Chemical functionalization of carbon nanotubes

There are many reasons why one would want to form chemical attachments to the walls or ends of carbon nanotubes: these chemical bonds might be used to tailor the interaction of the nanotube with other entities, such as a solvent, a polymer matrix, or other nanotubes. The chemically functionalized nanotube might have mechanical or electrical properties that are different from those of the unfunctionalized nanotube and thus might be used as a chemical sensor or a nanometer-scale electronic device. The challenge is to find a way to reproducibly and reliably chemically alter carbon nanotubes that, like graphite, are fairly unreactive. The various methods used to date and the possible application of the resulting functionalized nanotubes is discussed in this review paper.     

单壁碳纳米管制备研究新进展

碳纳米管由于具有独特的结构和奇异的物理、化学性质而倍受人们的青睐，并逐渐展示出巨大的应用前景。简要介绍了碳纳米管的结构、性质和应用，并详细评述了单壁碳纳米管制备的新进展。     

Deposition of metallic nanoparticles on carbon nanotubes via a fast evaporation process

A new technique was developed for the deposition of colloidal metal nanoparticles on carbon nanotubes. It involves fast evaporation of a suspension containing sonochemically functionalized carbon nanotubes and colloidal nanoparticles. It was demonstrated that metallic nanoparticles with different sizes and concentrations can be deposited on the carbon nanotubes with only a few agglomerates. The technique does not seem to be limited by what the nanoparticles are, and therefore would be applicable to the deposition of other nanoparticles on carbon nanotubes. PtPd and CoPt(3) alloy nanoparticles were used to demonstrate the deposition process. It was found that the surfactants used to disperse the nanoparticles can hinder the nanoparticle deposition. When the nanoparticles were washed with ethanol, they could be well deposited on the carbon nanotubes. The obtained carbon nanotube supported metal nanoparticles were characterized by transmission electron microscopy, energy dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, and cyclic voltammetry.     

KOH活化处理碳纳米管对其负载非晶态NiP催化性能的影响

经KOH活化处理和未经活化处理的碳纳米管分别用于负载非晶态NiP合金.以苯加氢为探针反应,研究了KOH活化处理温度和时间对碳纳米管的性质及其负载非晶态NiP催化剂活性的影响.研究结果表明:碳纳米管经KOH处理可以提高其负载非晶态NiP催化剂的催化活性,催化剂活性随活化温度升高和活化时间延长而增加.由于KOH处理改变了碳纳米管的微观结构,增加了其比表面积,所以非晶态NiP在碳纳米管上更易沉积分散,其负载的非晶态NiP合金催化剂的催化活性较高.     

A pullout model for inclined carbon nanotube

The mechanical properties of carbon nanotubes (CNTs) reinforced composites would mainly depend on the pullout behavior of carbon nanotubes which are randomly distributed in matrix. In this paper, an analytical pullout model is developed for an inclined CNT embedded into matrix to study the mechanisms for improving mechanical properties of inclined CNTs reinforced composites. In this model, by employing the assumptions of constant compression stress as well as the punch strength of matrix and a perfect plastic matrix near exit point, the maximum pullout load can be predicted analytically and the entire pullout process can be characterized. Moreover, by extending the definition for inclination angle this model can be fit to more complicated loading situations. Due to all the derivations are based on assumption of continuum mechanics, this model can be used for various inclined fibers besides CNTs.     

Effect of functionalized carbon nanotubes on the mechanical properties of epoxy-based composites

Abstract

In this research, composites reinforced with multi-walled carbon nanotubes (MWCNTs) in terms of their capability of absorbing energy during ballistic impact and tensile test were investigated. In order to investigate the effect of functional groups on mechanical properties of multi-wall carbon nanotubes composites, multi-walled carbon nanotubes were functionalized by COOH and NH₂. In order to investigate the penetration resistance of produced composites, the ballistic impact test with the high velocity was used. Results of the ballistic impact test imply that composites which benefit from carbon nanotubes with the carboxylic functional group have the highest value of the energy absorption. Results of the tensile test indicate, the interaction between carbon nanotubes with the carboxylic agent and the polymer matrix is much better. The ultimate stress for the sample containing nanotubes with hydroxyl functional group is 55% higher compared with the sample which does not contain any nanotubes. Reinforced composite samples which contain carbon nanotubes with the carboxylic functional group absorb 57.63% of the projectile energy and represent a better performance compared to the sample without nanotubes and the sample which consists of nanotubes with the amine functional group. The results of this study show that, uniform dispersion of nanotubes in the polymer matrix can profoundly affect mechanical properties especially the tensile strength. By functionalizing nanotubes and creating suitable functional groups, the cohesion between nanotubes and the matrix can be improved.     

Plumbing carbon nanotubes

Since their discovery, the possibility of connecting carbon nanotubes together like water pipes has been an intriguing prospect for these hollow nanostructures. The serial joining of carbon nanotubes in a controlled manner offers a promising approach for the bottom-up engineering of nanotube structures--from simply increasing their aspect ratio to making integrated carbon nanotube devices. To date, however, there have been few reports of the joining of two different carbon nanotubes. Here we demonstrate that a Joule heating process, and associated electro-migration effects, can be used to connect two carbon nanotubes that have the same (or similar) diameters. More generally, with the assistance of a tungsten metal particle, this technique can be used to seamlessly join any two carbon nanotubes--regardless of their diameters--to form new nanotube structures.     

由不同碳源合成及制备纳米碳管的进展

纳米碳管可通过石墨、煤炭及炭黑等高含碳固体物，甲烷、乙烯或苯之类的有机化合物，一氧化碳和碳化硅等含碳无机化合物的转化来制备，甚至还可由低分子芳烃化合物来逐级合成。根据各种不同碳源，按不同转化过程及制备方法进行了总结与归纳，期望能对纳米碳管的合成及制备有一总体理解；通过简要、系统地介绍各种转化过程及制备方法，并对其中一些有发展前途的方法特别是电弧法、激光烧蚀法及化学气相沉积法的最新改进和发展进行了考察，分析了这些方法的优缺点；最后概述了目前纳米碳管规模制备方法的进展情况。     

由煤或焦炭制备纳米碳质材料的新进展

评述了以煤为碳源制备富勒烯、纳米碳管、竹节形碳管、铁嵌入的纳米碳棒和由碳包覆的金属纳米粒子等各种纳米材料。认为：等离子体电孤放电法是由煤制备各种纳米碳质材料最常用的方法，随电弧条件及电极性质的不同，所制备的纳米碳质材料可有各种不同形态及结构、由于煤是分子固体而石墨是晶格固体，两种碳源的反应机理有明显不同。在等离子体电弧加热时，煤分解并产生许多具有简单芳烃结构的分子，在纳米碳质材料的形成过程中，这些分子可能作为纳米碳质材料的结构单元，同时原煤中的矿物质在合成过程中也起着重要作用，因此煤本身的性质对纳米材料的制备极为重要。煤是成本低廉且储量最丰富的碳源，将是大规模工业化生产纳米碳质材料最好的碳源之一。     

On the mechanical characterization of carbon nanotube reinforced epoxy adhesives

In this work, the mechanical properties of carbon nanotube reinforced epoxy adhesives are investigated experimentally. The investigations are intended to characterize the physical and mechanical properties of nano-reinforced structural epoxy adhesives and to further highlight some of the complex phenomena associated with these materials. We describe the dispersion methodology used to disperse the carbon nanotubes into the considered adhesive and provide details pertaining to adherent surface preparation, bondline thickness control and adhesive curing conditions. Furthermore, the following tests are described: (i) dogbone tensile testing, (ii) tensile bond testing, (iii) double lap shear and (iv) double cantilever beam fracture toughness testing. The experimental observations indicate a critical carbon nanotube concentration in the vicinity of 1.5 wt% that results in the largest improvements in the measured properties. At concentrations exceeding this critical value, the properties begin to degrade, in some cases, to levels below that of the pure epoxy. Advanced electron microscopy techniques and rheological assessments indicate that this is mainly due to the agglomeration of the carbon nanotubes at higher concentrations as a result of increased resin viscosity and the consequent resistance to dispersion.     

载气在CVD法制备纳米碳管工艺中的作用

纳米碳管是性能优异的具有准一维特征的纳米材料,CVD法是制备纳米碳管的典型工艺之一。本文以乙炔气体为原料气体、循环失效后的贮氢电极舍金材料作为反应催化剂,研究了在相同反应条件下,CVD法制备纳米碳管过程中载气对纳米碳管形貌和产率的影响。通过对产物TEM观察和TG分析发现,虽然载气不直接参与合成反应但对产物产率和形貌有很大的影响,氢气作为载气可以获得形貌和热稳定性更好的纳米碳管。     

Percolation threshold of carbon nanotubes filled unsaturated polyesters

This paper reports on the development of electrically conductive nanocomposites containing multi-walled carbon nanotubes in an unsaturated polyester matrix. The resistivity of the liquid suspension during processing is used to evaluate the quality of the filler dispersion, which is also studied using optical microscopy. The electrical properties of the cured composites are analysed by AC impedance spectroscopy and DC conductivity measurements. The conductivity of the cured nanocomposite follows a statistical percolation model, with percolation threshold at 0.026 wt.% loading of nanotubes. The results obtained show that unsaturated polyesters are a matrix suitable for the preparation of electrically conductive thermosetting nanocomposites at low nanotube concentrations. The effect of carbon nanotubes reaggregation on the electrical properties of the spatial structure generated is discussed.     

Multiwall carbon nanotubes from pyrolysis of tetrahydrofuran

Multiwalled carbon nanotubes have been prepared by pyrolysing tetrahydrofuran (THF) in the presence of nickelocene. Pyrolysis of the precursor mixture has been achieved at temperature as low as 600 °C. In this simple approach no carrier gas has been used. The yield of purified carbon nanotubes is found to be more than 65%. Characterization of the as-prepared and purified nanotubes are done by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy and Raman spectra.     

Opening and reversible filling of single-walled carbon nanotubes with various materials

Single-walled carbon nanotubes have been advocated as perfect candidates for the sustainable miniaturisation of electronic and mechanical nanoscale devices. The encapsulation of selected compounds within the inner hollow cavity of SWNTs allows controlled preparation of nano-meter size "nanowires" and "nanocables" with purpose-tailored physical properties. Therefore is crucial to have control of opening and closing their tips. In a previous study we showed that molten metal hydroxide [MOH (M==Cs, Na)] is filled into the carbon nanotubes and can be easily washed out with water leaving opened nanotubes. Following this approach we have explored the use of milder ways to open SWNTs that can be easily scalable for the production of large amount of opened SWNTs. The opened tubes have then successfully been filled in solution with various inorganic and organic materials.     

碳源对碳纳米管形态的影响

以苯和甲苯为碳源,二茂铁为催化剂,含硫化合物为助催化剂,采用浮游催化裂解法制备了碳纳米管,并采用TEM对不同条件下所得碳纳米管进行了形态分析。结果发现,碳源中苯和甲苯的配比对碳纳米管的形态有着重要的影响。以纯苯为碳源时,产物主要为直线型碳纳米管,并存在极少量短的弯曲型碳纳米管。随着碳源中甲苯比例的增加,产物中折线型碳纳米管增加。以纯甲苯为碳源,产物中仍有少量直线型碳纳米管,而不完全是折线型碳纳米管;此外,产物中还发现了极少量分支型碳纳米管。根据所得结果讨论分析了甲苯的加入对碳纳米管形态的影响以及各种碳纳米管的形成机理,认为可能是由于甲苯在催化热解过程中产生的碳种不同于苯催化热解所产生的碳种,造成碳在催化剂颗粒各处浓度不同,从而在碳纳米管的不同部位引入五元环和七元环而形成各种形态的碳纳米管。     

The reinforcement role of different amino-functionalized multi-walled carbon nanotubes in epoxy nanocomposites

Functionalization with different amino groups of multi-walled carbon nanotubes was achieved and nanotube-reinforced epoxy nanocomposites were prepared by mixing amino-functionalized multi-walled carbon nanotubes with epoxy resin. Differential scanning calorimetry, thermogravimetric analysis and bending tests were used to investigate the thermal and mechanical properties of the nanocomposites. The results showed that different kinds of amino-functionalized multi-walled carbon nanotubes would have different effects on the thermal and mechanical properties of the nanocomposites. The reinforcement mechanism of amino-functionalized multi-walled carbon nanotubes in epoxy resin was discussed.     

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.     

等离子体射流辅助双催化剂原位催化法合成碳纳米管

以甲烷为碳源，Fe2O3／Ni为固定相催化剂，在常压条件下利用等离子体射流的高温将甲烷裂解生成碳自由基和氢气。同时联合原位催化法将碳自由基在Fe2O3／Ni双催化剂的共同作用下生长出碳纳米管。运用TEM和元素分析等测试手段对所得碳纳米管进行形貌、含量、结构的表征分析。结果表明，在一定反应条件下，可获得外径为10nm-30nm，管长约数百纳米、产率为75％左右的碳纳米管。与单催化剂相比，双催化剂的联合催化作用更有利于碳管的生长。     

A pressure enhanced CVD method for large scale synthesis of carbon microtubes and their mechanical properties

Carbon microtubes (CMTs) are a new morphological form of carbon with micrometer scale internal diameters and thin walls made of a few graphitic layers. However, compared with carbon nanotubes, there is lack of a feasible and reliable synthetic method. Furthermore, the mechanical properties of CMTs have not been reported. In this paper, we report a gas pressure enhanced CVD method for large-scale preparation of high-purity, crystalline and thin-walled CMTs in a gas pressure furnace using urea as raw material in the absence of catalyst. The as-obtained CMTs have highly graphitized structure and have a homogenous morphology with an internal diameter of about 1 μm, a wall thickness of 5 nm and several millimeters in length. The Young's modulus of the CMTs was determined to be 0.652 TPa on average, which is comparable to that of carbon nanotubes reported in previous research.     

Sorption capacity of carbon nanotubes prepared by mechanochemical processing of amorphous carbon

We have studied the sorption properties of nanofibrous carbon (multiwalled nanotubes) produced by milling amorphous carbon prepared through sphagnum moss pyrolysis. The results demonstrate that the sorption capacity of the carbon nanotubes depends on storage time and that their oxidation behavior depends on nanotube preparation conditions.