Exposure to nanoscale particles and fibers during machining of hybrid advanced composites containing carbon nanotubes

This study investigated airborne exposures to nanoscale particles and fibers generated during dry and wet abrasive machining of two three-phase advanced composite systems containing carbon nanotubes (CNTs), micron-diameter continuous fibers (carbon or alumina), and thermoset polymer matrices. Exposures were evaluated with a suite of complementary instruments, including real-time particle number concentration and size distribution (0.005–20 μm), electron microscopy, and integrated sampling for fibers and respirable particulate at the source and breathing zone of the operator. Wet cutting, the usual procedure for such composites, did not produce exposures significantly different than background whereas dry cutting, without any emissions controls, provided a worst-case exposure and this article focuses here. Overall particle release levels, peaks in the size distribution of the particles, and surface area of released particles (including size distribution) were not significantly different for composites with and without CNTs. The majority of released particle surface area originated from the respirable (1–10 μm) fraction, whereas the nano fraction contributed ~10% of the surface area. CNTs, either individual or in bundles, were not observed in extensive electron microscopy of collected samples. The mean number concentration of peaks for dry cutting was composite dependent and varied over an order of magnitude with highest values for thicker laminates at the source being >1 × 10⁶ particles cm⁻³. Concentration of respirable fibers for dry cutting at the source ranged from 2 to 4 fibers cm⁻³ depending on the composite type. Further investigation is required and underway to determine the effects of various exposure determinants, such as specimen and tool geometry, on particle release and effectiveness of controls.

贵金属纳米粒子修饰碳纳米管的研究

碳纳米管具有独特的一维管状结构和优异的电、光、热和力学性能,是药物和纳米催化剂的理想载体。将具有独特光、电、磁和催化性能的贵金属纳米粒子负载在碳纳米管的表面,形成的碳纳米管/贵金属纳米粒子复合物不仅兼有两种纳米材料的优异性能,还可能产生新的特性,在催化、储能、燃料电池、电子器件和传感器等领域均有广阔的应用前景。本文主要从共价修饰和非共价修饰两种策略出发,综述了贵金属纳米粒子修饰碳纳米管的制备方法和研究进展。其中用天然高分子包覆的碳纳米管表面具有很好的贵金属配位结合能力,得到的纳米复合物具有良好的水分散性和生物相容性,在载药、生物传感器和肿瘤诊断治疗等生物领域具有明显的优势。     

Carbon nanotube-based fluorescence sensors

The one-dimensional π-conjugated structure endows carbon nanotube (CNT) with large specific surface area and excellent photophysical properties, thus providing a unique platform for the development of chemo- and biosensors based on optical signal output. Although CNT acts as an optical signal transducer, it does not own any intrinsic ability for the selective binding and recognition of analytes. Thus, hybridization of CNTs with functional components that specifically recognize various chemical and biomolecular analytes is often necessary in the preparation of CNT-based sensors. In this review, we summarize preparation and photophysical properties of CNT-based composites, and then highlight on fluorescence sensors based on CNT-composites. These composite sensors integrate the signal transduction property of CNT and the recognition properties of the hybridized functional components. The functional components selectively bind with the target analytes, whereas, CNTs transform the binding events into output signals detectable using spectrofluorometer. Particularly, we highlight on recent progress in the chemical and bimolecular sensors based on near-infrared fluorescence of semiconducting single-walled CNT (SWCNT) and the excellent fluorescence quenching ability of CNTs over conventional organic quenchers.     

Preparation,Characterization and Catalytic Performance of Carbon Nanotubes Promoted Ni‐B Amorphous Alloy

Ni‐B and Ni‐B/CNTs amorphous alloy catalysts were prepared by chemical reduction and impregnation‐chemical reduction methods, respectively, and characterized by TEM, ICP, XPS, XRD, BET and CO chemisorption techniques. Their catalytic activities were evaluated in acetylene selective hydrogenation reaction. Based on characterizations, the effects of carbon nanotubes on Ni‐B amorphous alloy were attributed to both its structure effect, dispersing Ni‐B particles, leading to bigger surface area of active nickel and enhancing the thermal stability, and the electronic effect, resulting in electron‐rich nickel centers. Therefore, the superior thermal stability and acetylene selective hydrogenation activities of Ni‐B/CNTs to Ni‐B amorphous catalyst were obtained in the present study.     

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。     

碳纳米管微结构的改变对其容量性能的影响

以KOH为活性剂，通过在高温下将碳纳米管进行活化处理来实现对碳纳米管管壁结构的改变，得到了比表面积和孔容分别是活化处理前约3倍和1.5倍的活性碳纳米管.将活化处理前后两种碳纳米管分别制作成电化学超级电容器电极，在充满氩气的无水手套箱组装成模拟电化学超级电容器，在恒流充放电模式下进行电化学可逆容量的测试，发现活性碳纳米管的电化学容量远高于活化前碳纳米管，是它的2倍.从而发现碳纳米管被打断，管壁变粗糙的活性碳纳米管比一般碳纳米管更适合用于电化学超级电容器电极材料.     

The use of organometallic transition metal complexes in the synthesis of shaped carbon nanomaterials

A review of the use of organometallic complexes in the synthesis of shaped carbon nanomaterials (SCNMs), in particular carbon nanotubes (CNTs) has been undertaken. This review reveals that a limited number of organometallic complexes have been used as catalysts (typically ferrocene, Fe(CO)₅) to make carbon materials that have distinctive shapes. Depending on the reaction conditions employed, ferrocene can be used to synthesize single walled (SWCNTs), double walled (DWCNTs) and multiwalled nanotubes (MWCNTs) as well as fibres and other SCNMs. The type of reactor used as well as the reaction conditions (temperature, pressure, gas flow rates, etc.) and the presence of hydrogen and heteroatoms (N, O, S, P, etc.) also play a role in determining the final carbon types (and their sizes) that have been synthesized. The influence of the various chemical and physical factors on the carbons produced are discussed. The current mechanism used to explain the formation of CNTs is described.     

Synthesis and optoelectronic behavior of conjugated polymer poly(3‐hexylthiophene) grafted on multiwalled carbon nanotubes

A nanocomposite of multiwalled carbon nanotubes (CNTs) and poly(3‐hexylthiophene) (P3HT) was prepared by grafting P3HT uniformly on the surface of CNTs (P3HT/P3HT‐g‐CNT) via a “grafting from” method with the coating thicknesses controlled. It was found that as the coating thickness decreased, the crystallinity of the P3HT decreased, along with significant red‐shifting of Raman that signified alterations of chain conformation. Furthermore, although the photoluminescence (PL) peak remained unchanged when grafted on CNTs, modifications of P3HT energy gap was observed, indicating variations of vibronic levels arising from the grafting. Moreover, broadening of the PL emission took place that suggested decreasing of lifetimes of the photo‐generated species when grafted on CNTs. Bilayer photovoltaic devices with the (6,6)‐phenyl C61‐butyric acid methyl ester as the electron acceptor have shown that the nanocomposite P3HT/P3HT‐g‐CNT performed much more efficiently as the electron donor, in both photocurrent density and power conversion efficiency, compared with the neat P3HT. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

基于新型二氧化锰-碳纳米管复合材料的高灵敏过氧化氢传感器

本文以多壁碳纳米管(MWCNTs)和KMnO4为原料,通过直接氧化还原反应合成了一种新型MnO2-C纳米复合材料,将其滴涂在玻碳(GC)电极表面,成功制备出一种非酶型H2O2传感器。采用循环伏安法和计时电流法研究了该传感器对H2O2的电催化氧化行为。实验结果表明,与GC电极和MWCNTs修饰电极相比,该电极对H2O2氧化显示出更好的催化活性。实验对影响电极性能的各种参数,包括pH值、工作电位及MnO2-C修饰量进行了探讨。在最佳实验条件下,传感器对H2O2响应的线性范围为5.0×10-7～0.2mol·L-1,检测限(S/N=3)为1.4×10-7 mol·L-1。该传感器选材新颖,制备方法简单,重现性好,稳定性和抗干扰能力强。     

Preparation of Core–Shell Nanofibers with Selectively Localized CNTs from Shish Kebab‐like Hierarchical Composite Micelles

A novel and facile bottom‐up strategy for preparing core‐shell nanofibers with selectively localized carbon nanotubes is developed using hierarchical composite micelles of crystalline‐coil copolymer and carbon nanotubes as the building blocks. An amphiphilic di‐block copolymer of poly (p‐dioxanone) (PPDO) and PEG (polyethylene glycol) functionalized with pyrene moieties at the chain ends of PPDO blocks (Py‐PPDO‐b‐PEG) is designed for constructing composite micelles with multiwalled carbon nanotubes (MWCNTs). The self‐assembly of Py‐PPDO‐b‐PEG and MWCNTs is co‐induced by the crystallization of PPDO blocks and the π–π stacking interactions between pyrene moieties and MWCNTs, resulting in composite micelles with “shish kebab”‐like nanostructure. A mixture of composite micelles and polyvinyl alcohol (PVA) water solution is then used as the spinning solution for preparing electrospun nanofibers. The morphologies of the nanofibers with different composition are investigated by SEM and TEM. The results suggest that the MWCNTs selectively localized in the core of the nanofibers of MWCNTs/Py‐PPDO‐b‐PEG/PVA. The alignment and interfusion of composite micelles during the formation of nanofibers may confine the carbon nanotubes in the hydrophobic core region. In contrast, the copolymer without pyrene moieties cannot form composite micelles, thus these nanofibers show selective localization of MWCNTs in the PVA shell region.