Carbon Nanotubes Grown on the Surface of Cathode Deposit by Arc Discharge

Abstract

Carbon nanotubes prepared by de arc discharge of graphite electrodes in He and CH₄ gas took markedly different morphology. Thick nanotubes embellished with many carbon nanoparticles were obtained by evaporation under high CH₄ gas pressure and high arc current. Thin and long carbon nanotubes were obtained under a CH₄ gas pressure of 50Torr and an arc current of 20A for the anode with a diameter of 6mm.     

Anode mode in cathodic arc deposition apparatus with various cathodes and ambient gases

The anode mode of a vacuum arc in a cathodic arc deposition apparatus was observed as a function of ambient gas pressure ranging from 0.01 to 300 Pa. The chamber (400 mm in diameter and 600 mm in length) made of stainless steel (SUS304) acted as the anode. The arc was operated at a relatively low constant current of 50 A. The cathode materials used were Al, Ti, Fe, Ni, and Cu, and ambient gases were He, Ne, Ar, H₂, N₂, O₂, and CH₄. The principal results are as follows. (1) As the pressure was increased, the anode mode changed from diffuse-arc to footpoint to plane luminous to anode-spot mode. (2) The anode mode and resultant arc voltage increase were strongly dependent on gas species, and weakly on the cathode material. (3) Comparing diatomic and polyatomic (H₂, N₂, O₂, and CH₄) with mono-atomic molecule gases (He, Ne, and Ar), the onset pressure of the anode mode transition in the former was lower, the arc voltage higher, and the footpoints more numerous, smaller, and clearer. Both the dependence of the ambient pressure and the influence of the cathode materials and gas species on the anode mode changes were explained by the ion deficiency theory.     

Hot-wire growth of multi-phase carbon nitride films

This paper describes the growth of multi-phase carbon nitride films using hot-wire chemical vapor deposition (HWCVD) on (100)-oriented crystalline Si substrates. A mixture of either CH₄/NH₃ or CH₄/N₂ was activated over a hot tungsten filament under varying deposition conditions. The samples were characterized by atomic force microscopy (AFM) and X-ray diffraction (XRD). AFM micrographs show the presence of facetted crystallites. The XRD peaks observed were compared with theoretical predictions for -C₃N₄ and β-C₃N₄—the two ultra-hard phases of carbon nitride. The results suggest the presence of -C₃N₄ and β-C₃N₄, as well as other unidentified phases in our films. We also calculated the equilibrium concentration of the various gas species as a function of temperature and pressure. Our results indicate that CN and C₂N₂ radicals are possible precursors to carbon nitride growth.     

Effects of oxygen on multiwall carbon nanotubes growth by PECVD

Multiwall carbon nanotubes (MWCNTs) were grown by dielectric barrier discharge (DBD)-type plasma enhanced chemical vapor deposition (PECVD) method in downstream. The temperature was 973 K and the compositions of gases were methane, hydrogen and oxygen in the total pressure of 0.05 MPa. The effect of O₂ concentration in the mixture on the configuration of carbon nanotubes (CNTs) was investigated in detail. Results from scanning electron microscope (SEM) and transmission electron microscope (TEM) showed that CNTs grown in CH₄/H₂ (38.6%/61.4%, volume) mixture have many defects and contained disordered graphitic materials. With the addition of appropriate amount of O₂ (∼ 0.67%), high-purity CNTs could be obtained. However, no CNT, even no carbon matrix existed under the condition of an excessive oxygen concentration (> 1.0%, volume) in the mixture. In order to understand the role of O₂ during CNTs growth, optical emission spectroscopy (OES) was in-situ employed and the results predicted that the improvement of CNTs quality in O₂ addition was attributed to the effect of OH oxidation from the reaction of atomic oxygen with hydrogen in the plasma.     

Soot and other Products Formation from the Submerged Carbon Arc in Halogenated Solvents

A series of selected halomethanes were treated with the submerged carbon arc using graphite electrodes at 10A. CCl₄ and CHCl₃ produce abundant soot which is double in comparison to the soot produced by arcing CH₂Cl₂ and is one order of magnitude higher than the amount of soot produced by arcing hydrocarbons such as n-hexane or decalin and two orders of magnitudes higher in comparison to the amounts of soot produced by arcing alcohols. It was found a anticorrelation between the amount of polyynes present in the solution of the arced solvent and the amount of soot produced by arcing. In the case of CCl₄ and CHCl₃ no polyynes were detected by liquid chromatographic analysis (HPLC-DAD), while polyynes were detected in CH₂Cl₂ and are present in higher concentration in arced hydrocarbon solutions. The soot produced from halomethanes was analyzed by FT-IR spectroscopy in comparison to the soot produced by arcing hydrocarbons and alcohols. Furthermore, the soot from halomethanes was analyzed by HPLC-DAD after extraction with acetonitrile and found to contain a mixture of halogenated polycyclic aromatic hydrocarbons (PAHs). Also CHClBr and CH₂I₂ were arced between graphite electrodes. The former compound produces free bromine and soot; bromine causes halogenation of the polyynes. In the case of the latter compound, free iodine is released from the arc and the amount of soot produced is comparable to that obtained by arcing CH₂Cl₂.     

初始压力和富氧系数对CH4/O2/N2预混气体爆炸特性的影响

为了探究甲烷CH4在富氧和非常压条件下的爆炸危险性,确保CH₄气体在不同工况下的安全使用,借助5 L圆柱形爆炸装置,研究了初始压力p₀和富氧系数E对CH₄/O₂/N₂爆炸特性的影响。包括最大爆炸压力p_max、最大压力上升速率（dp/dt）_max和最大压力到达时间t_c等衡量CH₄爆炸安全性的指标。结果表明:当E为 0.21、0.25和0.30时,p_max随p₀的增加始终线性上升;而当E为 0.35和0.40时,p_max随p₀的增加先缓慢线性上升、后快速线性上升;（dp/dt）_max随p₀的增加分为线性上升和一阶指数快速上升。在E为0.21和0.25时,t_c随p₀的增加而线性增大,因为在燃烧初始阶段CH₄活化自由基的销毁速率增加,降低了反应速率和燃速,引起预混气体t_c的延长;但随着E的增加,氧气的促进作用与自由基销毁的抑制作用形成新的竞争效应,使得t_c先增加、后下降。     

Kinetics of Carbon Multi-wall Nanotube Synthesis by Catalytic Pyrolysis of Methane

By method of isothermal gravimetry at 600-700°C, CH₄ concentration 32-100% in Ar and 91-100% in H₂ under atmospheric pressure the kinetics of CH₄ pyrolysis under Ni/La₂O₃ catalysts is studied. Estimated apparent activation energy of reaction is 73 kJ/mol for fresh catalyst and 71 kJ/mol for aged one. The reaction order on CH₄ changes from 1.05 at 600°C to 1.3 at 700°C. The influence of H₂ concentration on the reaction rate is more complicated. On the basis of kinetics measurements continuously working laboratory-scale reactor with gas and catalyst counter-flow is constructed and tested.     

Carburization performance of Incoloy 800HT in CH4/H2 gas mixtures

Carburization performance of Incoloy 800HT has been studied after cyclic and isothermal exposures to CH₄/H₂ carburizing gas mixtures at high temperatures for 500 h. At 800 °C in 2% CH₄/H₂, Incoloy 800HT suffered external oxidation and carburization, the external continuous layer of reaction products consists primarily of Cr₇C₃, Mn_1.5Cr_1.5O₄, and FeCr₂O₄ with Fe(Cr, Al)₂O₄ as a minor phase. At 1100 °C in 10% CH₄/H₂, external carburization did not occur likely due to high carbon dissolution in the alloy substrate at this temperature. A thermodynamic analysis indicated that 1000 °C was an approximate critical temperature, below which the environment should result in mixed oxidizing/carburizing behavior, while above this temperature reducing carburizing behavior should occur. The experimental results approximately agree with the thermodynamic analysis. Metal dusting was not observed under highly carburizing conditions (a_C>1). The size and morphology of Cr-rich phases (or Cr-carbides) are both temperature- and time-dependent, while the external continuity is more temperature-dependent rather than time-dependent.     

Effects of Fuel Compositions on the Structure and Yield of Flame Synthesized Carbon Nanotubes

Flame synthesis of carbon nanostructures including nanotubes on galvanized steel was investigated utilizing laminar diffusion flames of different types of fuel. Methane (CH₄), propane (C₃H₈) and acetylene (C₂H₂) were used as fuels. Distinctive carbon nanostructures were produced depending on fuel types and fuel flow rates. The qualitative and quantitative analysis of many transmission electron microscope (TEM) and scanning electron microscope (SEM) images were performed. Methane produced thin multi wall carbon nanotubes as well as nanorods and nanofibers within the fuel flow rate range of 7.18E-07 m³/s to 9.57E-07 m³/s. Propane yielded nanotubes only at the fuel flow rate of 4.20E-07 m³/s. The nanotubes synthesized by acetylene flames were of different types that included helically coiled and twisted nanotubes.     

Dissociation process of CH4/H2 gas mixture during EACVD

The dissociation process of CH₄/H₂ gas mixture during EACVD has been investigated using Monte Carlo simulation for the first time. The electron velocity distribution and H₂ dissociation were obtained over a wide range: 100<E/N<2000 Td. The variation of CH₄ dissociation with CH₄ concentration in the filling gas has been simulated. The electron velocity profile is asymmetric for the component parallel to the field. Most electrons possess non-zero velocity parallel to the substrate. The number of atomic H is a function of E/N. There are two peaks at E/N=177 Td and 460 Td. The appropriate E/N is suggested to be 500–800 Td for low temperature deposition. The main diamond growth precursor is proposed to be CH₃ and CH₃⁺.     

Fullerenes and Carbon Nanotubes Formed in an Electric Arc at and Above Atmospheric Pressure

[60]Fullerene and carbon nanotubes have been obtained with an electric arc discharge in helium or argon at the pressure of 0.1-3.0 bar (i.e. from -0.9 up to 2.0 bar above the atmospheric pressure, respectively). The yield of the process is about 10 times higher in helium with a maximum at the pressure of 0.2 bar, while in argon the maximum is observed at 0.4 bar. It is not very important, what kind of the inert gas (He or Ar) is used in a process carried out at the atmospheric pressure and higher. In this case, the yield is usually better or comparable with other alternative methods, e.g. the solar furnace synthesis. We found that the oxygen plays a crucial role reducing the yield of fullerenes and carbon nanotubes. Even traces of O₂ must be removed from the reactor chamber, otherwise yellow coloured fullerene derivatives (oxidation products) are formed instead of C₆₀.     

Optical Emission Measurements of Rotational Temperature of C2 Radicals in Fullerene Processing

In this work, the results of optical emission study of C₂ radicals generated in carbon arc plasma are presented. It was found that a rotational temperature of carbon vapor depends significantly on carbon concentration and inert gas pressure. Experimentally obtained rotational temperature of C₂ emission spectra has been fitted with calculated spectra.     

直流电弧等离子体制备纳米SiC及其催化特性

利用工业块体硅为硅源, CH₄为碳源, 在含有H₂和Ar混合气氛中, 采用直流电弧等离子体法制备SiC纳米粒子。CH₄含量影响SiC纳米粒子的化学组成和形貌。结果显示: 产物中含有3C-SiC和6H-SiC两种物相, 而在CH₄压力为0.005 MPa条件下制备的SiC纳米粒子还含有Si/SiC核壳结构。利用制备的SiC纳米颗粒作为催化剂, 在恒光强下光电催化还原脱除2,4-二氯酚中的Cl原子。结果显示在-1.02 V偏压下光电催化180 min后, 对2,4-二氯酚的去除效率达92.5%, SiC纳米粒子的吸附效率为19.6%。因此, SiC纳米颗粒可取代贵金属, 作为低成本光电催化候选材料用于污水处理。     

由二种烟煤制备碳纳米管的探索性研究

以一种中国烟煤和一种新西兰烟煤为原料,采用电孤等离子体法制备碳纳米管。碳纳米管及其副产物富勒烯烟灰的表征采用扫描电镜（SEM）和红外光谱（FT－IR）等技术。结果表明：电弧放电时的缓冲气体压力对碳纳米管的产率影响很大;在一定的缓冲气压下电极间电流和电极间距各存在一最佳值。在He气压力为0.0665MPa、工作电流为40A条件下进行电弧放电,阴极上棒状沉积物的内芯中碳纳米管含量高达75％以上。基于实验结果,讨论了以煤为原料用电弧等离子体法制备碳纳米管过程中的工艺参数对碳纳米管生长的影响。     

Effect of CH4 and H2 on CVD of SiC and TiC for possible fabrication of SiC/TiC/C FGM

SiC and TiC coatings were deposited by CVD on graphite substrates and the effect of the variation of the methane (CH₄) and hydrogen (H₂) ratio on deposition was investigated. SiCl₄, TiCl₄ and CH₄ were used as sources of Si, Ti and C. In case of the SiC coatings, stoichiometric SiC was obtained when the ratios of CH₄/(SiCl₄ + CH₄)andH₂/(SiCl₄ + CH₄) are 0.4 and 10, respectively. Stoichiometric TiC was also obtained under similar conditions. In order to obtain non-stoichiometric materials for possible fabrication of functionally gradient materials (FGM), a change of microstructure and composition was observed with changes of the CH₄ and H₂ ratio. As a result, SiC, TiC and C contents were more easily controlled by a change of the H₂ ratio compared to the CH₄ ratio for SiC and TiC deposition. It has been verified that the change of the H₂ ratio is more desirable for possible manufacturing of SiC/TiC/C FGM.     

THE INFLUENCE OF SYNTHESIS PARAMETERS ON THE PRODUCTION OF MULTIWALLED CARBON NANOTUBES BY THE FERROCENE CATALYZED PYROLYSIS OF TOLUENE

A high yield (∼32 wt.%) of multiwalled carbon nanotubes was obtained in an iron catalyzed reaction. This was achieved in the temperature range 800-1000°C under an atmosphere of H₂/Ar by an improved solution injection method in a horizontal reactor using toluene as carbon source and ferrocene as catalyst precursor. The pyrolysis temperature, ferrocene concentration, solution feeding rate and carrier gas flow rate all influenced the yield of carbon nanotubes and the thickness of the aligned carbon nanotube films. The carbon nanotubes was prepared in high purity using optimized pyrolysis conditions.     

Synthetic Routes to Novel Nanomaterials

Soon after the bulk production of carbon nanotubes was achieved, using arc discharge techniques, other methods involving gas phase processes (i.e. combustion ami pyrolysis of hydrocarbons, laser irradiation of graphite) were developed. Nowadays, it is possible to generate nanotubes and fullerene-related nanostructures from layered materials such as WS₂, MoS₂, BN, BC₂N and BC₃. Recently, a new technique, involving electrolysis of graphite electrodes in molten ionic salts, has been developed which may open up new synthetic routes to nanotubes in the liquid phase. In this paper, possible growth mechanisms for such processes are reviewed and other routes to nanstructures are discussed.     

碳纳米管和TiB2混杂增强铜复合材料的电弧侵蚀行为

采用放电等离子烧结（SPS）工艺制备出不同混杂比例碳纳米管（CNTs）和TiB₂混杂增强铜（CNTs-TiB₂/Cu）复合材料,对复合材料致密度、硬度、导电率、导热率和显微组织进行了对比和分析。同时对复合材料进行了电接触试验,研究了不同电流条件下CNTs与TiB₂混杂比例对CNTs-TiB₂/Cu复合材料电弧侵蚀行为的影响。结果表明:随着CNTs与TiB₂混杂比例的增加,CNTs-TiB₂/Cu复合材料的密度、硬度、导电率和导热率逐渐降低,铜基体晶界分离现象越来越明显;在特定电流条件下,合适的CNTs-TiB₂混杂比例可提高CNTs-TiB₂/Cu复合材料的抗电弧侵蚀性能;当电流为5 A和10 A时,CNTs与TiB₂混杂比例为4∶1的平均燃弧能量、平均燃弧时间和材料转移量达到最低,而电流为15 A时,CNTs与TiB₂混杂比例为1∶4的平均燃弧能量、平均燃弧时间和材料转移量达到最低。电弧侵蚀后阴极出现熔池、气孔及熔融金属铺展等特征,且随着CNTs与TiB₂混杂比的增加,CNTs-TiB₂/Cu复合材料熔池面积减小,气孔数量变少,熔融金属铺展的特征减弱。      

比表面积与入口气体分压对热解炭微观结构影响的数值模拟研究

本研究在炭/炭复合材料热解炭基体织构形成与转化的模型基础上, 基于石墨微晶片层的表面结构特点, 建立了蜂窝结构的热解炭沉积表面几何模型, 并运用Monte Carlo方法模拟了在等温等压化学气相渗透(CVI)过程中热解炭基体沉积的动力学过程, 研究了预制体比表面积(A_S/V_R)和入口气体分压对热解炭微观结构的影响。通过数值模拟并结合已公开发表的实验结果发现, 在CVI工艺过程中一定的压力条件下, 通过控制A_S/V_R可以获得不同织构的热解炭, 预制体的A_S/V_R存在两个临界值, 靠近反应器入口处的临界值为1.45 m^-1和8.9 mm^-1, 靠近反应器出口处的临界值为0.3 mm^-1, 当A_S/V_R处于这两个临界值之间时, 系统主要沉积高织构热解炭; 在同一A_S/V_R且压强小于30 kPa的条件下, 通过控制反应气体压强的值也可以得到不同织构的热解炭, 并且压强也存在一个临界值, 当压强大于这个临界值时, 系统主要沉积高织构热解炭。     

FTIR spectroscopy of hydrogen, carbon monoxide, and methane adsorbed and co-adsorbed on zinc oxide

Adsorption of dihydrogen, carbon monoxide and methane, and co-adsorption of H₂/CO, H₂/CH₄ and CO/CH₄ on zinc oxide was studied by means of Fourier transform infrared spectroscopy. Besides the already known dissociation of dihydrogen and molecular adsorption of CO, methane was found to be adsorbed molecularly on coordinatively unsaturated Zn²⁺ ions. Adsorption lowers the CH₄ symmetry from T_d to C_3v, which is reflected in activation of the v₁ (symmetric stretching) mode and discrete frequency shifts of the v₃ (antisymmetric stretching) and ν₄ (bending) modes. Co-adsorption of the above gases on ZnO having pre-adsorbed hydrogen results, in all cases, in a bathochromic shift of the v(Zn–H) band and a hypsochromic shift of the v(O–H) band, which originally appear at 1710 and 3492 cm⁻¹, respectively. The magnitude of these shifts depends upon the nature of the co-adsorbed gas.