Wetting of CVD carbon films by polar and nonpolar liquids and implications for carbon nanopipes

The handling, dispersion, manipulation, and functionalization of carbon nanotubes and nanopipes often require the use of solvents. Therefore, a good understanding of the wetting properties of the carbon nanotubes is needed. Such knowledge is also essential for the design of nanotube-based nanofluidic devices, which hold the promise of revolutionizing chemical analysis, separation, drug delivery, filtration, and sensing. In this work, we investigated the wetting behavior of individual nanopipes produced by the chemical vapor deposition (CVD) of carbon in porous alumina templates and of thin carbon films produced by the same technique. The carbon pipes and films have the same chemistry and structure as determined by Raman and infrared spectroscopies and, when similarly treated, demonstrate the same qualitative wetting behavior, as determined by optical microscopy. Thus, measurements conducted on the carbon film surface are relevant to the nanopipes. In the case of the nanopipes, filling with various liquids was monitored. Contact angle experiments with both polar (water, glycerol, ethylene glycol, ethanol, tetra-hydro furan, and 2-propanol alcohol) and nonpolar liquids (cyclohexane, hexadecane, poly(dimethylsiloxane), and a fluoro-silicone) were conducted on films using the sessile drop method. The contact angles on the CVD carbon films ranged from 0 to 79 degrees. The exposure of the carbon films to a NaOH solution, typically used to dissolve the alumina template, led to a significant decrease of the contact angle, especially in the case of polar liquids.     

Stable superhydrophobic surface via carbon nanotubes coated with a ZnO thin film

We report the formation of a stable superhydrophobic surface via aligned carbon nanotubes (CNTs) coated with a zinc oxide (ZnO) thin film. The CNT template was synthesized by chemical vapor deposition on an Fe-N catalyst layer. The ZnO film, with a low surface energy, was deposited on the CNT template by the filtered cathodic vacuum arc technique. Contact angle measurement reveals that the surface of the ZnO-coated CNTs is superhydrophobic with water contact angle of 159 degrees . Unlike the uncoated CNTs surface, the ZnO-coated CNTs surface shows no sign of water seepage even after a prolonged period of time. The wettability of the surface can be reversibly changed from superhydrophobicity to hydrophilicity by alternation of ultraviolet (UV) irradiation and dark storage.     

Novel conductive nanocomposites from perfluoropolyether waterborne polyurethanes and carbon nanotubes

The exceptional electrical conductivity of carbon nanotubes (CNTs) has been exploited for the preparation of conductive nanocomposites based on a large variety of insulating polymers. Among these, perfluoropolyether‐polyurethanes (PFPE‐PUs) represent a class of highly performing fluorinated materials with excellent water/oil repellency, chemical resistance, and substrate adhesion. The incorporation of highly conductive fillers to this class of highly performing materials allows them to be exploited in new technological and industrial fields where their unique properties need to be combined with the electrical conductivity or the electrostatic dissipation properties of carbon nanotubes. However, no studies have been presented so far on nanocomposites based on PFPE‐PUs and CNTs. In this work, polymer nanocomposites based on waterborne PFPE‐PUs and increasing amounts of carboxylated multiwall CNTs (COOH‐CNTs) were prepared and characterized for the first time. The effect of increasing concentration of COOH‐CNTs on the physical, mechanical, and surface properties of the nanocomposites was investigated by means of rheological measurements, dynamic mechanical analysis, thermal characterization, optical contact angle measurements, and scanning electron microscopy. In addition, electrical measurements showed that the highly insulating undoped PFPE‐PU system undergoes substantial modifications upon addition of COOH‐CNTs, leading to the formation of conductive nanocomposites with electrical conductivities as high as 1 S/cm. The results of this study demonstrate that the addition of COOH‐CNTs to PFPE‐PU systems represents a promising strategy to expand their possible use to technological applications where chemical stability, water/oil repellence and electrical conductivity are simultaneously required. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrowetting of aligned carbon nanotube films

Electrowetting is one approach to reducing the interfacial tension between a solid and a liquid. In this method, an electrical potential is applied across the solid/liquid interface which modifies the wetting properties of the liquid on the solid without changing the composition of the solid and liquid phases. Electrowetting of aligned carbon nanotube (CNT) films is investigated by the sessile drop method by dispensing deionized (DI) water or 0.03 M NaCl droplets (contacted by Au wire) onto aligned CNT films assembled on a copper substrate. The results demonstrate that electrowetting can greatly reduce the hydrophobicity of the aligned CNTs; the contact angle saturation for DI water and 0.03 M NaCl droplets occurs at 98 and 50 degrees , respectively. The combined effects of the geometrical roughness and the electrical potential on the contact angle are briefly discussed and modeled. Such a strategy may be invoked to controllably reduce the interfacial tension between carbon nanotubes (CNTs) and polymer precursors when infiltrating the monomers into the prealigned nanotube films.     

Influence of high vacuum annealing treatment on some properties of carbon nanotubes

Carbon nanotubes (CNTs) were synthesized using a chemical vapour deposition (CVD) method. The properties of CNTs before and after vacuum annealing treatment were studied using scanning electron microscopy (SEM), scanning tunneling microscopy/spectroscopy (STM/STS) and thermogravimetric analysis (TG). Field emission characteristics of the raw and vacuum heated (up to 650°C) carbon nanotube films (CNTFs) were measured in a diode system. Emissive properties of the CNTFs depend on an annealing process during which structural changes in the nanotube walls take place. The structural changes, related to saturation of dangling bonds, influence a rate of oxidation process and also improve the emissive field properties.     

Preparation of nylon MXD6/EG/CNTs ternary composites with excellent thermal conductivity and electromagnetic interference shielding effectiveness

In this article,hybrid fillers with different dimensions,namely,2-dimensional (2-D) expanded graphite (EG) and 1-dimensional (1-D) multi-walled carbon nanotubes (CNTs),were added to aromatic nylon MXD6 matrix via melt-blending,to enhance its thermal and electrical conductivity as well as electromagnetic interference shielding effectiveness (EMI SE).For ternary composites of MXD6/EG/CNTs,the electrical conductivity reaches up nine orders of magnitude higher compared to that of the neat MXD6 sample,which tumed the polymer-based composites from an insulator to a conductor,and the thermal conductivity has been enhanced by 477％ compared with that of neat MXD6 sample.Meanwhile,the EMI SE of ternary composite reaches ～50 dB at the overall filler loading of only 18 wt％.This work can provide guidance for the preparation of polymer composites with excellent thermal and electrical conductivity via using hybrid filler.     

AAO模板法生长碳纳米管阵列及形成机理研究

采用阳极刻蚀法制备得到多孔氧化铝模板(AAO)，通过在二茂铁苯溶液中浸润而后热解的方法，得到内壁附着纳米铁颗粒的AAO模板。用化学气相沉积(CVD)法在AAO模板孔内生长出两端开口的碳纳米管(CNTs)阵列。仅用盐酸浸泡就可除去CNTs表面上的催化剂颗粒，得到高纯的CNTs阵列。高分辨透射电镜(HRTEM)和拉曼图谱(Raman)表明CNTs具有很低的石墨化结构。通过对CNTs形貌和形成过程的剖析，认为AAO模板孔道的导向作用以及模板孔内壁催化剂铁颗粒大小分布不均是形成低石墨化碳纳米管的主要原因。     

Design and Synthesis of Carbon Nanotube Segments

The selective and predictable synthesis of structurally uniform carbon nanotubes (CNTs) represents a long‐standing goal in both nanocarbon science and synthetic organic chemistry. This Review focuses on synthetic studies toward the controlled synthesis of CNTs with single chirality through the organic synthesis of CNT segments and the organic template assisted growth of CNTs.     

甲烷部分氧化气氛制备碳纳米管

碳纳米管是由碳六元环构成的类石墨平面卷曲而成的纳米级中空管,其中每个碳原子通过sp2杂化与周围3个碳原子发生完全键合,管的直径在几个纳米到几十个纳米之间,而轴向长度却可达几十微米甚至更长,故被称为准一维分子纳米材料.由于这种特殊结构,碳纳米管具有许多奇异的物理化学性能,如独特的导电性、极高的机械强度、润滑性和吸附能力等.自发现碳纳米管以来[1],人们开展了多种方法进行制备研究,如电弧放电(Arcdischarge)[2]、激光烧蚀(Laserablation)[3]、碳氢化合物催化分解(Catalyticdecompositionofhydrocarbons)[4]和化学气相沉积(Chem…     

Carbon Nanotubes Act as Conductive Additives in the cathode of Lithium Ion Batteries

The layered compounds LiCoO2, LiNiO2 and spinel compound LiMn2O4 have served as very effective cathode active materials in lithium ion rechargeable batteries. Generally, their high conductive resistance easily results in a serious polarization and poor utilization of active materials.In order to make full use of the active materials and increase the capacity, the charge-discharge rate and the cycle life of lithium ion batteries, conductive additives are often added into the above cathode materials to form a conductive network. Carbon materials, such as carbon black, graphite powders and chemical vapor deposit carbon fibers have been widely used as conductive additives owing to their high electrical conductivity and chemical inertness. To effectively utilize the active materials, the contents of these carbon additives in the cathode often reach up to 10～20wt%. This leads to a great need for binder, for example, 10wt% or more. It follows therefore a considerable increase in volume of the lithium batteries and lower energy density because of the large amount of carbon additives and binder in the cathode.By substituting carbon nanotubes (CNTs) for carbon black, graphite powders or chemical vapor deposit carbon fibers, much conductive additives and binder are saved, and the cathode with only 3～5wt% of conductive additives CNTs shows excellent rate capacity. At the discharge rate 0.5C,2.0C and 3.0C, the LiCoO2 cathode with CNTs exhibits discharge capacity up to 134mAh/g, 126 and 120mAh/g, respectively. The explanation is given as follows. Firstly, their microstructure and graphitic crystallinity are very important for electron transport. CNTs employed in the experiments comprise an array of complete graphite sheets seamlessly wrapped into cylindrical tubes which are concentrically nested like the rings of a tree trunk. Thus, the process of -electrons transport occurs in graphite sheet in super-conjugative manner when they move from one end to the other end in CNTs. Apparently, the CNTs' microstructure does good to electron transport. On the other hand,being highly graphitic (concluded from XRD patterns), CNTs also displays high electron conductivity. Secondly, being smaller in diameter, CNTs possess much larger number of primary particles in unit mass than other carbon materials. Hence, it results in a lower percolation threshold in the case of CNTs. Finally, owing to their high surface energy, CNTs fallen into nano-materials tend to aggregate and then form firm webs effectively entrapping LiCoO2 particles during the preparation of the cathode to guarantee their close contact with the active materials.Accordingly, effective electron channels are provided to lessen the polarization loss.     

Pt/C和Pt/CNTs电极的电化学稳定性研究

采用恒电位氧化法研究了Pt/C和Pt/CNTs电极的电化学稳定性. 相同条件下, Pt/C电极的氧化电流大约为Pt/CNTs电极的2倍; 120 h氧化后, Pt/C电极Pt的电化学表面积下降了21.3%, 而Pt/CNTs电极仅下降了7.6%, 表明Pt/CNTs电极性能衰减较慢. X射线光电子能谱(XPS)分析表明, Pt/C的载体碳黑表面氧增加量大于Pt/CNTs中碳纳米管(CNTs)表面氧的增加量, 说明碳黑的被氧化程度较高, 电化学稳定性差; Pt的表面化学状态没有发生变化; 碳纳米管本身的抗电化学氧化性也大于碳黑. 所以, 载体的被氧化程度不同是两种电极性能衰减不同的主要原因之一, 并且排除了Pt表面状态的影响.     

Layer by Layer Electrode Surface Functionalisation Using Carbon Nanotubes,Electrochemical Grafting of Azide‐Alkyne Functions and Click Chemistry

Ferrocene was covalently bonded to a layer of adsorbed single‐walled carbon nanotubes on a glassy carbon electrode surface using electrochemical grafting and click chemistry. Grafting of the 4‐azidobenzenediazonium salt onto the surface was accomplished by electrochemical reduction. The surface‐bound azide groups, with the use of a copper(I) catalyst, were reacted with ethynylferrocene to form covalent 1,2,3‐triazole bonds by click chemistry. This layer by layer construction of the electrode surface results in stable electrodes by combining good electrical conductivity and increased surface area of the nanotubes with the versatility of the Sharpless click reaction.     

Design of superhydrophobic surfaces by synthesis of carbon nanotubes over Co-Mo nanocatalysts deposited under microwave irradiation on Ti-containing mesoporous silica thin films

The superhydrophobic surface has been designed by the synthesis of carbon nanotubes (CNTs) on Ti-containing mesoporous silica thin films (Ti-MSTFs) with Co-Mo binary nanocatalysts. The active Co-Mo catalysts have been successfully deposited on Ti-MSTFs under microwave irradiation. SEM and TEM observations after CNT synthesis revealed that surfaces of Ti-MSTFs were densely covered with CNTs having a diameter of 15 nm. Raman spectra indicated that the undesired structural defects in the carbon network of the synthesized CNTs, which would lead to the formation of hydroxyl groups, were scarce. Interestingly, hydrophobic properties of samples after CNT synthesis were enhanced with increasing titanium concentration of Ti-MSTF, and the water contact angle reached up to 165° on Ti-MSTF with a titanium concentration of 10 at%. The combination of dispersed titanium oxide moieties within the silica frameworks and the microwave irradiation made a great contribution to deposit active Co-Mo catalysts responsible for the formation of well-dense CNTs.     

Nanostructured films from phthalocyanine and carbon nanotubes: surface morphology and electrical characterization

We report on the investigation of the surface morphology and DC conductivity of nanostructured layer-by-layer (LbL) films from nickel tetrasulfonated phthalocyanine (NiTsPc) alternated with either multi-walled carbon nanotubes (MWNTs/NiTsPc) or multi-walled carbon nanotubes dispersed in chitosan (MWNTs+Ch/NiTsPc). We have explored the surface morphology of the films by using fractal concepts and dynamic scale laws. The MWNTs/NiTsPc LbL films were found to have a fractal dimension of ca. 2, indicating a quasi Euclidean surface. MWNTs+Ch/NiTsPc LbL films are described by the Lai-Das Sarma-Villain (LDV) model, which predicts the deposition of particles and their subsequent relaxation. An increase in the wetting contact angle of MWNTs+Ch/NiTsPc LbL films was observed, as compared with MWNTs/NiTsPc LbL films, which presented an increase in the fractal dimension of the first system. Room temperature conductivities were found be ca. 0.45 S/cm for MWNTs/NiTsPc and 1.35 S/cm for MWNTs+Ch/NiTsPc.     

形状记忆聚偏氟乙烯/丙烯酸酯/碳纳米管纳米复合材料的导电及导热性能

利用聚偏氟乙烯（PVDF）微小结晶的物理交联点作用,制备了形状记忆性能优异的聚偏氟乙烯/丙烯酸酯聚合物（PVDF/ACM）共混材料,为提高其导电及导热性能,于其中引入了碳纳米管（CNT）,系统研究了PVDF/ACM/CNT三元体系纳米复合材料的导热及导电性能。 结果表明,碳纳米管在PVDF/ACM体系中分散均匀;在基本保持其形状记忆性能的前提下,碳纳米管的加入使材料导热性能及导电性能有较大程度的提高：质量分数为4%的CNT使材料25 ℃的电阻值降低至5000 Ω/square,导热系数提高至0.157 W/(m·K)。     

碳纳米管/半导体复合材料光催化研究进展

碳纳米管具有良好的机械性能和导电性、高化学稳定性、大表面积以及独特的一维结构,与半导体光催化剂结合能够增强催化剂的吸附能力、提高光催化效率、扩展光响应范围,而且有利于回收催化剂,极大地提高了半导体光催化剂的综合性能。本文首先分析了半导体光催化剂和碳纳米管的特点,总结了碳纳米管增强半导体光催化的机理,然后分别从复合材料制备方法、复合半导体种类和典型的应用三个不同角度,归纳总结了近年来碳纳米管/半导体复合材料光催化的研究进展,最后对其发展趋势作了展望。     

Effect of nano‐size nodular structure induced by CNT‐promoted phase separation on the fabrication of superhydrophobic polyvinyl chloride films

The nonsolvent‐induced phase separation (NIPS) method was employed to fabricate the porous films based on polyvinyl chloride loaded with carbon nanotubes (CNTs). The combinational addition of CNTs and a proper nonsolvent (ethanol) resulted in a porous surface layer with the nano‐size nodular structure possessing an exact superhydrophobic behavior (water contact angle [WCA] = 157° and sliding angle [SA] <5°). The size of PVC nodules at the surface layer varies in the range of 200 to 800 nm depending on the nonsolvent concentrations, and polymer molecular weight. The effects of various nonsolvent concentrations as well as PVC molecular weight on the surface properties of the films were also investigated. Morphological and roughness analyses revealed the pronounced role of PVC molecular weight on the size of nodules, and the structural uniformity of the surface morphology based on the thermodynamic parameters such as relaxation time and dynamic of polymer chains. The concurrent use of CNTs and nonsolvent led to promote the NIPS process due to the nucleating role of CNTs, which were localized within the polymer‐rich phase leading to an ultra‐fine and packed nodular surface structure. Transmission electron microscopy results also proved the very well dispersion quality of CNTs. Glass transition temperature of PVC was also assessed, and the results were correlated to the associating ability of CNTs with polymer chains during the phase separation process. Overall, the promising potential of CNT/ethanol combination on the surface porosity and hydrophobicity of PVC nanocomposite films was revealed in this study, which could further extend its application window.     

A Review Featuring Fabrication,Properties and Applications of Carbon Nanotubes (CNTs) Reinforced Polymer and Epoxy Nanocomposites

Carbon nanotubes (CNTs) have long been recognized as the stiffest and strongest man-made material known to date.In addition,their high electrical conductivity has roused interest in the areas of electrical appliances and communication related applications.However,due to their miniature size,the excellent properties of these nanostructures can only be exploited if they are homogeneously embedded into light-weight matrices as those offered by a whole series of engineering polymers.In order to enhance their chemical affinity to engineering polymer matrices,chemical modification of the graphitic sidewalls and tips is necessary.The mechanical and electrical properties to date of a whole range of nanocomposites of various carbon nanotube contents are also reviewed in this attempt to facilitate progress in this emerging area.Recently,carbonaceous nano-fillers such as graphene and carbon nanotubes (CNTs) play a promising role due to their better structural and functional properties and broad range of applications in every field.Since CNTs usually form stabilized bundles due to van der Waals interactions,they are extremely difficult to disperse and align in a polymer matrix.The biggest issues in the preparation of CNTs reinforced composites reside in efficient dispersion of CNTs into a polymer matrix,the assessment of the dispersion,and the alignment and control of the CNTs in the matrix.An overview of various CNT functionalization methods is given.In particular,CNT functionalization using click chemistry and the preparation of CNT composites employing hyperbranched polymers are stressed as potential techniques to achieve good CNT dispersion.In addition,discussions on mechanical,thermal,electrical,electrochemical and applications ofpolymer/CNT composites are also included.     

碳纳米管/SnO2复合电极的制备及其电催化性能研究

采用液相沉积法制备碳纳米管(CNTs)/SnO₂复合材料, 并制备成电极, 分别与石墨/SnO₂及活性炭/SnO₂复合电极比较, 考察电催化降解有机废水的性能. 由于CNTs高的比表面积及优良的导电性能, 结合SnO₂良好的催化活性, CNTs/SnO₂复合电极电催化降解有机废水性能优越. 研究发现, CNTs的预处理情况、SnO₂负载量以及煅烧温度对复合电极的电催化性能有重要影响. 当功能化CNTs负载40% SnO₂, 煅烧温度600 ℃时, 所得CNTs/SnO₂复合电极电催化降解有机废水的能力是纯CNTs电极的2倍. 最后, 初步探讨了CNTs/SnO₂复合电极电催化降解有机废水的机理.     

Investigation of the electrical resistance of single-walled carbon nanotube films in the temperature range 4.2–290 K

Electrical resistance of films made of the source material and purified HiPCO and Arc single-walled carbon nanotubes (SWCNTs) with a thickness of 20−40 μm is 2.4 to 45 Ω (electrical conductivity of 0.42 × 10³ to 5.03 × 10³ S/m) at room temperature. The films have been formed by vacuum microfiltration of SWCNT suspensions in toluene and characterized by Raman and X-ray photoelectron spectroscopy and scanning electron microscopy. The conductivity of the films at room temperature depends on the type and degree of purity of the material of nanotubes. The resistance of the films decreases with the increasing temperature over the range of 4.2–290 K, and the rate of the step-down decreases with increasing purity of the material of the nanotubes. The conductivity of the films is semiconducting in character, and the electron transport is consistent with three-dimensional hopping conductivity.