Production of carbon nanotubes by self-propagating high-temperature synthesis

Carbon nanotubes are prepared by the method of self-propagating high-temperature synthesis for the first time. The initial components for this synthesis are carboniferous materials (soda, limestone, and Teflon) and reducers (magnesium, lithium, and sodium) with addition of a nickel or iron catalyst. The morphology of the nanotubes (straight multiwall nanotubes apparently free of a catalyst, bent nanotubes completely filled with a catalyst, and carbon nanofibers) is similar to that of nanotubes grown by chemical methods. The nanotubes account for 2–4 wt % of the product synthesized.     

Inorganic WS<Subscript>2</Subscript> nanotubes revealed atom by atom using ultra-high-resolution transmission electron microscopy

The characterization of nanostructures to the atomic dimensions becomes more important, as devices based on a single particle are being produced. In particular, inorganic nanotubes were shown to host interesting properties making them excellent candidates for various devices. The WS₂ nanotubes outperform the bulk in their mechanical properties offering numerous applications especially as part of high strength nanocomposites. In contrast, their electrical properties are less remarkable. The structure–function relationship can be investigated by aberration-corrected high-resolution transmission electron microscopy (HRTEM), which enables the insight into their atomic structure as well as performing spectroscopic measurements down to the atomic scale. In the present work, the deciphering of atomic structure and the chiral angle of the different shells in a multiwall WS2 nanotube is demonstrated. In certain cases, the helicity of the structure can also be deduced. Finally, first electron energy loss spectra (EELS) of a single tube are presented, acquired by a new acquisition technique that allows for high spatial resolution (denoted StripeSTEM). The measured band gap values correspond with the values found in literature for thin films, obtained by spectroscopic techniques, and are higher than the values resulting from STM measurements.     

Characterisation of Ni-C films obtained in PVD/CVD process

The work presents the results of the scanning electron microscopy (SEM) and Raman spectrometry studies of carbonaceous nanostructures containing nickel nanocrystallites. The films were obtained using a two-step method. In the first phase the Physical Vapour Deposition (PVD) method was applied, whereas in the second Chemical Vapour Deposition (CVD) method was used. The paper presents results for samples with various Ni content obtained with different parameters of the two-phase technological process. The research confirms that the thin films obtained by PVD method contain Ni nanocrystallites distributed in a carbonaceous matrix. The matrix is composed of various carbon allotropes (amorphous carbon, graphite, fullerene). The thin films made by CVD method make a matrix when multiwalled, carbonaceous nanotubes are obtained. Depending on the technological process parameters of each phase, we obtain multiwall nanotubes with a various degree of defects.     

Isotope effect on the thermal conductivity of boron nitride nanotubes

We have measured the temperature-dependent thermal conductivity kappa(T) of individual multiwall boron nitride nanotubes using a microfabricated test fixture that allows direct transmission electron microscopy characterization of the tube being measured. kappa(T) is exceptionally sensitive to isotopic substitution, with a 50% enhancement in kappa(T) resulting for boron nitride nanotubes with 99.5% 11B. For isotopically pure boron nitride nanotubes, kappa rivals that of carbon nanotubes of similar diameter.     

Probing nanoscale solids at thermal extremes

We report a novel nanoscale thermal platform compatible with extreme temperature operation and real-time high-resolution transmission electron microscopy. Applied to multiwall carbon nanotubes, we find atomic-scale stability to 3200 K, demonstrating that carbon nanotubes are more robust than graphite or diamond. Even at these thermal extremes, nanotubes maintain 10% of their peak thermal conductivity and support electrical current densities approximately 2 x 10{8} A/cm{2}. We also apply this platform to determine the diameter dependence of the melting temperature of gold nanocrystals down to three nanometers.     

Properties and microstructure of composites derived from polycaproamide and multiwall carbon nanotubes

Composites were synthesized by anionic in situ polymerisation of ?-caprolactam in the presence of 0.1–5.0% of multiwall carbon nanotubes. It is found that nanotube filling increases rigidity and improves the friction characteristics of polycaproamide. The friction coefficient decrease is especially significant at a nanotube concentration of 0.1%. It is shown that nanotubes affect the composite film microstructure.     

Thermal transport of oil and polymer composites filled with carbon nanotubes

We studied the thermal transport properties of multi-walled carbon nanotubes (MWNTs) in polymer and oil matrices. The thermal conductivity of the oils and polymers increased linearly when adding tubes. We observe a particularly high increase in the thermal diffusivity of carbon-nanotube-loaded liquid crystal polymers (6×10⁻⁵ cm²/s wt%), which is due to a spontaneous alignment of the MWNTs. Carbon nanotubes increased the thermal conductivity of oil by a factor of three for 20 wt% loading. We found little or no dependence of the thermal enhancement on the specific flavor of multiwall nanotubes used in the composites. Carbon nanotubes are excellent nanoscale fillers for composites in thermal management application.     

On the limiting physical adsorption of hydrogen in carbon materials

The specific features of hydrogen adsorption (and adsorption of other gases) at supercritical temperatures (specifically, the absence of capillary condensation and polymolecular adsorption and the appearance of a maximum in the adsorption isotherm in the pressure range 1–10 MPa) are discussed. Hydrogen adsorption decreases by an order of magnitude as the temperature increases from the critical temperature to the room value. The experimental adsorption isotherms in the supercritical range found in the literature are used to deduce a criterion of limiting hydrogen adsorption at various temperatures. Carbon adsorbents of different types (individual single-wall nanotubes, bundles of such nanotubes, multiwall nanotubes, and carbon fibers) are considered. A model of single graphite plane shows that the limiting hydrogen adsorption is 5 wt % at 77 K and 1 wt % at 293 K. These values can only be approached by adsorption in a material made of individual single-wall nanotubes. Methods to increase the adsorption are proposed.     

Tuning of nanotube mechanical resonances by electric field pulling

We show here that field emission (FE) can be used to directly observe the vibration resonances nu(R) of carbon nanotubes (CNTs) and that the tension created by the applied field allows the tuning of these resonances by up to a factor of 10. The resonances are observable by the changes they create in the FE pattern or the emitted FE current. The tuning is shown to be linear in voltage and to follow from the basic physics of stretched strings. The method allows one to study the mechanical properties of individual multiwall carbon nanotubes within an ensemble and follow their evolution as the CNTs are modified. The tuning and detection should be useful for nanometric resonant devices.     

与富勒烯C36直径(0.5nm)相等的碳纳米管及其制备

在电弧放电方法制备纳米管中,通过用碳纳米管填充阳极进行放电实验,成功地得到了小直径单层碳纳米管。同时在多层管的最内层得到了直径0.5nm的碳纳米管。这个结果表明直径小于C60（直径0.7nm）的碳纳米管是存在的。     

与富勒烯C_(36)直径(0.5nm)相等的碳纳米管及其制备

在电弧放电方法制备碳纳米管中 ,通过用碳纳米管填充阳极进行放电实验 ,成功地得到了小直径单层碳纳米管 .同时在多层管的最内层得到了直径 0 5nm的碳纳米管 .这个结果表明直径小于C60 (直径 0 7nm)的碳纳米管是存在的 .     

Synthesis and characterization of CdS nanoparticle based multiwall carbon nanotube–maleic anhydride–1-octene nanocomposites

CdS nanoparticles were synthesized by sonication from cadmium chloride and thiourea using a multiwall carbon nanotube (MWCNT)–maleic anhydride (MA)–1-octene system as the matrix. The matrix was obtained by the “grafting from” approach from oxidized carbon nanotubes and maleic anhydride–1-octene. Multiwall carbon nanotubes used for reinforcing the matrix were synthesized by Catalytic Chemical Vapor Deposition using Fe–Co/Al₂O₃ as the catalyst. The obtained nanostructures were characterized by FTIR, XRD, Raman spectroscopy, TEM, SEM and UV–vis spectroscopy. The average CdS particle diameter was 7.9 nm as confirmed independently by TEM and XRD. UV–vis spectroscopy revealed that the obtained nanostructure is an appropriate base material for making optical devices. The novelty of this work is the use of the MWCNT–MA–1-octene matrix obtained via the “grafting from” approach for the synthesis of uniformly dispersed CdS nanocrystals by ultrasonic cavitation to obtain a polymer nanocomposite.     

Effect of band structure on quantum interference in multiwall carbon nanotubes

We report conductance measurements on multiwall carbon nanotubes in a perpendicular magnetic field. A gate electrode with large capacitance is used to considerably vary the nanotube Fermi level. This enables us to search for signatures of the unique electronic band structure of the nanotubes in the regime of diffusive quantum transport. We find an unusual quenching of the magnetoconductance and the zero bias anomaly in the differential conductance at certain gate voltages, which can be linked to the onset of quasi-one-dimensional subbands.     

Electron microscope vualization of muliphase fluids contained in closed carbon nanotubes

Aqueous multiphase fluids trapped in closed multiwall carbon nanotubes are visualized with high resolution using transmission electron microscopy (TEM). The hydrothermally synthesized nanotubes have inner diameter of 70 nm and wall thickness 20 nm, on average. The nanotubes are hydrophilic due to oxygen groups attached on their wall surfaces. Segregated liquid inclusions contained in the nanotubes under high pressure can be mobilized by heating. A resistive heating stage is utilized to heat a thin membrane inside a nanotube, causing the membrane to evaporate slowly and eventually pinch off. Focused electron beam heating is employed as a second means of thermal stimulation, which results in localized heating. With the latter method, gas/liquid interface motion is observed inside the thin channel of a carbon nanotube. Experiments like the ones presented herein may help understand the dynamics of fluids contained in nanoscale channels.     

Mechanical detection of carbon nanotube resonator vibrations

Bending-mode vibrations of carbon nanotube resonators were mechanically detected in air at atmospheric pressure by means of a novel scanning force microscopy method. The fundamental and higher order bending eigenmodes were imaged at up to 3.1 GHz with subnanometer resolution in vibration amplitude. The resonance frequency and the eigenmode shape of multiwall nanotubes are consistent with the elastic beam theory for a doubly clamped beam. For single-wall nanotubes, however, resonance frequencies are significantly shifted, which is attributed to fabrication generating, for example, slack. The effect of slack is studied by pulling down the tube with the tip, which drastically reduces the resonance frequency.     

Reinforcement effects of multiwall carbon nanotubes in elastomeric matrices: Comparison with other types of fillers

Mechanical and electrical properties of composites based on butyl rubber and multiwall carbon nanotubes (MWNTs) are investigated. Gradual increases in elastic moduli are observed with the filler content. It was found that the degree of strain affects the electrical resistivity. Finally, the level of reinforcement imparted to a rubbery matrix by carbon nanotubes is compared with that provided by other types of fillers such as carbon black, clay fibers or layered silicates.     

Mechanical and AFM investigations of elastomers filled with multiwall carbon nanotubes

Strong reinforcing effects are observed when multiwall carbon nanotubes are incorporated in a styrene–butadiene copolymer. The good level of dispersion of carbon nanotubes in the host matrix that allows to take advantage of their high aspect ratio as well as their orienting capability under uniaxial extension, appear to be the main parameters for mechanical reinforcement. Atomic force microscopy carried out in the unstretched and stretched states has been shown to bring important insights for the understanding of the mechanical properties of the composites.     

Multiple ionic-plasmon resonances in naturally occurring multiwall nanotubes: infrared spectra of chrysotile asbestos

Chrysotile asbestos is formed by densely packed bundles of multiwall hollow nanotubes. Each wall in the nanotubes is a cylindrically wrapped layer of Mg(3)Si(2)O(5)(OH)(4). We show by experiment and theory that the infrared spectra of chrysotile present multiple ionic-plasmon resonances in the Si-O stretching bands. These collective charge excitations are universal features of the nanotubes that are obtained by cylindrically wrapping an anisotropic material. The multiple plasmons can be observed if the width of the resonances is sufficiently small as in chrysotile.     

基于可调控多肽纳米管和石墨烯复合纳米结构的光吸收催化平台

近年来, 自组装纳米结构因为其容易制备、稳定、环保以及与各种功能基团、粒子等的多样结合能力吸引了科学家们的目光, 成为人们研究的热点课题, 在光电池、光催化、水凝胶、药物缓释等方面的实验科学领域得到了广泛的应用. 尤其是光催化方面, 自组装结构的重复性为激子的传递创造了比较良好的条件, 成为众多激子传递平台中的佼佼者. 本文报道了一种以苯丙氨酸二肽纳米管和羧基石墨烯为基础的自组装光吸收催化平台, 对其结构进行研究, 并使用该体系进行了烟酰胺腺嘌呤二核苷酸到它的还原态的催化实验. 该体系的微观结构由纳米管和石墨烯膜复合而成, 羧基石墨烯的存在能够降低纳米管直径, 实现纳米管的形态操控, 石墨烯与多肽纳米管复合纳米结构的存在实现了多通道协同激子传递, 降低了激子传递的距离, 极大增强了催化中心对于激子的接受和使用效率. 在复合了光敏剂和催化中心之后, 该体系具有较高的稳定性, 均一的分散性, 很强的光能吸收和转化能力等性质. 对于从NADP⁺往NADPH转变的催化实验表明, 该体系有较高的反应速率和催化效率, 并且比两种单一结构催化平台效果之和更好, 实现了一加一大于二的效应, 展现了复合纳米结构光吸收催化平台的巨大潜力和广阔应用前景.