Preparation and characterization of biocompatible magnetic carbon nanotubes

Magnetic carbon nanotubes consisting of multi-wall carbon nanotubes (MWNTs) core and Fe₃O₄ shell were successfully prepared by in situ thermal decomposition of Fe(acac)₃ or FeCl₃ or Fe(CO)₅ in 2-pyrrolidone containing acid treated MWNTs at 240 °C with the protection of nitrogen gas. The samples were characterized by TEM, XRD, SEAD, XPS and superconducting quantum interference device. Also, their biocompatibility was compared with naked carbon nanotubes. The results showed that after coated with Fe₃O₄ nanoparticles, the obtained magnetic carbon nanotubes show superparamagnetic characteristic at room temperature, and their blocking temperature is about 80 K. The magnetic properties of the nanotubes are relevant to the content of magnetic particles, increasing content of magnetic nanoparticles leads to higher blocking temperature and saturation magnetization. The results of antimicrobial activities to bacterial cells (Escherichia coli) showed that the MWNTs have antimicrobial activity, while the magnetic nanotubes are biocompatible even with a higher concentration than that of MWNTs.     

模板法合成多壁碳纳米管复合材料

以包覆在碳纳米管表面的薄层二氧化锰作为表面再包覆聚苯胺的反应性模板合成了聚苯胺和碳的复合的多壁纳米管的结构,该复合材料在水中显示出很好的分散性．该方法还可以用来合成如聚3,4-乙撑二氧噻吩、聚吡咯、二氧化硅、无定形碳等材料与碳纳米管的复合材料.     

Structure comparison of nanotubes produced by different processes

Several methods used for the synthesis of carbon nanotubes have been developed in the last decade. The preparation techniques used, and their associated parameters, have an ultimate effect on the structure of the resulting nanotubes. Consequently, it is of great interest to compare the structure of carbon nanotubes synthesized by different techniques. We investigated a range of nanotubes of different origin by scanning probe microscopy (TM-AFM), and by scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS). Three different types of nanotubes have been investigated: commercial SWNT and MWNT, MWNT (synthesized using a CCVD process) and its SiO₂ coated variant, and nanostructures produced using an electrochemical method. A preparative technique is described and different tube parameters are measured. The quality of coated MWNT-s is investigated and nano-structured rings are revealed in samples obtained by electrolysis of molten salts on graphite electrodes.     

Nickel-containing carbon nanotubes and nanoparticles prepared in a high-frequency arc plasma

This paper presents the results of an investigation of nickel-containing carbon nanostructures prepared by plasma-chemical synthesis in a carbon-helium plasma jet at atmospheric pressure with the arc fed by a high-frequency current. It is demonstrated that, under these conditions, the conversion of graphite into a carbon condensate reaches 98 wt % and the contents of carbon nanotubes and nickel in this condensate are 72 and 10 wt %, respectively. Sequential treatment with nitric and hydrochloric acids has made it possible to extract purified carbon nanotubes and nickel nanoparticles coated with a carbon shell (approximately 50 nm thick) in which the nickel content is 4 wt %. Data are presented on the diameters of the prepared nanotubes and on the state of carbon in the samples.     

初始温度及碳源对碳纳米管气相爆轰法合成的影响

改变初始温度以及分别使用甲烷和乙炔气体作碳源时气相爆轰合成碳纳米管,研究了初始温度与不同碳源对碳纳米管的影响。利用X射线衍射(XRD)、透射电镜(TEM)、拉曼(Raman)光谱等对碳纳米管进行表征。结果表明,随着初始温度的升高,所合成的碳纳米管的产量减少且石墨化程度降低,但管壁会变得光滑且管径有所增加。当使用乙炔时,所合成的产物中没有碳纳米管,而是合成了石墨化程度较高的无定形碳,随着催化剂量的增加,产物中碳包覆颗粒增多且包覆层清晰可见,但存在结构缺陷。当初始温度在110~130 ℃时,使用甲烷气体运用气相爆轰的手段是合成碳纳米管的较佳方案。     

微量水对碳纳米管形貌的影响及其机理研究

利用介质阻挡放电等离子体化学气相沉积技术,在蒸镀有25nm Ni催化剂层的Si基片上,以CH₄和H₂作为反应气体,在973K下制备了碳纳米管,并研究了微量水的引入对碳纳米管形貌的影响.场发射扫描电子显微镜结果表明,不加水时,制备出的碳纳米管直径不均匀,分布在40—90nm之间,呈链节状的结构;加入少量水时,制备出的碳纳米管直径比较均匀,集中在70nm左右,表面为瘤状结构;当水的流量进一步增加时,得到的碳纳米管表面光滑,出现了枝状结构.原位测量了加水前后等离子体区的发射光谱,分析了微量水的引入对于碳纳米管形貌变化的影响机理. 关键词： 碳纳米管 介质阻挡放电 水 发射光谱     

可溶性聚噻吩甲烯包覆碳纳米管的三阶非线性光学响应

采用原位聚合的方法合成了聚(3-己基噻吩)-2,5-二(4-羟基-3-甲氧基苯甲烯)包覆的多壁碳纳米管(PHTHMOBQ/MWNTs). 荧光光谱分析表明, PHTHMOBQ/MWNTs复合体中, 碳纳米管与共轭聚合物PHTHMOBQ之间形成光致电子转移体系, 使得π电子离域程度增加, 并且导致荧光量子效率降低. 根据E_g与入射光子能量hν的关系, 拟合了PHTHMOBQ/MWNTs薄膜的光学禁带宽度. 发现随着碳纳米管含量的增加, E_g逐步减小. 采用简并四波 关键词： 共轭聚合物 碳纳米管 光致电子转移 三阶非线性光学效应     

Multifunctional Polymer‐Coated Carbon Nanotubes for Safe Drug Delivery

Although progress in the use carbon nanotubes in medicine has been most encouraging for therapeutic and diagnostic applications, any translational success must involve overcoming the toxicological and surface functionalization challenges inherent in the use of such nanotubes. Ideally, a carbon‐nanotube‐based drug delivery system would exhibit low toxicity, sustained drug release, and persist in circulation without aggregation. Here, carbon nanotubes (CNTs) coated with a biocompatible block‐co‐polymer composed of poly(lactide)‐poly(ethylene glycol) (PLA‐PEG) are reported to reduce short‐term and long‐term toxicity, sustain drug release of paclitaxel (PTX), and prevent aggregation. The copolymer coating on the surface of CNTs significantly reduces in vitro toxicity. Moreover, the coating reduces the in vitro inflammatory response. Compared to non‐coated CNTs, in vivo studies show no long‐term inflammatory response with CNT coated with PLA‐PEG (CLP) and the surface coating significantly decreases acute toxicity by doubling the maximum tolerated dose in mice. In vivo biodistribution and histology studies suggest a lower degree of aggregation in tissues.     

可溶性高聚物-多壁碳纳米管复合物的吸收光谱和光限幅性能研究

合成了三种可溶性高聚物嫁接的多壁碳纳米管复合物,包括聚乙烯基咔唑-多壁碳纳米管复合物(MWNTs-PVK),聚苯乙烯-多壁碳纳米管复合物(MWNTs-PSt)和聚甲基丙烯酸甲酯-多壁碳纳米管复合物(MWNTs-PMMA)。合成样品的TEM图显示出高聚物成功地包裹在碳纳米管外。样品的氯仿溶液UV-Vis 吸收谱显示,复合物的紫外区与纯的多壁碳纳米管不同,有一些复杂的特征吸收峰,反映了高聚物与碳纳米管共价连接的作用。利用Z扫描技术通过527 nm的纳秒激光脉冲激发研究了这三种复合物的非线性光学性质和光限幅性能。这三种复合物的氯仿溶液的光限幅性能很相似,并且优于纯多壁碳纳米管氯仿悬浮液和C60甲苯溶液。为解释观察到的结果,研究了样品的非线性折射,非线性吸收和非线性散射机制。结果显示,非线性吸收是引起样品光限幅的主要机制。     

Effect of passivating Al<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films on MnO<Subscript>2</Subscript>/carbon nanotube composite lithium-ion battery anodes

MnO₂/carbon nanotube composite electrodes for Li-ion battery application were directly coated with ultrathin thicknesses of aluminum oxide film by atomic layer deposition (ALD). The non-reactive Al₂O₃ layer not only provides a stable film to protect the manganese oxide and carbon nanotubes from undesirable reaction with the electrolyte but also restrains the volume change strain of manganese oxide during cycling. The first cycle Coulombic efficiency of coated samples was increased to different extents depending on the coating thickness. In the following cycles, the coated electrodes denote high specific capacity, good capacity retention ability, and perfect rate charge/discharge performance.     

Effect of carbon nanotubes addition on thermoelectric properties of Ca3Co4O9 ceramics

Increasing the phonon scattering center by adding nanoparticles to thermoelectric materials is an effective method of regulating the thermal conductivity. In this study, a series of Ca$_{3}$Co$_{4}$O$_{9}/x$ wt.% CNTs ($x=0$, 3, 5, 7, 10) polycrystalline ceramic thermoelectric materials by adding carbon nanotubes (CNTs) were prepared with sol-gel method and cold-pressing sintering technology. The results of x-ray diffraction and field emission scanning electron microscopy show that the materials have a single-phase structure with high orientation and sheet like microstructure. The effect of adding carbon nanotubes to the thermoelectric properties of Ca$_{3}$Co$_{4}$O$_{9}$ was systematically measured. The test results of thermoelectric properties show that the addition of carbon nanotubes reduces the electrical conductivity and Seebeck coefficient of the material. Nevertheless, the thermal conductivity of the samples with carbon nanotubes addition is lower than that of the samples without carbon nanotubes. At 625 K, the thermal conductivity of Ca$_{3}$Co$_{4}$O$_{9}$/10 wt.% CNTs sample is reduced to 0.408 W$\cdot$m$^{-1}\cdot$K$^{-1}$, which is about 73% lower than that of the original sample. When the three parameters are coupled, the figure of merit of Ca$_{3}$Co$_{4}$O$_{9}$/3 wt.% CNTs sample reaches 0.052, which is 29% higher than that of the original sample. This shows that an appropriate amount of carbon nanotubes addition can reduce the thermal conductivity of Ca$_{3}$Co$_{4}$O$_{9}$ ceramic samples and improve their thermoelectric properties.     

电化学阴极沉积制备氧化镍/碳纳米管复合电极的准电容特性

采用催化裂解的方法制备了碳纳米管,其比容量为12F/g.采用碳纳米管作为电极基体,采用阴极电化学还原Ni(NO3)2的方法在碳纳米管基体表面均匀的沉积了纳米氧化镍颗粒并由此制备了氧化镍碳纳米管复合电极材料.采用循环伏安、恒流充放电、交流阻抗及扫描电镜等方法考察了复合电极材料的容量特性、阻抗特性、自放电特性以及电极表观特征.实验表明复合电极具有良好的电化学特性,碳纳米管基体在明显降低氧化镍材料的阻抗的同时还提高了电极材料的电化学容量并拓宽了电极材料的有效工作电位窗,复合电极在6mol/LKOH电解液中比容量达到25F/g且表现了良好的电化学可逆性.与碳纳米管基电容器相比,采用氧化镍复合电极材料组装的电容器具有较低的自放电率.     

Synthesis and application of iron-filled carbon nanotubes coated with FeCo alloy nanoparticles

FeCo alloy nanoparticles were coated onto the iron-filled carbon nanotubes by an electroless plating method. As-prepared samples were then annealed at different temperatures. The morphologies and structures of the samples were characterized, and the relationship between the soft magnetic properties and the Fe/Co ratios of the samples was established. The microwave absorbing characteristics of the samples were also evaluated. The results show that the soft magnetic characteristics of iron-filled carbon nanotubes can be improved after being coated with FeCo alloy nanoparticles and then heat treated, which results in more effective microwave absorption.     

Synthesis and characterization of polycaprolactone-grafted carbon nanotubes via click reaction

Polycaprolactone (PCL) was covalently grafted on the surface of carbon nanotubes by a simple click reaction of propargyl-terminated PCL (propargyl-PCL) and carbon nanotubes (CNTs) containing azide groups (MWNT-N₃). Propargyl-PCL was synthesized by the ring-opening polymerization of ε-caprolactone using propargyl alcohol and stannous octoate. MWNT-N₃ was prepared from MWNT having 2-bromoisobutyryl groups (MWNT-Br) with sodium azide by azidation. The melting temperature of propargyl-PCL was shifted to the high temperature in PCL-grafted MWNT. The thermal stability of PCL-grafted MWNT was enhanced as compared to that of propargyl-PCL. PCL was coated on the surface of MWNT with a high density of PCL chains, which showed good solubility of PCL-grafted MWNT in organic solvents. PCL-grafted MWNT was characterized with FT-IR, ¹H NMR, Raman, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy.     

Imaging as-grown single-walled carbon nanotubes originated from isolated catalytic nanoparticles

Discrete catalytic nanoparticles with diameters in the range of 1–3 nm are obtained by placing controllable numbers of metal atoms into the cores of apoferritin. With nanoparticles placed on transmission electron microscope (TEM) grids coated with ultra-thin alumina membranes, isolated single-walled carbon nanotubes are grown by chemical vapor deposition and directly examined by TEM. The characterizations, carried out at single-tube and single-particle level, obtain clear evidence that the diameters of the nanotubes are determined by the diameters of catalytic nanoparticles. For the first time, both ends of an as-grown single-walled nanotube are imaged by TEM, leading to a microscopic picture of the nanotube-growth mechanism. Received: 19 September 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Preparation of carbon nanotubes as the conductive coating layer on flexible thermal-resistant substrate by permeating method and its residual stress analysis

A polyarylate (PAR) substrate was first prepared by hot pressing and then carbon nanotubes (CNTs) were coated on its surface by a low-temperature spraying method. In order to eliminate the residual stress and enhance the adhesive ability between the substrate and the coated CNT layer, an optimal thermo-permeating process is proposed. The relationship between the thickness of the permeating layer and the residual stress of coating layers was investigated. Triple-layer structure models were provided to evaluate the residual stress of coating layers. The experimental results show that if the sample was treated by the optimal thermo-permeating process, its residual stress was dramatically reduced from 1.7×10³ MPa to 0.45 Pa; meanwhile, its adhesive ability was intensively enhanced from 1B to 5B according to ASTM D3359 adhesion classifications.     

Preparation of carbon nanosheets deposited on carbon nanotubes by microwave plasma-enhanced chemical vapor deposition method

Carbon nanosheets were synthesized by microwave plasma-enhanced chemical vapor deposition method on carbon nanotubes substrate which was treated by hydrogen plasma. The results showed that the diameters of carbon nanotubes first got thick and then “petal-like” carbon nanosheets were grown on the outer wall of carbon nanotubes. The diameters of carbon nanotubes without and with carbon nanosheets were 100-150 and 300-500 nm, respectively. Raman spectrum indicated the graphite structure of carbon nanotubes/carbon nanosheets. The hydrogen plasma treatment and reaction time greatly affected the growth and density of carbon nanosheets. Based on above results, carbon nanosheets/carbon nanotubes probably have important applications as cold cathode materials and electrode materials.     

New aspects on pulsed laser deposition of aligned carbon nanotubes

We have grown carbon nanotubes (CNT) by pulsed laser deposition (PLD) at 1000 °C in Ar atmosphere. A Nd/YAG laser was used for irradiation of a graphite target containing Ni and Co rods. High-resolution scanning electron microscopy (HRSEM) and transmission electron microscopy (TEM) images showed that “closed” carbon nanotubes were grown between clusters of metallic particles, so that the individual nanotubes were arranged in parallel to each other forming a shape of “Rope-Bridge”. The nanotubes structure was analyzed by high-resolution transmission electron microscopy (HRTEM) and their type was found to be of MWNT, containing about five SWNT. Total diameter was 5-20 nm and their length was about 1 μm. High homogeneous distribution carbon nanotubes were grown and different structures were observed such as well-aligned carbon nanotubes, bamboo-like and Y-junction carbon nanotubes.     

多壁碳纳米管对p型Ba0.3FeCo3Sb12化合物热电性能的影响

用两步固相反应法合成了P型Ba填充方钴矿化合物Ba0.3FeCo3Sb12，并采用放电等离子烧结法(SPS)制备了Ba0.3FeCo3Sb12／多壁碳纳米管复合材料．研究了Ba0.3FeCo3Sb12／多壁碳纳米管复合材料的结构及多壁碳纳米管对其热电性能的影响规律：SEM分析表明多壁碳纳米管比较均匀地分布在Ba0.3FeCo3Sb12基体中；随着碳纳米管添加量的增加，Ba0.3FeCo3Sb12／多壁碳纳米管复合材料的电导率下降、塞贝克系数略微下降、晶格热导率大幅度降低，当碳纳米管含量为5％时其晶格热导率最小；当碳纳米管的含量为3％时，本研究得到的Ba0.3FeCo3Sb12／碳纳米管复合材料的最大ZT值达0．78．     

Fabrication of barium/strontium carbonate coated amorphous carbon nanotubes as an improved field emitter

Amorphous carbon nanotubes (aCNTs) were synthesized by a chemical reaction between ferrocene and ammonium chloride at a temperature ～250 ^°C in an air furnace. As-synthesized aCNTs were coated with the barium/strontium carbonate through a simple chemical process. The coating of barium/strontium carbonate was confirmed by a high resolution transmission electron microscopy, X-ray diffraction, and Fourier transformed infrared spectroscopy. Morphology of the as-prepared samples was studied by field emission scanning electron microscopy. Thermal gravimetric analysis showed that barium/strontium carbonate coated aCNTs are more stable than the pristine aCNTs. As-prepared barium/strontium carbonate coated aCNTs showed significantly improved field emission properties with a turn-on field as low as 2.5 V/μm. The variation of field emission characteristics of the barium/strontium carbonate coated aCNTs with interelectrode distances was also studied.