Influence of pyrolysis temperature on the growth of Y-junction carbon nanotubes

Y-junction carbon nanotubes, grown through thermal pyrolysis of acetylene over nanocrystalline Ni-P deposited SiC whiskers, were investigated by transmission electron microscopy. The pyrolysis temperature, which ranged from 800 °C to 1000 °C, was found to be crucial for the growth of different Y-junction carbon nanotubes. At pyrolysis temperatures below the partial melting point of the Ni-P alloy catalyst, only single-junction nanotubes could be synthesized. Whereas, due to partial melting of the alloy catalyst at higher pyrolysis temperatures, liquid-assisted growth of multiple Y-junction nanotubes could occur. PACS 61.46.+w; 61.48.+c; 68.37.Lp     

Synthesis of carbon nanotubes by ECR plasma-assisted chemical vapor deposition

Carbon nanotubes have been grown using an electron cyclotron resonance (ECR) plasma source at a substrate temperature of 500 °C. Methane has been used as the source gas. A network of carbon nanotubes has been observed in scanning electron microscopy. Transmission electron microscopy revealed that the structure consists of straight, Y-junction and ring-like nanotubes. Further, electron diffraction of the nanotubes confirms a graphite crystal structure. PACS 81.16.He; 68.37.Lp; 68.37.Hk; 85.35.Kt; 75.75.+a     

Catalytic production of carbon nanotubes by vapor phase growth method using tungsten-containing organic compound

We report the production of carbon nanotubes of high purity by a vapor phase growth method using a catalytic reaction of a tungsten-containing organic compound (C₁₄H₁₀O₇W) and acetylene mixture. The products were multi-walled carbon nanotubes with hollow cores. Transmission electron microscopy investigation revealed that the graphitic layers at the inner region were highly crystallized but the graphitic layers at the outer region had a wavy structure. We have demonstrated the effective production of carbon nanotubes using a tungsten-based catalyst. PACS 81.07.De; 61.46.+w; 68.37.-d     

拉曼描述碳纳米管系统:缺陷探测,产物热处理,过程分析和催化剂(英文)

利用拉曼散射技术从多角度研究了碳纳米管合成系统。发现拉曼散射技术不仅可表征碳纳米材料本身的特性,而且可分析宏观的多壁碳纳米管与单壁碳纳米管的生长过程。针对不同的碳纳米材料的生长特性提出了催化剂与反应器设计及过程控制的研究方向。同时还发展了一种基于拉曼光谱法的定量测定单壁碳纳米管含量的方法。     

Matchstick-like carbon nanotube synthesis and structure

Matchstick-like carbon nanotubes (CNTs) have been synthesized by catalytic pyrolysis of thiophene, using a mixture of cobalt nitrate and calcium nitrate as a catalyst. The nanotubes thus grown are aligned, straight, and short, and have spherical heads at their tips. High resolution transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray spectroscopy results indicate that the spherical heads of the matchstick-like CNTs are crystalline Co₉S₈ nanoparticles and the CNTs have herringbone-type graphite structure. The effect of temperature on the formation of the matchstick-like CNTs has been investigated. A simple growth model is proposed to describe the growth process of the matchstick-like CNTs. PACS 81.05.Uw; 61.46 Fg; 81.15.Gh; 68.37.Hk; 68.37.Lp     

金镍复合膜上碳纳米管的定向生长及生长过程中金的作用

以金镍复合膜作催化剂，在96%的高氢气浓度下实现了碳纳米管的定向生长，并对其生长过 程进行了深入探讨.结果表明，高氢气浓度下碳纳米管生长的实现与本实验所选用的催化剂 ——金镍复合膜有密切关系.催化剂中金的参与，促进了碳在催化剂中的扩散，提高了碳在 催化剂中的活度.与催化剂中没有金的情况相比较，金的参与有利于镍吸收气氛中的碳，从 而使镍更容易达到碳饱和，有利于在高的氢气浓度下实现碳纳米管的定向生长. 关键词： 金镍复合膜 高氢气浓度 原子氢 碳活度     

Probing induced defects in individual carbon nanotubes using electrostatic force microscopy

Structural defects greatly affect the electronic properties of single wall carbon nanotubes (CNT’s), for instance by increasing the sensitivity to their environment; an effect which can be utilized for better performance of CNT based chemical sensors. Here we show that electrostatic force microscopy (EFM) can be used as a non-invasive technique for probing defects in individual CNT’s supported on insulating substrates. The technique is demonstrated by monitoring the change in EFM signal upon intentionally inducing defect by an oxygen plasma etch, and is applied to assess the quality of as-grown CNT samples and to study the effect of exposing CNT’s to the low energy electron irradiation of a scanning electron microscope (SEM). PACS 68.37.-d; 68.37.Ps; 61.46.Fg; 68.35.Dv     

Hydrogen adsorption on activated carbon nanotubes with an atomic-sized vanadium catalyst investigated by electrical resistance measurements

Activated multi-walled carbon nanotubes were prepared with appended vanadium as a hydrogen storage medium. The pore structure was significantly improved by an activation process that was studied using Raman spectroscopy, field emission transmission electron microscopy and pore analysis techniques. X-ray photoelectron spectroscopy and X-ray diffraction results reveal that the vanadium catalyst was introduced into the carbon nanotubes in controlled proportions, forming V₈C₇. The improved pore structure functioned as a path through the carbon nanotubes that encouraged hydrogen molecule adsorption, and the introduced vanadium catalyst led to high levels of hydrogen storage through the dissociation of hydrogen molecules via the spill-over phenomenon. The hydrogen storage behavior was investigated by electrical resistance measurements for the hydrogen adsorbed on a prepared sample. The proposed mechanism of hydrogen storage suggests that the vanadium catalyst increases not only the amount of hydrogen that is stored but also the speed at which it is stored. A hydrogen storage capacity of 2.26 wt.% was achieved with the activation effects and the vanadium catalyst at 30 °C and 10 MPa.     

Effects of gravity on single-wall carbon nanotubes synthesized by arc in water

The method using arc discharge in liquid is a simple and inexpensive route for synthesis of carbon nanotubes and other related nano-materials. In this study, we report the synthesis of single-wall carbon nanotubes (SWCNTs) by means of the arc-in-water method under extremely low gravity conditions. The strong heat convection caused by the arc plasma is suppressed under such conditions. Therefore, the boiling flow behavior and temperature distribution have been stabilized in low gravity. As a result, the possibility of the chirality control of SWCNTs by applying extremely low gravity was revealed; namely, the yield of semiconducting SWCNTs was increased and several SWCNTs of specific diameters turned out to be prominent under extremely low gravity conditions. PACS 52.80.Wq; 68.37.Lp; 81.07.De; 81.70.Ha; 82.80.Gk     

碳纳米管在银基底上的表面增强拉曼散射光谱研究(英文)

介绍了一种单壁碳纳米管表面增强拉曼散射的新方法。依据碳纳米管独特的力学性能,在银表面直接研磨单壁碳纳米管,在形成纳米级粗糙银表面的同时,单壁碳纳米管也吸附在银表面上。在银表面粗糙程度和单壁碳纳米管厚度适中的区域得到了高质量的单壁碳纳米管SERS谱。该方法消除了溶剂的干扰,保证了结果的准确性,理论分析和实验结果表明该方法是正确的、可行的     

Hydrogen adsorption on N-decorated single wall carbon nanotubes

Using density functional theory and molecular dynamics we found that N-decorated single walled (8,0) carbon nanotubes are potential high capacity hydrogen storage media. This system could store up to 6.0 wt% hydrogen at 300 K and ambient pressure, with average adsorption energy of −80 meV/(H₂). Nitrogen coverage was C₈N.     

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.     

Electronic structure,magnetic properties,and microstructural analysis of thiol-functionalized Au nanoparticles: role of chemical and structural parameters in the ferromagnetic behaviour

The present work describes the field emission characteristics of nanocrystalline metal clusters decorated multi walled carbon nanotubes (MWNT) field emitters fabricated over flexible graphitized carbon cloth. MWNT have been synthesized by catalytic chemical vapour decomposition (CCVD) of acetylene over Rare Earth (RE) based AB₂ (DyNi₂) alloy hydride catalyst. Fine powders of RE based AB₂ alloy hydride catalysts have been prepared by hydrogen decrepitation technique. The as-grown carbon nanotubes (CNTs) are purified by acid and heat treatments and characterized using XRD, SEM and TEM. Purified MWNT have been decorated with nanocrystalline Pd, Pt and Pt–Ru metal clusters using a simple chemical reduction method. The characterization of metal decorated CNTs were done by using XRD, SEM, TEM, HRTEM and EDX. Nanocrystalline Pd, Pt and Pt–Ru metal clusters decorated MWNT field emitters have been fabricated over graphitized carbon fabric using spin coating method. The field emission characteristics have been studied using an indigenously fabricated set up and the results are discussed. The samples show excellent emission properties with a fairly stable emission current over a period of 4 h. As the presence of the graphitic layer provides strong adhesion between the nanotubes and carbon cloth, the use of graphitized carbon cloth as substrate opens new possibilities for CNT field emitters.     

Experimental study of the influence of hydrogenation on synthesis of carbon nanostructures in a reactor with activated hydrogen

The role of backward pyrolysis of carbon during hydrogenation of unstructured carbon black and nanotube growth in a reactor with hydrogen activated by diffusion through a heated metallic wall is studied. If the wall is heated nonuniformly, the amorphous unstructured carbon deposit “climbs” in the course of hydrogenation by active hydrogen and deposits again when falling on the heated metal surface, self-organizing into more ordered nanofibers and nanotubes as a result of forward pyrolysis. It is shown that this effect can be used for raising the concentration of carbon nanotubes growing on catalyst particles in the deposited layer.     

Selective growth, characterization, and field emission performance of single-walled and few-walled carbon nanotubes by plasma enhanced chemical vapor deposition

Single-walled carbon nanotubes (SWCNTs) and few-walled carbon nanotubes (FWCNTs) have been selectively synthesized by plasma enhanced chemical vapor deposition at a relative low temperature (550 °C) by tuning the thickness of iron catalyst. The parametric study and the optimization of the nanotube growth were undertaken by varying inductive power, temperature, catalyst thickness, and plasma to substrate distance. When an iron film of 3-5 nm represented the catalyst thickness for growing FWCNT arrays, SWCNTs were synthesized by decreasing the catalyst thickness to 1 nm. The nanotubes were characterized by field emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. Electron field emission properties of the nanotubes indicate that the SWCNTs exhibit lower turn-on field compared to the FWCNTs, implying better field emission performance.     

Sulfur impregnation of multi‐walled carbon nanotubes via SF6/NH3 plasma exposure

Plasma treatments are established methods to functionalise carbon nanotubes (CNTs) and modify their surface structure. This paper presents a mild glow‐discharge plasma treatment of aligned arrays of multi‐walled carbon nanotubes employing sulfur hexafluoride (SF₆), ammonia (NH₃), and their mixtures as process gases. For the latter, sulfur was detected at the tip and sidewalls of the nanotubes via energy‐dispersive X‐ray spectroscopy, while electron microscopy served as method to verify the structural integrity of the CNTs after the plasma treatment. This approach provides the basis for an easy and quick alternative to existing sulfur functionalisation methods of MWCNTs. Furthermore, the proposed method can conveniently be applied to carbon nanotube arrays on substrate while preserving their structure and alignment.

SEM‐EDX map of SF₆/NH₃ plasma‐treated multi‐walled carbon nanotubes on substrate. Green, yellow and red correspond to silicon, carbon and sulfur signals, respectively.     

Effect of hydrogen on the growth and morphology of single wall carbon nanotubes synthesized on a FeMo/MgO catalytic system

Single wall carbon nanotubes were synthesized from thermal pyrolysis of methane on a FeMo/MgO catalyst by radio frequency catalytic chemical vapor deposition (RF-CVD) using argon as a carrier gas. Controlled amounts of hydrogen (H₂/CH₄=0-1 v/v) were introduced in separate experiments along with the carbon source. The properties and morphology of the synthesized single wall carbon nanotubes were monitored by transmission electron microscopy, Raman scattering, and thermogravimetric analysis. The nanotubes with the highest crystallinity were obtained with H₂/CH₄=0.6. By monitoring the Radial Breathing Modes present in the Raman spectra of the single-wall carbon nanotube samples, the variation of the structural and morphological properties of the carbon nanotubes with the flow level of hydrogen, reflect changes of the catalyst systems induced by the presence of hydrogen.     

Effects of catalysts on the internal structures of carbon nanotubes and corresponding electron field-emission properties

Using a chemical vapor deposition (CVD) method, multi-walled carbon nanotubes with uniform diameters of approximately 10 nm were synthesized on silicon substrates by the decomposition of acetylene using Fe, Co and Ni as the catalysts. Catalyst effects on the internal structures of the carbon nanotubes were evident in the Fe, Co and Ni catalyzed nanotubes. Although these nanotubes demonstrated similar morphologies, due to the variety of internal structures, the nanotubes synthesized from different catalysts demonstrated various electron field-emission characteristics including turn-on field, threshold field and field enhancement factor. Compared with carbon nanotubes from Ni catalyst, nanotubes from Fe and Co with the same diameters have better field-emission properties. Graphite layers in nanotubes from Fe and Co are much straighter and more parallel to the tube axis with fewer defects. For instance, the turn-on field and threshold field for nanotubes from Ni are 5 V/m and 9 V/m, respectively. These electric fields are much higher than those for nanotubes from Fe, which are 0.35 V/m and 2.8 V/m, respectively. This could be due to the effect of catalysts on the work function of nanotubes, since the catalyst particle usually terminates the free end of the nanotube, and the influence of internal structure on electron transportation along the nanotube axis. Therefore, this study suggests that besides a small diameter, good graphitization (crystallization) is an important prerequisite for a good carbon nanotube emitter. PACS 79.70.+q; 68.37.Lp; 81.07.De     

The effects of static magnetic field on microwave absorption of hydrogen plasma in carbon nanotubes: A numerical study

We theoretically investigate the microwave absorption properties of hydrogen plasma in iron-catalyzed highpressure disproportionation-grown carbon nanotubes under an external static magnetic field in the frequency range 0.3 GHz to 30 GHz, using the Maxwell equations in conjunction with a general expression for the effective complex permittivity of magnetized plasma known as the Appleton–Hartree formula. The effects of the external static magnetic field intensity and the incident microwave propagation direction on the microwave absorption of hydrogen plasma in CNTs are studied in detail. The numerical results indicate that the microwave absorption properties of hydrogen plasma in iron-catalyzed high-pressure disproportionation-grown carbon nanotubes can be obviously improved when the external static magnetic field is applied to the material. It is found that the specified frequency microwave can be strongly absorbed by the hydrogen plasma in iron-catalyzed high-pressure disproportionation-grown carbon nanotubes over a wide range of incidence angles by adjusting the external magnetic field intensity and the parameters of the hydrogen plasma.     

MEAM study of carbon atom interaction with Ni nano particle

Carbon, Ni, and C-Ni alloy modified embedded atom method (MEAM) potentials were developed to study the initial process of carbon nanotube growth on Ni catalyst particles. The MEAM potentials were used to study the atomistic interaction between a carbon atom and a fcc Ni nano particle, both on the particle surfaces and inside the Ni nano particles. The result shows that surface carbon atom is more stable than those in the bulk and sub-surface interstitial positions. Carbon atoms are expected to diffuse from the bulk to the surface, and the single walled and double-walled carbon nanotubes would be more favorable to form on Ni nano particle catalyst. The carbon and Ni nano particle interaction calculation shows that the corner and the edge of the particle are the energetically more favorable sites for the carbon adatom. The carbon nanotube may grow from the corner and edge of the particle.