Carbon nanotubes and nanostructures grown from diamond-like carbon and polyethylene

We report a simple way to synthesize carbon nanotubes and nanostructures from the solid phase. Vacuum annealing of diamond-like carbon (DLC) films or polyethylene mixed with catalyst in argon atmosphere leads to the formation of nanotubes and nanostructures. High-resolution transmission electron microscopy studies reveal highly graphitized multi-walled nanotubes (MWNTs) or amorphous fibre-like structures, depending on the catalyst amount. This synthesis process may give a new approach to understanding the phase transition of different carbon allotropes into nanotubes or nanostructures. Received: 3 July 2001 / Accepted: 3 July 2001 / Published online: 2 October 2001     

Functional multi-walled carbon nanotube/polyaniline composite films as supports of platinum for formic acid electrooxidation

Embedding of carbon nanotubes in conducting polymeric matrices for various nanocomposites material is now a popular area. In this article, a concise chemical method has been described for the preparation of homogeneous nanocomposite of multi-walled carbon nanotube (MWNT)/polyaniline (PANI) by electrochemical codeposition. For this we functionalized the MWNTs via the diazotization reaction. This helped to disperse the nanotubes in aniline. The composite films were dispersed Pt by electrodeposition technique. The presence of MWNTs and platinum in the composite films was confirmed by XRD analysis and transmission electron microscopy (TEM). Four-point probe investigations revealed that the MWNT/PANI composite films exhibited a good conductivity. Cyclic voltammograms (CV) showed that Pt-modified MWNT/PANI composite films perform higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formic acid oxidation. The results imply that the MWNT/PANI composite films as a promising support material improves the electrocatalytic activity for formic acid oxidation greatly.     

Raman and SERS studies of carbon nanotube systems

In this paper, we report on Raman studies carried out on different carbon nanotube systems, namely single-walled and multi-walled carbon nanotubes and polymer/nanotube composites. We focus on different types of interactions which can take place in these materials. In single-walled nanotubes, the introduction of van der Waals interactions between tubes when arranged in bundles leads to an upshift of the radial breathing mode (RBM) ranging from 11 to 16 cm⁻¹ depending on the size of the bundle. In multi-walled carbon nanotubes, similar interactions between concentric tubes permit to interpret the low frequency Raman modes. In composites, PMMA/nanotubes, an upshift of the RBM is also observed, explained by the dynamical strain applied by the polymer on the bundles, in response to the breathing vibration. In addition, surface enhanced Raman scattering experiments have demonstrated the occurrence of interfacial reactions between the nanotubes and the metallic support. This is put in evidence by the degradation of tubes, especially metallic ones, and reconstruction of C₆₀-like molecules are in some cases observed.     

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.     

Carbon nanotube-epoxy composites: The role of acid treatment in thermal and electrical conductivity

Wet acid oxidation treatment methods have been widely reported as an effective method to purify and oxidize the surface of industrial multi-walled carbon nanotubes. This work examines the use of a concentrated HNO₃/H₂SO₄ mixture in an attempt to optimize the purification procedure of industrial multi-walled carbon nanotubes with diameter distribution statistics. It is shown that acid treatments of several hours are enough to purify the nanotubes. The electrical and thermal conductivities of epoxy composites containing 0.05–0.25 wt% of an acid-treated multi-walled carbon nanotube have been studied. The electrical conductivity of the composites decreases by more than three orders, whereas the thermal conductivity of the same specimen increases very modestly as a function of the filler content.     

Charge‐transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E_laser = 1.17 eV suggest that a charge‐transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright © 2010 John Wiley & Sons, Ltd.     

Electrical, dielectric and surface wetting properties of multi-walled carbon nanotubes/nylon-6 nanocomposites

This paper reports that the multi-walled carbon nanotubes(MWCNT)/nylon-6 (PA6) nanocomposites with different MWCNT loadingshave been prepared by a simple melt-compounding method. Theelectrical, dielectric, and surface wetting properties of theCNT/PA6 composites have been studied. The temperature dependence ofthe conductivity of the CNT/PA6 composite with 10.0 wt{\%} CNTloading ($\sigma _{\rm RT} \sim 10^{-4}$ S/cm) are measured, andafterwards a charge-energy-limited tunnelling model (ln $\sigma (T)\sim T^{-1/2})$ is found. With increasing CNT weight percentage from0.0 to 10.0 wt%, the dielectric constant of the CNT/PA6composites enhances and the dielectric loss tangent increases twoorders of magnitude. In addition, water contact angles of theCNT/PA6 composites increase and the composites with CNT loadinglarger than 2.0 wt%even become hydrophobic. The obtainedresults indicate that the electrical and surface properties of thecomposites have been significantly enhanced by the embedded carbonnanotubes.     

Preparation of highly conductive CNTs/polyaniline composites through plasma pretreating and in-situ polymerization

In this study, carbon nanotubes (CNTs) were pretreated by plasma, and further in-situ polymerized with aniline to achieve uniform CNTs/polyaniline (PANI) composites with high conductivity. The highest conductivity (2.946 S/cm) of CNTs/PANI composites under optimum plasma treating parameters is much higher than those without CNTs pretreatment or premodified by acid oxidation method. The scanning electronic microscope (SEM) pictures indicate that smooth surfaces of pristine CNTs (diameter: 20-40 nm) changes into rough structures and the size increases to around 90 nm, which is further proved by the X-ray diffraction (XRD), the Fourier transform infrared spectroscopy (FTIR), and the Raman measurements. Thermogravimetric analysis (TGA) results reveal that the thermal stability of CNTs/PANI composite is better than that of pure PANI.     

聚苯胺/碳纳米管复合体的制备及其三阶非线性光学性能研究

通过原位吸附-受限生长聚合法成功制备了聚苯胺/碳纳米管(PANI/MWCNT)复合体.红外光谱和拉曼光谱证实了在碳纳米管(MWCNT)表面的包覆层为聚苯胺(PANI).紫外—可见吸收光谱表明随着MWCNT含量的增加PANI的吸收发生红移且强度提高.扫描电子显微镜和透射电子显微镜观察发现，PANI/MWCNT复合体直径为40—70nm，其中PANI的包覆层厚度约为15—20nm.利用四波混频方法测试它们的三阶非线性光学系数，结果发现PANI/MWCNT复合体的三阶非线性光学系数比纯PANI大，这说明在MWC 关键词： 碳纳米管 聚苯胺 复合体 三阶非线性光学系数     

Proton energy loss in multilayer graphene and carbon nanotubes

Results of a study of electronic energy loss of low keV protons interacting with multilayer graphene targets are presented. Proton energy loss shows an unexpectedly high value as compared with measurements in amorphous carbon and carbon nanotubes. Furthermore, we observe a classical linear behavior of the energy loss with the ion velocity but with an apparent velocity threshold around 0.1?a.u., which is not observed in other carbon allotropes. This suggests low dimensionality effects which can be due to the extraordinary graphene properties.     

Tubular composite of doped polyaniline with multi-walled carbon nanotubes

We report on the synthesis of tubular composite of doped polyaniline (PANI) with carboxylic groups contained multi-walled carbon nanotube (MWNTs) by in situ polymerization. Based on the interaction between aniline monomers and c-MWNTs , aniline molecules were adsorbed and polymerized on the surface of c-MWNTs . The structural characterization showed that tubular composites are core (c-MWNTs )-shell (doped-PANI) structures with diameters of several tens of nanometers, and lengths of up to several hundreds of nanometers. The conductivities of these tubular composites are several times higher than that of PANI without MWNT, which will offer new application possibilities. PACS 81.05.Qk; 81.05.Tp     

Ultrasound-assisted synthesis of unzipped multiwalled carbon nanotubes/titanium dioxide nanocomposite as a promising next-generation energy storage material

Carbon-based systems have been discussed as prospective alternatives for conventional metal-based catalysts over the past decade. These studies were motivated by the abundance, low cost, lightweight and diversity of structural allotropes of carbon. We reported here the synthesis of a new type of unzipped multiwalled carbon nanotubes/titanium dioxide (UzMWCNT/TiO₂) nanocomposite by the two-stage procedure. By the modified Hummers method, multiwalled carbon nanotubes (MWCNTs) were converted to oxidized multi-walled carbon nanotubes (O-MWCNT). Then, through a facile ultrasound-assisted route prepared UzMWCNT/TiO₂ nanocomposite. For this, the oxidized multiwalled carbon nanotubes are treated with TiCl₄ under an ultrasonic probe for 3 h to generate UzMWCNT/TiO₂ and then explored its environmental friendliness and energy applications as a supercapacitor. This novel UzMWCNT/TiO₂ nanocomposite was characterized using XRD, TGA, FT-IR, Raman, TEM and EDX analysis. The electrochemical performance can be evaluated by using cyclic voltammetry (CV) and galvanostatic charging-discharging (GCD) study. Finally, the electrodes prepared using UzMWCNT/TiO₂ nanocomposite have been analyzed through electrochemical impedance spectroscopy (EIS) to probe the charge transfer characteristics and the results are consistent with other electrochemical measurements.     

Enhanced interlaminar fracture toughness of unidirectional carbon fiber/epoxy composites modified with sprayed multi-walled carbon nanotubes

A recently reported solvent spraying technique was used herein for incorporation of multi-walled carbon nanotubes (MWCNTs) on unidirectional carbon fiber/epoxy prepregs. The role of the agglomerates reduction of oxidized MWCNTs on Mode-I interlaminar fracture toughness (G_IC) of laminated composites was investigated using double cantilever beam tests. Multiscale laminate composites were fabricated using MWCNTs without and with an acid oxidation, agglomerates reduction (AR) and a sequential treatment based on oxidation and AR. For comparison, specimens without MWCNTs were also prepared and tested. Fourier transform infrared analysis shows evidence of an important amount of oxygenated functional groups on the surface of as-received and oxidized MWCNTs. The results also show Mode-I fracture toughness improvements for all the laminated composites compared to reference samples. A substantial 52% increase in the average G_IC initiation was achieved for laminated composites reinforced with oxidized AR-MWCNTs prepared with only 0.05 wt.% MWCNTs.     

Interfacial mechanical properties of carbon nanotube-deposited carbon fiber epoxy matrix hierarchical composites

Functionalized multiwalled carbon nanotubes were successfully deposited on carbon fibers using four different techniques including dip coating, hand layup, spray up and electrophoretic deposition (EPD). A uniform coating of nanotubes was achieved from EPD in comparison to other coating techniques. Later nanotube-coated fibers by EPD were introduced in epoxy resin to investigate interfacial mechanical properties of the developed hierarchical composites by vacuum bagging technique. The increases in flexural and interlaminar shear properties up to 15% and 18% were observed in composites containing nanotube-coated carbon fibers than composites with virgin carbon fibers, respectively. Microscopic observation revealed the proper impregnation of multiscale reinforcements, i.e., carbon fibers and carbon nanotubes, in resin along with the modification of fiber/matrix interface due to the presence of nanotubes at interface. Finally, the mechanisms for improved mechanical properties were identified along with the presentation of a schematic model for better understanding of the improved performance of hierarchical composite after depositing uniformly dispersed nanotubes on carbon fibers.     

In situ surface modification of natural fiber by conducting polyaniline

Newly modified biofibers made up of kenaf fibers (KF) and conducting polyaniline (PANI) were successfully prepared via in situ polymerization. Several characterization methods were done to elucidate the interaction between the KF surfaces and the in situ polymerized PANI. The PANI coated KF (KF/PANI) achieved new electronic properties, without sacrificing its mechanical properties and natural fiber characteristic. Initial mercerization on the KF yielded better PANI coated fibers compared to the untreated KF. Fiber bundle tensile test on the untreated KF/PANI revealed a drop in the unit break of about 48% compared to the untreated neat KF. Meanwhile, the mercerized KF/PANI showed reduction of about 17% compared to the uncoated mercerized KF. The mercerized KF/PANI exhibits polaronic transitions, existence of favorable IR peaks and Raman scattering, enhanced DC conductivity, and better morphological characteristic as a result of the in situ PANI coating. Such electronically modified natural fibers could be suitable as green conducting fillers in composites to replace other synthetic fibers.     

A study on the electrical conductivity of multi-walled carbon nanotube aqueous solution

The electrical conductivity was investigated for multi-walled carbon nanotubes (MWNTs) dissolved in chloroform and toluene, respectively. The electrical conductivity remarkably increased with increase in the content of MWNTs, which is in accordance with Archie's equation . Furthermore, a hypothesis of the electronic transport process was proposed to explain the difference between the solution and the solid compound. In addition, the temperature dependence of the electrical conductivity shows that log σ vs. 1/T exist in a good linear relationship. The activation energy of the electrical conductivity decreased with increase in concentration and an inflexion was observed at 60 °C in MWNT/toluene solution.     

Functionalization of carbon nanotubes/graphene by polyoxometalates and their enhanced photo-electrical catalysis

Carbon nanotubes and graphene are carbon-based materials, which possess not only unique structure but also properties such as high surface area, extraordinary mechanical properties, high electronic conductivity, and chemical stability.Thus, they have been regarded as an important material, especially for exploring a variety of complex catalysts. Considerable efforts have been made to functionalize and fabricate carbon-based composites with metal nanoparticles. In this review,we summarize the recent progress of our research on the decoration of carbon nanotubes/graphene with metal nanoparticles by using polyoxometalates as key agents, and their enhanced photo-electrical catalytic activities in various catalytic reactions. The polyoxometalates play a key role in constructing the nanohybrids and contributing to their photo-electrical catalytic properties.     

Improvement of the adhesion between polyaniline and commercial carbon paper by acid treatment and its application in supercapacitor electrodes

Commercial carbon paper was coated with polyaniline (PANI) using in situ polymerization of aniline. Prior to the PANI coating, acid treatment was performed to carboxylate the surface of the carbon paper for enhancing PANI adhesion by sonication of the carbon paper in a mixture of concentrated sulfuric and nitric acids. The loading mass density of PANI on the acid-treated carbon paper increased more than three times compared to that on the carbon paper without acid treatment. The specific capacitance also increased from 112 to 174 F/g in a two-electrode system (calculated using a total mass of carbon paper and PANI) due to better PANI coating on the acid-treated carbon paper. The simple acid treatment provides good adhesion of PANI to the commercial carbon paper and can be applied to prepare supercapacitor electrodes.     

Thermal properties of carbon nanotubes and nanotube-based materials

The thermal properties of carbon nanotubes are directly related to their unique structure and small size. Because of these properties, nanotubes may prove to be an ideal material for the study of low-dimensional phonon physics, and for thermal management, both on the macro- and the micro-scale. We have begun to explore the thermal properties of nanotubes by measuring the specific heat and thermal conductivity of bulk SWNT samples. In addition, we have synthesized nanotube-based composite materials and measured their thermal conductivity. The measured specific heat of single-walled nanotubes differs from that of both 2D graphene and 3D graphite, especially at low temperatures, where 1D quantization of the phonon bandstructure is observed. The measured specific heat shows only weak effects of intertube coupling in nanotube bundling, suggesting that this coupling is weaker than expected. The thermal conductivity of nanotubes is large, even in bulk samples: aligned bundles of SWNTs show a thermal conductivity of >200 W/m K at room temperature. A linear K(T) up to approximately 40 K may be due to 1D quantization; measurement of K(T) of samples with different average nanotube diameters supports this interpretation. Nanotube–epoxy blends show significantly enhanced thermal conductivity, showing that nanotube-based composites may be useful not only for their potentially high strength, but also for their potentially high thermal conductivity. Received: 17 October 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Electron microscopy characterization of nanostructured carbon obtained from chlorination of metallocenes and metal carbides

In this work we report some new well-defined carbon nanostructures produced by direct chlorination of metallocenes (ferrocene and cobaltocene) and NbC, at temperatures from 100 to 900 degrees C. Thus, amorphous carbon nanotubes with variable dimensions depending on reaction temperature were produced from ferrocene. When cobaltocene is the carbon precursor the main product are solid amorphous nanospheres. The high refractory metal carbide NbC as carbon source favours the growth of nanospherical cabbage-like particles with a higher degree of graphene sheets order. Besides, NbC crystallites encapsulated in an amorphous carbon shell were also found at lower temperatures (T< or =700 degrees C).