工业级原料制备碳纳米管的研究

为降低碳纳米管批量制备的原料成本,以焦化苯和二茂铁为主要原料(工业级),采用浮游催化热解法制备碳纳米管,用TEM、SEM、Raman、XRD等对产物的形貌和结构进行观察和表征,着重讨论了二茂铁的分解温度和苯的挥发温度对碳纳米管的制备及其形貌的影响,并对其影响机理进行了分析.研究表明:在噻吩体积分数为0.55 mL/100 mL苯、炉膛反应温度为1170℃的前提下,当二茂铁的分解温度为150℃、苯的挥发温度为50℃时,用工业级原料完全可以制备出碳纳米管,此时,碳纳米管的内径分布在0.88~1.15 nm.     

Fe-Mo/Al_2O_3催化剂催化分解甲烷制备碳纳米管:温度对碳管结构的影响

利用化学气相沉积法,以Fe-Mo/Al_2O_3为催化剂,催化分解甲烷气体制备碳纳米管(CNTs).研究了温度,反应时间和气体流速对碳纳米管结构的影响.结果显示:温度是影响碳纳米管壁厚的关键参数.低温导致壁厚为2 nm～7 nm的多壁碳纳米管(MWCNTs)的生成.相对地,高温有利于双壁碳纳米管(DWCNTs)的生长,而更高的温度促使单壁碳纳米管(SWCNTs)的产生.进一步升高温度,得到了壁厚为3 nm～15 nm的MWCNTs和大的炭颗粒.     

Fabrication of highly crystalline NbOx nanotube/cup-stacked CNT nanocomposites

Carbon nanotubes (CNTs) are promising catalyst supports for fuel cell applications. Metal oxide/CNT nanocomposites are also being studied for dye-sensitized solar-cell, photocatalyst, and sensor applications. The fabrication of nanocomposites consisting of highly crystalline NbOx nanotubes and cup-stacked carbon nanotubes (CSCNTs) is reported herein. The CSCNTs were selected for the carbon materials because of their distinctive structure. The CSCNTs were photochemically treated with vacuum ultraviolet light, which increased the amount of oxygen-containing functional groups therein. NbOx nanotubes with no defects were successfully prepared with the chemical treatment of highly crystalline, layered, flux-grown K4Nb6O17 crystals. First, K4Nb6O17 crystals were grown from a KCl flux at a holding temperature of 800 degrees C. Next, NbOx nanosheets were prepared from the layered K4Nb6O17 crystals via a two-step exfoliation process, which consists of proton exchange in an acid solution and intercalation of the tetrabutylammonium ions. The NbOx nanosheets were rolled up into nanotubes with diameters of about 20 nm and lengths of 100-500 nm on the surfaces of the CSCNTs; thus, unique and complex NbOx/CSCNT nanocomposites were successfully fabricated.     

HRTEM observations on composites of tin and tin dioxide nanoparticles dispersed on carbon nanotubes by single-atoms-to-clusters method

Nano-composites of tin and tin dioxide particles were synthesized on carbon nanotubes by the single-atoms-to-clusters (SAC) method, and their structures were investigated by high-resolution transmission electron microscopy. By changing the heat-treatment temperature during the SAC process, two different types of samples were obtained. The samples prepared around 450 K were aggregates of 2–4 nm-sized tin dioxide nanoparticles, and their size distributions on carbon nanotubes are in the range 20–40 nm. The other samples formed above 600 K had a core–shell structure of diameter 20–40 nm. The core and shell were made of tin single crystal and disordered oxidized tin, respectively. The thickness of the oxidized layers was ca. 4 nm.     

Physical properties of CVD boron-doped multiwalled carbon nanotubes

The effects of boron doping and electron correlation on the transport properties of CVD boron-doped multiwalled carbon nanotubes are reported. The boron-doped multiwalled carbon nanotubes were characterized by TEM as well as Raman spectroscopy using different laser excitations (viz. 488, 514.5 and 647 nm). The intensity of the D-band laser excitation line increased after the boron incorporation into the carbon nanotubes. The G-band width increased on increasing the boron concentration, indicating the decrease of graphitization with increasing boron concentration. Electrical conductivity of the undoped and boron-doped carbon nanotubes reveal a 3-dimensional variable-range-hopping conductivity over a wide range of temperature, viz. from room temperature down to 2 K. The electrical conductivity is not found to be changed significantly by the present levels of B-doping. Electron Paramagnetic Resonance (EPR) results for the highest B-doped samples showed similarities with previously reported EPR literature measurements, but the low concentration sample gives a very broad ESR resonance line.     

HRTEM observations on composites of tin and tin dioxide nanoparticles dispersed on carbon nanotubes by single-atoms-to-clusters method

Nano-composites of tin and tin dioxide particles were synthesized on carbon nanotubes by the single-atoms-to-clusters (SAC) method, and their structures were investigated by high-resolution transmission electron microscopy. By changing the heat-treatment temperature during the SAC process, two different types of samples were obtained. The samples prepared around 450 K were aggregates of 2-4 nm-sized tin dioxide nanoparticles, and their size distributions on carbon nanotubes are in the range 20-40 nm. The other samples formed above 600 K had a core-shell structure of diameter 20-40 nm. The core and shell were made of tin single crystal and disordered oxidized tin, respectively. The thickness of the oxidized layers was ca. 4 nm.     

Comparison of Fe/Al/sub 2/O/sub 3/ and Fe, Co/Al/sub 2/O/sub 3/ catalysts used for production of carbon nanotubes from acetylene by CCVD

Characterization of iron containing alumina supported catalysts was performed by transmission electron microcopy (TEM), Mo/spl uml/ssbauer, and XPS spectroscopy during formation of multiwall carbon nanotubes from acetylene at 1000 K. TEM images showed that carbon fibers (outer diameter is around 20-40 nm) were generated on Fe/Al/sub 2/O/sub 3/ samples while on the bimetallic Fe,Co/Al/sub 2/O/sub 3/ carbon nanotubes with an average diameter of 8-12 nm were formed. XPS spectra revealed that Fe-Co alloy formed during the interaction of Fe,Co/Al/sub 2/O/sub 3/ and acetylene at 1000 K. The formation of the bimetallic alloy was proven by Mo/spl uml/ssbauer spectroscopy as well.     

Synthesis, electrical and magnetic characterization of core-shell silicon carbo-nitride coated carbon nanotubes

We demonstrate synthesis, electrical and magnetic characterization of silicon carbo-nitride (SiCN) coated multiwalled carbon nanotubes in a core-shell structure. The core formed by a carbon nanotube had a diameter in the range of 10-100 nm. The shell was synthesized by pyrolysis of an SiCN precursor on the surface of carbon nanotubes. Electrical resistivity of an individual composite nanotube was measured to be ~ 2.55 × 10³ Ω cm. The magnetic measurements performed by a superconducting quantum interference device on the composite nanotubes in the temperature range of 5-300 K show a reduced coercive field with increasing temperatures. The monolayer thick coating of an ultra high temperature multifunctional ceramic SiCN makes these composite nanotubes very promising for sensing applications in harsh environments.     

Carbon nanotubes grafted on silicon oxide nanowires

In this article, we report the grafting of multi-walled carbon nanotubes on silica nanowires by directly growing nanotubes on the surfaces of the nanowires via chemical vapor deposition (CVD) using ferrocene and xylene as Fe catalyst precursor and carbon source, respectively. The grafted carbon nanotubes are a few micrometers long with diameters of 10 to approximately 30 nm, and grow uniformly along the lengths of the nanowires. The distribution density of the grafted carbon nanotubes on the silica nanowires can be tuned by simply adjusting the CVD growth temperature. Our method provides a simple approach for synthesizing nanometer scale grafted heterostructures between nanotubes and nanowires, which could be used to design and construct high-performance filters, chemical sensors and reinforced composites.     

Room-temperature deposition of carbon nanomaterials by excimer laser ablation

Numerous investigators have reported on pulsed laser deposition of carbon nanotubes, mostly using the Nd:YAG laser for ablation. In all cases the depositions have been conducted at high-temperatures and high pressures. Here we report on the deposition of carbon nanostructures at room temperature using a 248 nm excimer laser nm to ablate mixed graphite-nickel/cobalt targets. We find that the formation of the carbon nanomaterials is dependent on the particular ambient gas employed. In O₂ gas, carbon nanotubes and nano-onions are produced. The nanotubes have notably large channel diameters of 100-200 nm and the nano-onion structures are 100-200 nm in diameter, also much larger than previously observed. High-resolution, in-situ, time-resolved emission spectroscopy has been used to follow the production of molecular carbon species such as C₂ and C₃, as well as metals such as Ni or Co in the different ambients employed. Spectral modeling reveals significant differences in the vibrational-rotational temperatures of C₂ spectra in O₂ versus Ar. Mechanistic details of the formation of carbon nanotubes and nano-onions, and in-situ optical emission spectroscopy are described.     

环己烷浮游催化法在碳纤维表面生长碳纳米管

以环己烷为碳源、二茂铁为催化剂前躯,采用浮游催化法成功的在碳纤维表面生长了碳纳米管(CNT),制备了多尺度杂化材料CNTs/CF。实验重点考察了反应温度、二茂铁浓度、载气等参数对CNT在纤维表面生长的影响,通过扫描电镜(SEM)、投射电镜(TEM)研究了CNTs/CF的形貌及产物CNT的微观结构。当固定反应温度为820℃、二茂铁-环己烷浓度为2g/100mL时,随着氢气在载气中含量在0～100%范围内变化,产物CNT直径亦有86nm降低至39nm。通过单丝拉伸测试发现,相比初始碳纤维,不同长度的CNTs/CF单纤维强度下降幅度均在10%以内。     

Improving the Economic Values of the Recycled Plastics Using Nanotechnology Associated Studies

Recycled polystyrene （PS） cups were chopped up and separately incorporated with multiwall carbon nanotubes （MWCNTs） and NiZn ferrite （Ni0.6Zn0.4Fe2O4） nanoparticles prior to electrospinning under different conditions. These nanoscale inclusions were initially dispersed well in dimethylformamide （DMF）, and then known amounts of the recycled PS pieces were added to the dispersions prior to 30 min of sonication followed by 4 h of high-speed agitation at 750 r/min. The thermal, dielectric, surface hydrophobic, and magnetic properties of the resultant nanocomposite fibers were determined by thermal comparative, capacitance bridge, vibrating sample magnetometer （VSM）, and goniometer techniques, respectively. Test results confirmed that the physical properties of recycled nanofibers were significantly increased as a function of the inclusion concentrations, which may be because of their excellent properties. The consumption of polymeric products as well as their waste materials has dramatically grown worldwide. Although plastic recycling, reprocessing, and reusing rates are growing, the physical properties and economic value of recycled plastics are significantly low. Consequently, this work provides a detailed explanation of how to improve recycled plastics, making them into highly valued new nanoproducts for various industrial applications, including filtration, textile, transportation, construction, and energy.     

Controlling electron-beam-induced carbon deposition on carbon nanotubes by Joule heating

Electron-beam-induced deposition (EBID) of carbon on the surface of carbon nanotubes was well controlled by passing different electrical currents through the nanotubes. The control is due to Joule heating and the temperature of the carbon nanotubes was estimated. The deposition rate was found to increase and then decrease with the temperature and was maximized at about 310?K and approached zero at about 400?K. The method can be used to control the deposition rate of EBID in nanowelding and nanofabrication and to eliminate amorphous carbon contamination in in situ study of nanostructures.     

The growth of aligned carbon nanotubes on quartz substrate by spray pyrolysis of hexane

Vertically aligned multiwall carbon nanotubes were grown by spray pyrolysis of hexane as the carbon source in the presence of ferrocene as catalyst precursor on a quartz substrate. In recent work we used optimal experimental parameters for the feeding method, reactor conditions, reaction temperature and time, concentration of catalyst and flow rate of feed and gas. The process parameters were chosen so as to obtain multiwall carbon nanotubes and aligned multiwall carbon nanotubes. The tubes are around 15-80?nm in diameter. The morphology and structure of the samples were characterized by x-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy analyses.     

Hydrogen storage in carbon nanotubes through the formation of stable C-H bonds

To determine if carbon-based materials can be used for hydrogen storage, we have studied hydrogen chemisorption in single-walled carbon nanotubes. Using atomic hydrogen as the hydrogenation agent, we demonstrated that maximal degree of nanotube hydrogenation depends on the nanotube diameter, and for the diameter values around 2.0 nm nanotube-hydrogen complexes with close to 100% hydrogenation exist and are stable at room temperature. This means that specific carbon nanotubes can have a hydrogen storage capacity of more than 7 wt % through the formation of reversible C-H bonds.     

Carbon nanotubes synthesis in microwave plasma torch at atmospheric pressure

Well aligned multi-walled carbon nanotubes were synthesized at atmospheric pressure using a microwave plasma torch on silicon substrates with silicon oxide buffer layer and catalyst overlayer in the mixture of argon, hydrogen and methane. Iron or nickel was used as catalysts. The optimum substrate temperature for the deposition on Si/SiO₂/Fe substrates was about 970 K. In this case SEM micrographs of the deposits revealed a presence of vertically aligned nanotubes with the diameters around 15 nm. TEM micrographs showed a presence of amorphous carbon particles in the samples and some defects in the wall structure of the produced nanotubes. In Raman spectra two peaks at 1332 and 1584 cm⁻¹ were observed. The CNTs were also synthesized on the substrates without SiO₂ buffer layer but their quality was lower. The synthesis with Ni instead of Fe catalyst required lower temperature and the alignment of the nanotubes was worse. The deposition process was monitored by optical emission spectroscopy. Atomic lines of hydrogen and argon, an emission of CN due to a presence of nitrogen impurities from atmosphere, a weak molecular band of CH and strong C₂ emission were detected in the spectra.     

Effects of hydrogen on the formation of aligned carbon nanotubes by chemical vapor deposition

Well-aligned carbon nanotubes with controllable properties were grown on porous silicon substrates by thermal chemical vapor deposition. The morphologies of the carbon nanotubes were varied with the introduction of H2 during the catalyst activation and/or carbon nanotube growth processes. It was found that H2 promotes the growth of carbon nanotubes while preventing the formation of spherical amorphous carbon particles. Without the introduction of H2 during the C2H2 thermal decomposition, aligned carbon nanotubes mixed with spherical carbon particles were formed on the substrate. However, with the introduction of H2, pure carbon nanotubes were synthesized. These nanotubes also had uniform diameters of 10-20 nm, which is much smaller than nanotubes synthesized without H2. The average growth rate of nanotubes was also affected by the introduction of hydrogen into the reaction chamber during nanotube growth. With the addition of hydrogen, the average growth rate changed from 78 nm/s to 145 nm/s. A possible growth mechanism, including the effect of a high ratio of H2 to C2H2, is suggested for the growth of these well-aligned carbon nanotubes with uniform diameters.     

Direct ion beam deposited carbon films and clusters

Carbon films and clusters have been formed by direct ion beam deposition. In all experiments crystalline n-Si 〈1 0 0〉 wafers with the 300 nm thermal SiO₂ film have been used as substrates. Effects of thermally microstructured Ni and substrate temperature were studied. Chemical structure of the carbon films was investigated using Raman spectroscopy. Surface morphology was studied by atomic force microscopy (AFM). Supplemental research on sheet resistance of the films has been performed. Rough diamond-like carbon film was grown onto the catalytic layer at 400 K temperature, and surface of the diamond-like carbon film deposited directly onto the SiO₂ layer at 400 K temperature was very smooth. At 750 K growth of the array of cylindrically shaped clusters was observed by AFM in the case of catalytically assisted deposition. Raman spectra of deposited films were typical for glassy carbon and/or carbon nanotubes with the carbonaceous deposits. Catalyticless deposition at 750 K temperature resulted in the formation of the conductive polymer-like carbon film with the graphite clusters in it.     

Modifying the Properties of Tungsten Based Plasma Facing Materials with Single-Wall Carbon Nanotubes

Tungsten is one of the best candidates for plasma-facing components in fusion reactors owing to its unique properties. But disadvantages such as its brittleness and high ductile-to-brittle transition temperature have restricted its fusion energy application. Single-walled carbon nanotubes （SWCNTs） have the potential to be used as reinforcements due to their excellent mechanical properties. A new method of modifying the properties of tungsten by doping with SWCNTs was introduced. An efficient way of dispersing SWCNTs into the tungsten matrix with strong interfaces by heterocoagulation and ultrasonication was employed, and hot explosive compaction （HEC） technology was selected to compact and sinter the composite powders. The sintering properties, microstructure, densification effect, thermal conductivity, hardness and fracture toughness of the obtained SWCNTs/W bulk samples were tested, and compared with pure tungsten. The influences of SWCNTs on these properties and the main toughening mechanism of SWCNTs in a tungsten matrix were discussed.     

Synthesis and thermal transport studies of nanofluids based on metal decorated photochemically oxidized multiwalled carbon nanotubes

Nanoparticle fluid suspensions were prepared using photochemically functionalized multiwalled carbon nanotubes in polar base fluids. Multiwalled carbon nanotubes prepared by catalytic chemical vapour deposition technique have been functionalized by irradiating with ultraviolet light of wavelength 254 nm. The photochemical oxidation of multiwalled carbon nanotubes under UV irradiation introduces oxygen containing functional groups onto the surface of the nanotubes, generating new defects on their structure. Silver nanoparticles have been deposited over multiwalled carbon nanotubes by chemical method. The enhancement in thermal conductivity of the prepared nanofluids using functionalized multiwalled carbon nanotubes and Ag nanoparticles deposited functionalized multiwalled carbon nanotubes with volume fraction, temperature and aspect ratio has been demonstrated. Silver deposited functionalized multiwalled carbon nanotubes based nanofluids in DI water with 0.02% volume fraction exhibit a thermal conductivity enhancement of 9.9% and 47% at room temperature and at 50 degrees C respectively.