Electrodeposition of composite materials containing functionalized carbon nanotubes

New methods have been developed for the synthesis and electrodeposition of functionalized single-walled carbon nanotubes (f-SWNTs). Polystyrene sulfonate functionalized nanotubes (PSS-f-SWNTs) and poly(ethylene imine) functionalized nanotubes (PEI-f-SWNTs) were co-deposited with cationic chitosan macromolecules. It was shown that chitosan promotes cathodic deposition of anionic PSS-f-SWNTs. The strategies for charging and electrodeposition of PEI-f-SWNTs include partial protonation of PEI in acidic chitosan solutions or formation of cationic Ag⁺–PEI complexes. The thickness of chitosan–PSS-f-SWNTs and chitosan–PEI-f-SWNTs composite films was varied in the range of up to 0.5–5 μm. The amount of f-SWNTs in the deposits was varied by controlling the SWNT concentration in the solutions. It was shown that the use of chitosan enabled co-deposition of other materials, such as hydroxyapatite (HA). The proposed method enabled the fabrication of composite films.     

Interlaminar and intralaminar reinforcement of composite laminates with aligned carbon nanotubes

Three-dimensional reinforcement of woven advanced polymer–matrix composites using aligned carbon nanotubes (CNTs) is explored experimentally and theoretically. Radially-aligned CNTs grown in situ on the surface of fibers in a woven cloth provide significant three-dimensional reinforcement, as measured by Mode I interlaminar fracture testing and tension-bearing experiments. Aligned CNTs bridge the ply interfaces giving enhancement in both initiation and steady-state toughness, improving the already tough system by 76% in steady state (more than 1.5 kJ/m² increase). CNT pull-out on the crack faces is the observed toughening mechanism, and an analytical model is correlated to the experimental fracture data. In the plane of the laminate, aligned CNTs enhance the tension-bearing response with increases of: 19% in bearing stiffness, 9% in critical strength, and 5% in ultimate strength accompanied by a clear change in failure mode from shear-out failure (matrix dominated) without CNTs to tensile fracture (fiber dominated) with CNTs.     

取向碳纳米管/环氧树脂复合薄膜制备及结构与性能表征

碳纳米管(Carbon nanotube, CNT)/环氧树脂(Epoxy resin, EP)纳米复合材料中树脂含量、分布、CNT取向及其与树脂间界面结合是制备高性能纳米复合材料的关键因素。为了探究树脂分布和CNT/EP复合材料性能之间的关系,采用浮动催化化学气相沉积法制备的CNT薄膜和EP为原料,通过浸渍、牵伸、清洗和热压固化工艺制备CNT/EP复合薄膜。利用聚焦离子束结合扫描电子显微镜定性表征树脂在复合膜中的分布状态。结果表明,随着树脂含量增加,树脂在复合薄膜表面富集程度增加。在最优工艺条件下制备的纳米复合材料中CNT含量为66.14wt%, 拉伸强度和拉伸模量达到1405 MPa和46.7 GPa。      

Biocompatibility of immobilized aligned carbon nanotubes

In vivo host responses to an electrode-like array of aligned carbon nanotubes (ACNTs) embedded within a biopolymer sheet are reported. This biocompatibility study assesses the suitability of immobilized carbon nanotubes for bionic devices. Inflammatory responses and foreign-body histiocytic reactions are not substantially elevated when compared to negative controls following 12 weeks implantation. A fibrous capsule isolates the implanted ACNTs from the surrounding muscle tissue. Filamentous nanotube fragments are engulfed by macrophages, and globular debris is incorporated into the fibrous capsule with no further reaction. Scattered leukocytes are observed, adherent to the ACNT surface. These data indicate that there is a minimal local foreign-body response to immobilized ACNTs, that detached fragments are phagocytosed into an inert material, and that ACNTs do not attract high levels of surface fouling. Collectively, these results suggest that immobilized nanotube structures should be considered for further investigation as bionic components.     

Effect of patterned and aligned carbon nanotubes on field emission properties

The field emission (FE) properties of carbon nanotubes (CNTs) films with different morphologies were simulated and examined. Based on the FE mechanism of aligned CNTs’ emitter the theoretical analysis exhibited the following relations: the FE enhancement factor with the distance between the emitters, the electric field with work function, and the work function with FE enhancement factor. Using the structure-induced CNTs growing method and theoretical results the direction of aligned CNTs could be controlled and the special morphology with different aligned CNTs’ film could be fabricated. Comparing to the experimental results (the medium density and patterned CNTs’ emitters) with the theoretically calculating results the I-V curves had the same trend with only 0.05 mA deviation. Based on the better experimental methods and means the accurate of formula could be further improved by modified the FE properties (Φ, β).     

纳米碳管/羟基磷灰石复合材料的凝胶注模

采用凝胶浇注成型工艺制备了纳米碳管/ 羟基磷灰石复合材料坯体。研究了p H 值、分散剂、固相含量(纳米碳管和羟基磷灰石在料浆中的质量分数) 、分散工艺等因素对料浆和复合材料坯体性能的影响, 对坯体的力学性能进行了测试, 借助扫描电镜分析了坯体的微观组织。实验发现, 料浆的p H 值应控制在10～12 的范围内;聚甲基丙烯酸铵的浓度为0. 6 %时, 羟基磷灰石悬浮体流动性最好; 十二烷基磺酸钠的浓度在SDS/ CNTs = 1 %～2 %时, 纳米碳管/ 羟基磷灰石复相料浆的粘度最低; 采用球磨法制备的复相料浆固相含量达到55 % , 复合材料坯体的抗弯强度达到57. 403 MPa 。      

Infrared photoluminescence of composite films containing quasi-isolated multiwalled carbon nanotubes and carbon nanoshells

Films of small irregular-shaped aggregates composed by several layers of turbostratic graphite encapsulating iron nanoparticles, like carbon nanoshells, and quasi-isolated multi-walled carbon nanotubes (MWCNTs), were synthesized by the chemical vapor deposition method on glass substrates. Quasi-isolated MWCNTs were found emerging in different directions on the agglomerates composed of carbon nanoshells. The morphological properties of the films were characterized using scanning electron microscopy, high-resolution transmission electron microscopy and Raman spectroscopy, whereas their optical properties were investigated using optical absorption and photoluminescence (PL) spectroscopy. The studies show a high-intensity PL signal in the infrared at room temperature. This PL signal shows several peaks, which cannot be explained by a blackbody emission. However, the overall PL signal could be a combination of the black emission and electronic transitions. Furthermore, the observed infrared PL emission could be ideal for potential applications such as in gas sensors, infrared detectors and so on.     

A composite index to quantify dispersion of carbon nanotubes in polymer-based composite materials

Several methods with various levels of sophistication exist to quantify dispersion of carbon nanotubes (CNTs) in a polymer matrix, such as the ASTM D2663 standard that is often used in engineering practice. However, most methods are limited by their accuracy, complexity of implementation, and scalability. In this paper, we present a new technique and index to quantify dispersion of CNTs in a composite material. The technique is partially based on a quadrat method, and takes into account the dispersion and agglomerate size distribution of the CNTs. This index is benchmarked against the ASTM index using computer generated images and images experimentally obtained from thirty CNT composite material specimens with different CNT loading rates up to twenty volume percent. The new index is shown to be more versatile and reliable than the ASTM index. It is easily implementable in engineering practice as opposed to other more sophisticated techniques available in the literature.     

电场诱导多壁碳纳米管有序排列对多壁碳纳米管/环氧树脂复合材料性能的影响

采用交流（AC）电场诱导法制备了多壁碳纳米管（MWCNTs）均匀分散且定向有序排列的MWCNTs/环氧树脂复合材料。采用SEM、偏振拉曼光谱等研究了电场强度、MWCNTs含量、加电时间及温度（黏度）等因素对MWCNTs定向排列的影响,讨论了MWCNTs有序排列对MWCNTs/环氧树脂复合材料电学和力学性能的影响。结果表明：MWCNTs沿电场方向有序排列;MWCNTs/环氧树脂复合材料施加AC电场后的拉曼强度明显高于未施加电场的情况;当MWCNTs含量从0wt%增加到0.025wt%时,MWCNTs/环氧树脂复合材料导电率从2.3×10^-12 S/cm增加到1.3×10^-8 S/cm,增加了约4个数量级;MWCNTs含量为2.5wt%时,MWCNTs/环氧树脂复合材料拉伸强度提高了26.3%。     

Dielectric properties and microwaves response behavior of polypyrrole-derived N-doped carbon nanotubes

A series of N-doped carbon nanotubes (NCNTs) have been synthesized via a temperature-controlled annealing of polypyrrole (PPy) hierarchical nanostructures. The microstructures, dielectric properties and microwaves response behavior of these NCNTs were systematically investigated. The results indicate that initial pyrrolic N in PPy was gradually converted into pyridinic and graphitic N during the annealing process. NCNT prepared at 700 °C exhibits excellent broadband microwave absorption performance, where its effective absorption bandwidth (reflection loss value lower than ? 10 dB) reaches 8.20 GHz in the frequency range of 9.80–18.00 GHz. A model refers to conductive loss and polarization relaxation was adopted to explain the high-performance microwave absorption. This research greatly expands the development of N-doped CNTs for the application in microwave areas.

     

Highly oriented carbon nanotube papers made of aligned carbon nanotubes

Paper-like carbon nanotube (CNT) materials have many important applications such as in catalysts, in filtration, actuators, capacitor or battery electrodes, and so on. Up to now, the most popular way of preparing buckypapers has involved the procedures of dispersion and filtration of a suspension of CNTs. In this work, we present a simple and effective macroscopic manipulation of aligned CNT arrays called 'domino pushing' in the preparation of the aligned thick buckypapers with large areas. This simple method can efficiently ensure that most of the CNTs are well aligned tightly in the buckypaper. The initial measurements indicate that these buckypapers have better performance on thermal and electrical conductance. These buckypapers with controllable structure also have many potential applications, including supercapacitor electrodes.     

Controlled two-dimensional pattern of spontaneously aligned carbon nanotubes

We report a simple solution process to form controlled patterns of aligned single-walled carbon nanotubes on solid substrates. The essential step of the process is to deposit a dilute solution of DNA-wrapped carbon nanotubes (DNA-CNTs) on a SiO(2) surface covered with a thin hydrophobic layer. This leads to deposition of fully aligned CNTs. The alignment pattern can be controlled by metal electrodes in the deposition region and can be quantitatively modeled by the behavior of a quasi-two-dimensional DNA-CNT nematic phase near the solution/SiO(2) interface. These results point to the possibility of rational design and economical fabrication of CNT alignment patterns on solid substrates.     

High-rate low-temperature growth of vertically aligned carbon nanotubes

We report the low-temperature growth of vertically aligned carbon nanotubes (CNTs) at high growth rates by a photo-thermal chemical vapour deposition (PTCVD) technique using a Ti/Fe bilayer film as the catalyst. The bulk growth temperature of the substrate is as low as 370?°C and the growth rate is up to 1.3 μm min(-1), at least eight times faster than the values reported by traditional thermal CVD methods. Transmission electron microscopy observations reveal that as-grown CNTs are uniformly made of highly crystalline 5-6 graphene shells with an approximately 10 nm outer diameter and a 5-6 nm inner diameter. The low-temperature rapid growth of CNTs is strongly related to the unique top-down heating mode of PTCVD and the use of a Ti/Fe bimetallic solid solution catalyst. The present study will advance the development of CNTs as interconnects in nanoelectronics, through a CMOS-compatible low-temperature deposition method suitable for back-end-of-line processes.     

A biocompatible chitosan composite containing phosphotungstic acid modified single-walled carbon nanotubes

Surface modification of carbon nanotubes is crucial for the dispersion and interfacial adhesion of carbon nanotubes in polymer composites. Here we present a novel method to construct single-walled carbon nanotube/chitosan composites using phosphotungstic acid as an anchor reagent to modify single-walled carbon nanotubes. The most direct benefit from this method is that this modification is mild but effective: the induced defects on single-walled carbon nanotubes are negligible based on Raman and transmission electron microscopy observations; and homogeneous dispersion of single-walled carbon nanotubes in chitosan matrices and strong binding between single-walled carbon nanotubes and chitosan are achieved. Moreover, according to the results of tetrazolium-based colorimetric assays in vitro, we demonstrate that the produced phosphotungstic-acid-modified single-walled carbon nanotube/chitosan composites have good biocompatibility. Thus, our study provides a feasible route to fabricate biocompatible composites containing single-walled carbon nanotubes for potential application in bone tissue engineering.     

Coherent phonon anisotropy in aligned single-walled carbon nanotubes

By time-resolved reflectivity measurements with sub-10 fs laser pulses at 395 nm, the coherent phonons of aligned bundles of single-walled carbon nanotubes are observed for various polarization directions of the pump and probe pulses. In the isotropic reflectivity measurement, we observe the radial breathing modes, G, and even D modes, while in the anisotropic reflectivity mode, only the G mode appears. A complex polarization dependence of the G band phonon amplitude in the isotropic reflectivity is explained by the superposition of G band phonons with different symmetries.     

Re-grown aligned carbon nanotubes with improved field emission

In this work, a simple technique to improve the field emission property of multi-walled carbon nanotubes is presented. Re-grown multi-walled carbon nanotubes are grown on the same substrates after the as-grown multi-walled carbon nanotubes are transferred to other substrates using polydimethylsiloxane as intermediation. For the duration of the synthesis of the re-grown multi-walled carbon nanotubes, similar synthesis parameters used in growing the as-grown multi-walled carbon nanotubes are utilized. As a form of possible application, field emission studies show -2.6 times improvement in field enhancement factor and more uniform emission for the re-grown multi-walled carbon nanotubes. In addition, the turn-on field is reduced from 2.85 V/microm to 1.40 V/microm. Such significant improvements are attributed to new emission sites comprising of sharp carbonaceous impurities encompassing both tip and upper portion of the multi-walled carbon nanotubes. As such, this technique presents a viable route for the production of multi-walled carbon nanotubes with better field emission quality.     

水辅助化学气相沉积制备定向碳纳米管

为提高定向碳纳米管(Aligned carbon nanotubes,ANTs)的长度与面积,以二茂铁为催化剂前驱体、二甲苯为碳源,生长温度为850℃,采用水辅助化学气相沉积法在石英基底上制备ANTs。借助透射电镜(TEM)、扫描电子显微镜(SEM)分析了ANTs的形貌。结果表明,在优化的生长条件下,可获得面积为60×140 mm2、长为2.05 mm的ANTs;在微波辐射下ANTs会产生灼热的白光,是潜在的吸波材料。     

Adsorption of fluoride from water by aligned carbon nanotubes

Aligned carbon nanotubes (ACNTs), a new type of carbon material, were prepared by catalytic decomposition of xylene using ferrocene as catalyst. The kinetics experiment of ACNTs shows that fluoride adsorption rate is fast in the first 60 min and the adsorption capacity reaches 3.0 mg/g rapidly, then it decreases and adsorption achieves equilibrium gradually in about 180 min. The fluoride adsorption of ACNTs depends slightly on the solution pH value. The highest adsorption capacity of ACNTs occurs at pH 7 and reaches 4.5 mg/g at equilibrium fluoride concentration of 15 mg/l. The experimental results indicate that ACNTs are promising candidate materials for fluoride removal.     

Modeling electrical conductivities of nanocomposites with aligned carbon nanotubes

We have developed an improved three-dimensional (3D) percolation model to investigate the effect of the alignment of carbon nanotubes (CNTs) on the electrical conductivity of nanocomposites. In this model, both intrinsic and contact resistances are considered, and a new method of resistor network recognition that employs periodically connective paths is developed. This method leads to a reduction in the size effect of the representative cuboid in our Monte Carlo simulations. With this new technique, we were able to effectively analyze the effects of the CNT alignment upon the electrical conductivity of nanocomposites. Our model predicted that the peak value of the conductivity occurs for partially aligned rather than perfectly aligned CNTs. It has also identified the value of the peak and the corresponding alignment for different volume fractions of CNTs. Our model works well for both multi-wall CNTs (MWCNTs) and single-wall CNTs (SWCNTs), and the numerical results show a quantitative agreement with existing experimental observations.