碳纳米管端口的场蒸发

将单根多壁碳纳米管(multi-walled carbon nanotube,MWCNT)组装在W针尖上并送入超高真空场发射/场离子显微镜(Ultrahigh Vacuum Field-emission/Field-Ion microscope,UHV-FEM/FIM)进行场蒸发及场发射研究.结果表明,场蒸发可以降低MWCNT的逸出功,从而增强其场发射能力.估算MWCNT的蒸发场低于1.3×10⁸V·cm^-1,且在此场强下的平均蒸发速率为9.4nm·min^-1.定性讨论了MWCNT的蒸发场大大低于C的理论值的原因.首先,通过场解吸获得的清洁端口上有较多悬挂键,平均每个C原子的配位数较小,所以升华热较低.其次,可能存在于MWCNT中的H原子会在强场下碰撞端口的C原子,使其更易蒸发.以上结果显示了利用场蒸发剪短碳纳米管从而改善其场发射特性的可行性. 关键词： 碳纳米管 场蒸发 场发射     

Facile synthesis of a sulfur/multiwalled carbon nanotube nanocomposite cathode with core–shell structure for lithium rechargeable batteries

A novel sulfur/multiwalled carbon nanotube nanocomposite (S/MWCNT) was prepared by a facile quasi-emulsion template method in an O/W system. Transmission and scanning electronic microscopy show the formation of a highly developed core–shell tubular structure consisting of S/MWCNT composite with uniform sulfur coating on its surface. The homogenous dispersion and integration of MWCNT in the S/MWCNT composite create a highly conductive and mechanically flexible framework, enhancing the electronic conductivity and consequently the rate capability of the material. The S/MWCNT composite cathode could deliver a stable discharge (the fifth cycle) capacity of about 903 mAh g^?1 at 0.1 C, 751 mAh g^?1 at 0.5 C, and 631 mAh g^?1 at 1 C.     

多壁碳纳米管束储氢机理的X射线吸收谱研究

采用X射线吸收精细结构光谱探索性地研究了多壁碳纳米管束.在多壁碳纳米管束不同入射角的X射线吸收精细结构光谱中，观察到C—H σ^*共振峰强度随入射角的变化而发生变化.在常温常压下出现C—H键可能与多壁碳纳米管束中存在缺陷有关，缺陷数量越大C—H σ^*共振峰的强度越大.光谱中C—C π^*和C—C σ^*共振峰强度的变化趋势都不同于C—H σ^*共振峰，这有力地证明了在常温常压条件下氢原子是吸附在多壁碳纳米 关键词： X射线吸收精细结构光谱 碳纳米管 储氢 化学吸附     

Synthesis and elevated temperature performance of a polypyrrole-sulfur-multi-walled carbon nanotube composite cathode for lithium sulfur batteries

A sulfur-multi-walled carbon nanotube composite (S/MWCNT) was prepared using a two-step procedure of liquid-phase infiltration and melt diffusion. Polypyrrole (PPy) conductive polymer was coated on the surface of the as-prepared S/MWCNT composite by in situ polymerization of pyrrole monomer to obtain PPy/S/MWCNT composite. The composite materials were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The electrochemical performance of the as-prepared cathode material was investigated at 25, 40, and 70 °C at various rates. It was found that temperature has dual effects on the performance of Li/S cells. Increasing the temperature, on one hand, facilitates the lithium ion transport through the cathode and, on the other hand, leads to faster dissolution of active material into the electrolyte. The PPy coating can effectively trap polysulfides in its porous structure, even at elevated temperatures, leading to the improvement of the discharge capacity, the cycle stability, and the coulombic efficiency. The electrochemical impedance spectroscopy (EIS) results reveal that the PPy coating reduces the formation of passive layer on the cathode surface, even at high temperatures, resulting in a better elevated temperature performance. A high reversible capacity of 945 mAh g^?1 was maintained after 50 cycles for the PPy/S/MWCNT composite at 70 °C at a rate of 0.5 C.     

Designing of multiwalled carbon nanotubes reinforced low density polyethylene nanocomposites for suppression of electromagnetic radiation

High aspect ratio multi-walled carbon nanotubes (MWCNTs) reinforced low density polyethylene (LDPE) composites were prepared by solvent casting followed by compression molding technique. Electromagnetic interference (EMI) shielding effectiveness (SE) of these composites was investigated in the frequency range of 12.4?C18 GHz (Ku-band) for the first time. The experimental results indicate that the EMI-SE of these composites is sensitive to the MWCNT loading. The average value of EMI-SE reaches 22.4 dB for 10 wt% MWCNT-LDPE composites, indicating the usefulness of this material for EMI shielding in the Ku-band. The main reason for improved SE has been attributed to significant improvement in the electrical conductivity of the composites by 20 orders of magnitude, i.e., from 10^?20 for pure LDPE to 0.63 S/cm for MWCNT-LDPE, which is three order of magnitude higher than the previous reports for MWCNT-LDPE composites. Differential scanning calorimetry of the MWCNT-LDPE composites showed around 37% improvement in the crystalline contents over pure LDPE samples which resulted into enhanced thermal stability of the composites. The thermal decomposition temperature of LDPE is shifted by 40 °C on addition of 5 wt% MWCNT. The studies therefore show that these composite can be used as light weight, thermally stable EMI shielding, and antistatic material.     

Effect of dispersion state of carbon nanotube on the thermal conductivity of poly(dimethyl siloxane) composites

Herein, the effect of dispersion uniformity of multi-walled carbon nanotube (MWCNT) on the thermal conductivity of poly(dimethyl siloxane) (PDMS) composites was investigated by comparing experimentally obtained and calculated results based on simple models. Two different MWCNTs, i.e., raw and oxidized/masterbatched MWCNTs, were used and compared. For raw MWCNT, the dispersion in PDMS was poor, resulting in the significant reduction in the aspect ratio of MWCNT. However, for composites using masterbatched MWCNT, the thermal conductivity was always about 10% greater than those prepared with raw MWCNT and the aspect ratio calculated by the model equation was also 1.7 times greater. Above 1.5 phr masterbatched MWCNT concentrations, the aspect ratio of 430 was maintained. Finally, the results suggest that the thermal conductivity can be correlated with the degree of dispersion and aspect ratio obtained from the model equation used.     

Characterisation of carbonaceous materials using Raman spectroscopy: a comparison of carbon nanotube filters,single‐ and multi‐walled nanotubes,graphitised porous carbon and graphite

Multi‐walled carbon nanotube (MWCNT) filters have been recently synthesised which have specific molecular filtering capabilities and good mechanical strength. Optical and scanning electron microscopy (SEM) reveals the formation of highly aligned arrays of bundles of carbon nanotubes having lengths up to 500 µm. The Raman spectra of this material along with four other carbonaceous materials, commercially available single‐walled carbon nanotubes (SWCNTs) and MWCNTs, graphitised porous carbon (Carbotrap) and graphite have been recorded using two‐excitation wavelengths, 532 and 785 nm, and analysed for band positions and shape with special emphasis paid to the D‐, G‐ and G′‐bands. A major difference between the different MWCNT varieties analysed is that G‐bands in the MWCNT filters exhibit almost no dispersion, whereas the other MWCNTs show a noticeable dispersive behaviour with a change in the excitation wavelength. Spectral features similar to those of the MWCNT filter varieties were observed for the Carbotrap material. From the line shape analysis, the intensity ratio, I_D/I_G, of the more ordered MWCNT filter material using the integral G‐band turns out to be two times lower than that of the less ordered MWCNT filter product at both excitation wavelengths. This parameter can, therefore, be used as a measure of the degree of MWCNT alignment in filter varieties, which is well supported also by our SEM study. Copyright © 2008 John Wiley & Sons, Ltd.     

多壁碳纳米管薄膜的压阻效应研究

对多壁碳纳米管薄膜的压阻效应进行了研究. 实验所用的多壁碳纳米管用热灯丝化学气相沉积法合成, 压阻效应用三点弯曲法测量. 研究发现: 在室温下与500微应变内, 原始的多壁碳纳米管薄膜无明显压阻效应, 而经化学修饰处理的碳纳米管膜的压阻因子最高可达120左右, 大大超过多晶硅(Si)在35°C时的压阻因子30, 并且压阻因子与制备方法密切相关. 重点讨论了多壁碳纳米管薄膜产生压阻效应的机制.     

Fabrication of cross-linked multi-walled carbon nanotube coatings with improved adhesion and intrinsic strength by a two-step synthesis: electrochemical deposition and hyperthermal proton bombardment

A two-step synthesis for multi-walled carbon nanotube (MWCNT) coating was reported that includes an electrochemical deposition followed by 10 eV hyperthermal proton bombardment at a dose as low as 1×10¹⁶ H⁺/cm². Electrochemical deposition ensures an improved adhesion of MWCNT coating on metal substrates, while hyperthermal proton bombardment effectively induces inter-chain cross-linkages among MWCNTs, leading to a coating with both higher stiffness and mechanical strength. It was found experimentally that the MWCNT film made by the proposed two-step synthesis can better resist spinning and ultrasonic rinsing in both organic (hexane) and aqueous (water) media. PACS 61.46.+w; 68.35.Np; 68.37.Ps; 81.15.Pq     

Continuous dry dispersion of multi-walled carbon nanotubes to aerosols with high concentrations of individual fibers

The assessment of the toxicity of airborne nanofibers is an important task. It relies on toxicological inhalation studies and validated exposure measurement techniques. Both require nanofiber-containing aerosols of known morphological composition and controlled fraction of individual fibers. Here, a dry powder dispersion method is presented that operates with mixtures of nanofibers and microscale beads. Aerosolization experiments of mixtures of multi-walled carbon nanotubes (MWCNTs) and glass beads that were continuously fed into a Venturi nozzle enabled high generation rates of aerosols composed of individual and agglomerate nanofiber structures. The aerosol process achieved good stability over more than 2 h with respect to concentration and aerodynamic size distribution. Its operation duration is limited only by the reservoir volume of the cyclone used to separate the beads from the aerosol. The aerosol concentration can be controlled by changing the mass ratio of MWCNTs and glass beads or by adapting the mass feed rate to the nozzle. For two agglomerated MWCNT materials, aerosol concentrations ranged from 1700 to 64,000 nano-objects per cm³. Comprehensive scanning electron microscope analysis of filter samples was performed to categorize and determine the morphological composition of the aerosol, its fiber content as well as fiber length and diameter distributions. High fractions of individual fibers of up to 34% were obtained, which shows the setup to be capable of dispersing also highly tangled MWCNT agglomerates effectively.     

Nitrobenzene electrochemical sensor based on silver nanoparticle supported on poly-melamine functional multi-walled carbon nanotube

A novel and convenient electrochemical sensor, based on multi-walled carbon nanotube (MWCNT)–poly-melamine(PMel)–silver nanoparticle (AgNP) composite-modified glassy carbon electrode (GCE), was fabricated for the determination of nitrobenzene (NB). The modified electrode not only played an efficient electrocatalytic role for the reduction of NB but also significantly reduced the overpotential of NB, and the peak current increased greatly compared with bare GCE or other modified electrodes. The excellent performance of NB sensor can be ascribed to the synergistic effect between MWCNT and AgNP. The synergistic effect promoted the electron transfer between MWCNT and AgNP significantly and enhanced the electrochemical reduction ability of NB remarkably. Besides, PMel has huge nitrogen and amine groups, which contributes to the dispersion of silver nanoparticles and also improves the electrocatalytic activity and sensitivity of the sensor. The integration of PMel/MWCNT with AgNP provided a high-performance platform for the NB determination. Under the optimized experimental conditions, the developed sensor showed a wide linear calibration ranges from 20 to 1000 μM and from 1000 to 6000 μM, with a low detection limit (0.55 μM) for the detection of NB. At the same time, the modified electrode exhibited good stability and reproducibility and acceptable selectivity. Moreover, the proposed sensors were successfully employed to determine NB in real samples, and the recoveries were between 97.2 and 104.6 %.     

Reduced graphene oxide/MWCNT hybrid sandwiched film by self-assembly for high performance supercapacitor electrodes

A reduced graphene oxide/multiwalled carbon nanotube (RGO/MWCNT) hybrid sandwiched film with different MWCNTs content was prepared by vacuum-assisted self-assembly from a complex dispersion of graphene oxide (GO) and MWCNTs followed by heat-treating at 200 °C for 1 h in a vacuum oven to reduce the GO into RGO. The free-standing RGO/MWCNT hybrid sandwiched film before heat-treatment showed a layered structure with an entangled network of MWCNTs sandwiched between the GO sheets. This unique structure not merely contribute to remove the oxygen-containing groups in GO during the heat-treatment, but also decrease the defects for electron transfer between RGO layers, which enhances the electrochemical capacitive performances of graphene-based films. A specific capacitance up to 379 F/g was achieved based on RGO/MWCNT with 30 % MWCNTs mass fraction at 0.1 A/g in a 6 M KOH electrolyte. The excellent performance of RGO/MWCNT hybrid sandwiched film signifies the importance of controlling the surface chemistry and sandwiched nanostructure of graphene-based materials.     

Effect of cross-linkable polymer on the morphology and properties of transparent multi-walled carbon nanotube conductive films

In this study, we fabricated optically transparent and electrically conductive multi-walled carbon nanotube (MWCNT) thin films using a spray-coating technique. The transparency and the electrical resistance of thin film are dependent on the nanotube content deposited on the polyethylene terephthalate (PET) substrate. Poly(acrylic acid) (PAA) and poly(N-vinyl pyrrolidone) (PVP) were used as adhesion promoters to improve MWCNT coating more significantly. The cross-linked polymer resulted in a superior bond between the MWCNTs and the substrates. The surface electrical resistance was significantly lower than the original sheet after nitric acid (HNO₃) treatment because of the removed surfactant and the increased interconnecting networks of MWCNT bundles, thus improving the electrical and optical properties of the films. Stronger interaction between the MWCNTs and the substrates resulted in lower decomposition of the polymer chain and less amounts of MWCNTs separated into the HNO₃ solution. The lower sheet electrical resistance of PVP/PAA-g-MWCNT conductive films on the PET substrate was because of a more complete conductive path with the cross-linked polymer than that without. Such an improved sheet of electrical resistance varied from 8.83 × 10⁴ Ω/□ to 2.65 × 10³ Ω/□ with 5.0 wt.% PVP/PAA-g-MWCNT sprayed on the PET after acid treatment.     

Milling and dispersion of multi-walled carbon nanotubes in texanol

Rheological results were used to determine the optimum type of dispersant and its concentration for six commercial dispersants for the dispersion of multi-walled carbon nanotube (MWCNT) agglomerates in texanol. An unsaturated polycarboxylic acid copolymer (BYK P-104) exhibited the optimum performance with the lowest MWCNT slurry viscosity in texanol. The cutting and dispersion efficiencies of MWCNTs with 20 wt.% of BYK P-104 dispersant were compared using conventional ball milling and high energy milling, whereby the latter was found to be more effective. High energy milling for 2 h produced a large portion of MWCNT agglomerates smaller than 150 nm, showing a drastic increase in slurry viscosity due to the dispersion into individual CNTs. On the other hand, 120 h ball milling was required to achieve the agglomerate size of 300 nm with less viscosity increase upon milling. Decrease in the degree of MWCNT crystallinity was observed by both milling, even though 2 h high energy milling showed slightly less damage than 120 h ball milling based on XRD and Raman spectroscopy results.     

不同参数多壁碳纳米管的拉曼光谱研究

拉曼光谱是进行碳材料结构与性质研究的有力手段,为了研究多壁碳纳米管(MWCNT)的管径和长度对其拉曼光学性质的影响,本研究对一系列不同管径和长度的多壁碳纳米管进行拉曼光谱的测试和分析。研究发现: 与高取向的石墨相比,多壁碳纳米管一阶拉曼光谱的G峰中心和D峰中心都会向低波数发生不同程度的红移;MWCNT两个主要特征峰(G峰和D峰)峰强在其他条件相同的情况下,与MWCNT的管径成正比,与长度成反比;G峰的频移与MWCNT的管径和长度两个因素密切相关,与管径成反比关系(这与单壁碳纳米管的径向呼吸模有着一致的结果),与管长成正比关系,而D 峰的频移受MWCNT的管径和长度的影响很弱,并对此现象进行了初步分析。在此基础上,我们以MWCNT的长径比为横坐标,G峰频移为纵坐标作图,进行线性拟合,得到了G峰频移与长径比成一定的线性递增关系。采用同样的分析方法,我们将G峰和D峰强度分别对MWCNT的长径比作图,进行线性拟合,得到了G峰和D峰强度分别与MWCNT的长径比成一定的线性递减关系。     

Viscoelastic and Dielectric Behavior of Poly(1‐Butene)/Multiwalled Carbon Nanotube Nanocomposites

Linear viscoelastic properties and dielectric behavior of poly(1‐butene)/multiwalled carbon nanotube (MWCNT) nanocomposites were investigated. Dynamic mechanical analysis showed significant increase in storage modulus in the rubbery regime. The tan δ peak temperature remained constant; however, the peak intensity was lowered for the nanocomposites. In melt rheological studies the nanocomposites showed a shift in crossover frequency to the lower side, suggesting delayed relaxation of the molecular chains in the presence of MWCNT and this shift was found to depend on the content of MWCNT. The dielectric constant increased from 2.2 to 70 for the nanocomposite with 7 wt. % MWCNT. The electrical conductivity increased significantly, from 10^?15 to 10^?3 S/cm. The results of rheology and dielectric studies indicate that a percolation network is formed that is responsible for the observed changes.     

Characterization of carbon nanotube filters and other carbonaceous materials by Raman spectroscopy—II: study on dispersion and disorder parameters

Recently, we have reported on the characterization of various carbonaceous materials including multiwalled carbon nanotube (MWCNT) filters, which have specific molecular filtering capabilities and good mechanical strength and can be produced in bulk as highly aligned arrays of bundles of CNTs. We have extended our studies using Fourier transform‐Raman spectroscopy with 1064 nm excitation wavelength and a rotating sample holder in the region 1000–2800 cm⁻¹, in addition to 532 and 785 nm, which were used for Raman excitation in our previous study. Raman spectra were analyzed for band positions and line shape with special emphasis on the D‐, G‐ and G′‐ bands. For the single‐walled species, Carbotrap and graphite spectra were also recorded with 488 nm excitation. A dispersion study has been made from the Raman data available with the different excitation wavelengths. Slight band shifts and band broadening could be observed under the two sample conditions, one with the stationary sample and the other with sample rotation. The spectral changes are related to the excessive heating caused in a stationary sample by laser irradiation. Based on our findings in this study combined with our earlier study, we can state that only a careful line shape analysis and study of intensity pattern of the D‐ and G‐Raman bands under well‐defined measurement conditions lends itself as a good measure of degree of alignment in the MWCNT bundles. Copyright © 2010 John Wiley & Sons, Ltd.     

多壁碳纳米管/聚丙烯复合材料热导率研究

用Pt细丝代替已有3ω方法中的薄膜热线,并设计了基于Labview程序的虚拟测量系统,准确、方便地测量了聚丙烯复合材料的热导率. 测量结果发现,多壁碳纳米管/丁苯橡胶/聚丙烯三元复合材料的热导率随着多壁碳纳米管/丁苯橡胶粉末含量的增加变化不大;多壁碳纳米管/聚丙烯复合材料的热导率随着多壁碳纳米管含量增加而增大;复合材料热导率远小于简单混合规则预测的结果,而与有效介质理论符合很好. 关键词： ω法')" href="#">3ω法 多壁碳纳米管 聚丙烯复合材料 热导率     

Multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes nanocomposite preparation via cross-linking reaction in acidic media

Multiwalled carbon nanotubes have unique properties allowing their use in a wide range of applications—from microelectronics to biomedical and polymer fields. Nevertheless, a crucial aspect for their use resides in the ease of handling them during the process. Here, we report a facile route to prepare multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes (MWCNT@POSS) nanocomposite. The method involves the formation of a covalent bond between carboxylated MWCNTs and OV-POSS using acid-catalyzed electrophilic addition reaction. The resulting nanocomposite have been characterized by Fourier transform infrared spectroscopy (FTIR), powder X-Ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results confirmed that the formation of MWCNT@POSS nanocomposite did not deteriorate MWCNT structure or morphology. Here, we used a 1:1 ratio of carboxylated MWCNTs and OV-POSS and the POSS content in the nanocomposite was 39.5 wt%.     

Advanced LiTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C anode by incorporation of carbon nanotubes for aqueous lithium-ion batteries

Inferior rate capability is a big challenge for LiTi₂(PO₄)₃ anode for aqueous lithium-ion batteries. Herein, to address such issue, we synthesized a high-performance LiTi₂(PO₄)₃/carbon/carbon nanotube (LTP/C/CNT) composite by virtue of high-quality carbon coating and incorporation of good conductive network. The as-prepared LTP/C/CNT composite exhibits excellent rate performance with discharge capacity of 80.1 and 59.1 mAh g^?1 at 10 C and 20 C (based on the mass of anode, 1 C = 150 mA g^?1), much larger than that of the LTP/C composite (53.4 mAh g^?1 at 10 C, and 31.7 mAh g^?1 at 20 C). LTP/C/CNT also demonstrates outstanding cycling stability with capacity retention of 83.3 % after 1000 cycles at 5 C, superior to LTP/C without incorporation of CNTs (60.1 %). As verified, the excellent electrochemical performance of the LTP/C/CNT composite is attributed to the enhanced electrical conductivity, rapid charge transfer, and Li-ion diffusion because of the incorporation of CNTs.