carbon nanotubes were grown on hydrogen-treated Fe catalyst at 700 degrees C using a thermal chemical vapor deposition method. During the growth, acetylene was used as the carbon source, which is balanced by hydrogen and/or ammonia. Raman analysis shows that the introduction of ammonia to the gaseous carbon source can lead to defect structures in the carbon nanotubes due to the incorporation of nitrogen atoms into the carbon nanotubes. Furthermore, the growth rate of carbon nanotubes was also affected by the introduction of ammonia into the gaseous carbon source. We show that the dependence of the growth rate on the gaseous source composition is better described in terms of the ratio of ammonia to acetylene than the overall ammonia concentration. It is proposed that there is a competition between the ammonia and the acetylene during the growth of CNTs. At low ammonia/acetylene ratios the growth increases with ammonia concentration; while at high ammonia/acetylene ratios the growth decreases with the ammonia concentration. A critical ammonia/acetylene ratio of 4.4, at which the growth peaks, was found and discussed.     

Synthesis of nanocomposite powders of γ-alumina-carbon nanotube by sol–gel method

The nanocomposite powders of γ-alumina-carbon nanotube were successfully synthesized by a sol–gel process. The homogeneous mixture of carbon nanotubes and alumina particles was obtained by mixing the carbon nanotubes within alumina solution and followed by heating into gel. The resultant gel was dried and calcined at 200 °C into boehmite-carbon nanotubes composite powders. The mean particle size of synthesized boehmite was of the order of 4 nm. The boehmite-carbon nanotubes composite powders were calcined at different temperatures and XRD investigations revealed that as the amount of carbon nanotube increases, γ- to α-alumina phase transformation is completed at higher temperatures. The specific surface area and mean particle size of resultant nanocomposite powders increased and decreased, respectively by increasing the content of carbon nanotubes.     

Template directed formation of nanoparticle decorated multi-walled carbon nanotube bundles with uniform diameter

Bundles of multi-walled carbon nanotubes of uniform diameter decorated with Ni nanoparticles were synthesized using mesoporous silicates as templates. The ordered morphology and the narrow pore size distribution of mesoporous silicates provide an ideal platform to synthesize uniformly sized carbon nanotubes. In addition, homogeneous sub-10?nm pore sizes of the templates allow in?situ formation of catalytic nanoparticles with uniform diameters which end up decorating the carbon nanotubes. The resulting carbon nanotubes are multi-walled with a uniform diameter corresponding to the pore diameter of the template used during the synthesis that are decorated with the catalysts used to synthesize them. They have a narrow size distribution which can be used in many energy related fields of research.     

催化裂解天然气于碳毡内低成本合成碳纳米管

基于制备碳/碳(C/C)复合材料的等温化学气相渗透(ICVI)技术,在1010～1100℃用Fe催化裂解工业天然气可在碳毡内原位合成出碳纳米管(CNTs).扫描电镜(SEM)观察结果表明,1060℃合成的CNTs具有较好的覆盖形貌和均匀管径(110～120nm)且纯净度高.高分辨率透射电镜(HRTEM)和Raman光谱测试结果进一步表明,该温度下合成的CNTs结晶度高,与碳纤维间结合力强.     

载气种类对单壁碳纳米管管径的影响研究

单壁碳纳米管的管径对其性能、特别是储氢性能有极其重要的影响,但至今未见制备过程中系统控制单壁碳纳米管管径的报道.本文分别以氦气、氮气和氩气为载气,采用催化裂解法制备了不同直径范围的单壁碳纳米管.HRTEM和Raman光谱分析表明,以氦气、氩气为载气制得的碳管直径分布范围相对较窄,平均直径分别约为1.6和5.0nm.以氮气为载气时碳管直径分布相对较宽,约为2.0～4.5nm.氮气与碳反应生成氮化碳可能是导致单壁碳纳米管直径分布相对较宽的主要原因.分别以氦气、氮气和氩气为载气制得的单壁碳纳米管,在273K,15MPa时质量储氢分数依次为4.21%、6.30%和8.05%.