Encapsulation and convex-face thiozonolysis of triatomic sulfur (S(3)) with carbon nanotubes

Nanotubes are a class of host cavities increasingly used to encapsulate unstable molecules, yet none have been exploited to host reactive sulfur species, such as thiozone (S(3)). In this paper, density functional theory and (ONIOM) calculations were used to compute single-walled carbon nanotube (SWNT)-thiozone combinations for the inclusion of S(3) into the hollow nanotube space and to rationalize when 1,2,3-thiozonide formation can take place. Nanotube diameter selectivity for the isomerization of the C(2v) form of S(3) to the D(3h) form proved to be elusive. Acyclic C(2v) S(3) was ~6 kcal/mol more stable than cyclic D(3h) S(3) whether it was free or encapsulated within an SWNT. 1,2,3-Thiozonide formation took place on the convex side of nanotubes of low tube radii, such as the armchair (4,4) and (5,5) SWNTs. In terms of the reaction mode of C(2v) S(3), the 1,3-dipolar addition reaction was preferred compared with the [2 + 2] cycloaddition and chelotrope paths.     

Rheological and Mechanical Characterization of Multi-Walled Carbon Nanotubes/Polypropylene Nanocomposites

The rheology and morphology of multi-walled carbon nanotube (MWNT)/polypropylene (PP) nanocomposites prepared via melt blending was investigated. The minor phase content of MWNT varied between 0.25 and 8 wt%. From morphological studies using a scanning electron microscopy technique a good dispersion of carbon nanotubes in the PP matrix was observed. The rheological studies were performed by a capillary rheometer, and mechanical properties of the nanocomposites were studied using a tensile and flexural tester. Both PP and its nanocomposites showed non-Newtonian behavior. At low shear rates the addition of MWNT content causes an increase in viscosity; however, viscosity is less sensitive to addition of MWNT content at higher shear rates. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. From this calculation it was concluded that the temperature sensitivity of nanocomposites was increased by increasing of nanotube content. An increase in tensile and flexural moduli and Izod impact strength was also observed by increasing the MWNT content. From rheological and mechanical tests it was concluded that the mechanical and rheological percolation threshold is at 1.5 wt%.     

聚苯胺-碳纳米管复合体的制备及其光响应

纳米尺寸导电材料对功能分子材料及分子器件的作用越来越显得重要.采用原位乳液聚合法制备聚苯胺 碳纳米管复合体，SEM和TEM照片显示复合管的直径为60—70nm，聚苯胺的包裹层厚度约25—30nm.x射线衍射及热分析表明纳米复合管的结晶性能增强，热稳定性得到提高.光电响应试验表明复合管的光吸收增强，光电流增大，说明聚苯胺 碳纳米复合管薄膜受光照射后发生了光诱导电荷分离现象. 关键词： 聚苯胺 碳纳米管 复合纳米管 光电流     

Fabrication and Properties of Carbon Nanotube and Poly(vinyl alcohol) Composites

Dispersion of carbon nanotubes in a polymer matrix is one of the most critical issues in carbon nanotube/polymer composites. In this paper we discuss the considerable improvement in the dispersion of multiwalled carbon nanotubes (MWNTs) in poly(vinyl alcohol) (PVA) matrix that was attained through gum arabic treatment. The mechanical properties of these MWNT/PVA composites show that only 2 wt% nanotube loading increases the tensile modulus by more than 130%.     

Thermal properties of carbon nanotubes and nanotube-based materials

The thermal properties of carbon nanotubes are directly related to their unique structure and small size. Because of these properties, nanotubes may prove to be an ideal material for the study of low-dimensional phonon physics, and for thermal management, both on the macro- and the micro-scale. We have begun to explore the thermal properties of nanotubes by measuring the specific heat and thermal conductivity of bulk SWNT samples. In addition, we have synthesized nanotube-based composite materials and measured their thermal conductivity. The measured specific heat of single-walled nanotubes differs from that of both 2D graphene and 3D graphite, especially at low temperatures, where 1D quantization of the phonon bandstructure is observed. The measured specific heat shows only weak effects of intertube coupling in nanotube bundling, suggesting that this coupling is weaker than expected. The thermal conductivity of nanotubes is large, even in bulk samples: aligned bundles of SWNTs show a thermal conductivity of >200 W/m K at room temperature. A linear K(T) up to approximately 40 K may be due to 1D quantization; measurement of K(T) of samples with different average nanotube diameters supports this interpretation. Nanotube–epoxy blends show significantly enhanced thermal conductivity, showing that nanotube-based composites may be useful not only for their potentially high strength, but also for their potentially high thermal conductivity. Received: 17 October 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Activation behavior and dielectric relaxation in polyvinyl alcohol and multiwall carbon nanotube composite films

The dc and ac electrical transport property of Polyvinyl Alcohol-Multiwall Carbon Nanotubes (PVA-MWNT) composites has been investigated within a temperature range and in the frequency range 20Hz-1MHz. The temperature variation of dc conductivity gives the presence of two different activation energies. The dielectric properties of the samples have been explained in terms of electric modulus vector.The dielectric relaxation has been explained in terms of interfacial polarization occurring in between the insulating PVA matrix and MWNT conductive filler. The variation of the relaxation time with temperature also indicates the presence of two different activation energies.     

170keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响

碳纳米管具有优异的导电性, 是未来电子元器件的理想候选材料, 应用前景广阔. 针对碳纳米管在空间电子元器件的应用需求, 本文研究了170 keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响. 采用扫描电子显微镜(SEM)、拉曼光谱仪(Raman)、X射线光电子能谱仪(XPS)及电子顺磁共振谱仪(EPR)对辐照前后碳纳米管试样的表面形貌和微观结构进行分析; 利用四探针测试仪对碳纳米管薄膜进行导电性能分析. SEM分析表明, 170 keV质子辐照条件下, 当辐照注量高于5×10¹⁵ p/cm² (protons/cm²)时, 碳纳米管薄膜表面变得粗糙疏松, 纳米管发生明显弯曲、收缩及相互缠结现象. 目前, 质子辐照纳米管发生的收缩现象被首次发现. 基于Raman和XPS分析表明, 170 keV质子辐照后碳纳米管的有序结构得到改善, 且随辐照注量增加, 碳纳米管的有序结构改善明显. 结构的改善主要是由于170 keV质子辐照碳纳米管所产生的位移效应导致缺陷重组. EPR分析表明, 随着辐照注量的增加, 碳纳米管薄膜内的非局域化电子减少. 利用四探针测试分析表明, 碳纳米管薄膜的导电性能变差, 这是由于170 keV质子辐照导致碳纳米管薄膜中的电子特性及形态发生改变. 本文研究结果有助于利用质子辐照对碳纳米管膜结构和性能进行调整, 从而制备出抗辐射的纳米电子器件.     

Well-defined single-walled carbon nanotube fibers as quantum wires: Ballistic conduction over micrometer-length scales

We report quasi-ballistic conduction in single-walled carbon nanotube (SWNT) fibers at room temperature, with a measured mean free path of 1.0–2.6 μm. The dynamic submersion of vertical SWNT fibers into liquid mercury (Hg) electrode shows plateaus and steps indicative of quasi-ballistic electron transport. This response is described with a newly developed network model that uses surface impurities to simplify the parallel conducting channels. The quasi-ballistic SWNT fibers exhibit a resistance per unit length of 2.5–6.5 kΩ/μm and a mean free path exceeding 1 μm, a length longer than typical via dimensions in existing Si-chip technologies. These results highlight that SWNT fiber conductivity can be enhanced by increasing the metallic to semiconducting SWNT ratio and reducing the surface impurities.     

Preparation and characterization of multiwall carbon nanotube/polypyrrole coaxial fibrils

Multiwall carbon nanotube (MWNT)/polypyrrole (PPy) fibrils were fabricated by template-free in situ electrochemical deposition of PPy over MWNTs, and characterized by electron microscopy and electrical measurements. Scanning and transmission electron microscopy studies reveal that PPy coating on the surface of nanotube is quite uniform throughout the length, with the possibility of forming unique Y-junctions. Current (I)-voltage (V) characteristics at various temperatures show nonlinearity due to tunneling and hopping contributions to transport across the barriers. AC conductivity measurements (300-4.2 K) show that the onset frequency scales with temperature, and the nanoscale connectivity in MWNT/PPy fibrils decreases with the lowering of temperature.     

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.     

Electron field emission from single-walled carbon nanotube nonwoven

Field emission from single-walled carbon nanotube (SWNT) nonwoven has been investigated under high vacuum with different vacuum gaps. A low turn-on electric field of 1.05\,V/$\mu $m is required to reach an emission current density of 10 $\mu $A/cm$^{2}$. An emission current density of 10 mA/cm$^{2}$ is obtained at an operating electric field of 1.88\,V/$\mu $m. No current saturation is found even at an emission current of 5\,mA. With the vacuum gap increasing from 1 to 10 mm, the turn-on field decreases monotonically from 1.21 to 0.68\,V/$\mu $m, while the field amplification is augmented. The good field-emission behaviour is ascribed to the combined effects of the intrinsic field emission of SWNT and the waved topography of the nonwoven.     

碳纳米管掺杂对聚合物聚(2-甲氧基-5-辛氧基)对苯乙炔-PbSe量子点复合材料性能的影响

基于碳纳米管的良好导电性、激子传输性能和量子点聚合物复合材料高的光电转换性能, 采用原位缩合法制备了聚合物聚(2-甲氧基-5-辛氧基)-对苯乙炔(MOPPV)功能化碳纳米管(SWNT)-PbSe量子点复合材料, 通过对复合材料的X射线衍射、透射电子显微镜和紫外可见吸收光谱研究, 发现MOPPV, SWNT与PbSe量子点可以有效地复合, 且SWNT与MOPPV形成网状结构; PbSe量子点尺寸为5.75 nm, 其可均匀地分散在MOPPV-SWNT基体中形成包覆或镶嵌结构, 并发生了光诱导电荷转移.通过对复合材料的光电性能研究发现, 当MOPPV, SWNT, PbSe三者的质量比为1: 0.3 : 1 时其光电性能最好, 开路电压为0.556 V, 短路电流为2.133 mA, 填充因子为34.48%, 转换效率为0.452%, 与聚合物MOPPV-PbSe量子点复合材料材料相比, 光电性能提高了2–3倍. 关键词： 量子点 碳纳米管 复合材料 转换效率     

Functional multi-walled carbon nanotube/polyaniline composite films as supports of platinum for formic acid electrooxidation

Embedding of carbon nanotubes in conducting polymeric matrices for various nanocomposites material is now a popular area. In this article, a concise chemical method has been described for the preparation of homogeneous nanocomposite of multi-walled carbon nanotube (MWNT)/polyaniline (PANI) by electrochemical codeposition. For this we functionalized the MWNTs via the diazotization reaction. This helped to disperse the nanotubes in aniline. The composite films were dispersed Pt by electrodeposition technique. The presence of MWNTs and platinum in the composite films was confirmed by XRD analysis and transmission electron microscopy (TEM). Four-point probe investigations revealed that the MWNT/PANI composite films exhibited a good conductivity. Cyclic voltammograms (CV) showed that Pt-modified MWNT/PANI composite films perform higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formic acid oxidation. The results imply that the MWNT/PANI composite films as a promising support material improves the electrocatalytic activity for formic acid oxidation greatly.     

Demetalization of single-walled carbon nanotube thin films with microwave irradiation

The microwave irradiation effects on purified HiPCO and CoMoCat single-walled carbon nanotube (SWNT) thin films are investigated. The surface conductivities of the SWNT films are extracted from the measured THz transmission coefficients to provide a direct indication of the metallic content in the films. The observed drastic conductivity decrease indicates a significant metallic content reduction after the microwave irradiation. Two different laser excitations are applied for Raman spectroscopy to reveal the response of different nanotube species. The Raman spectra of both HiPCO and CoMoCat thin films confirm the decrease of metallic carbon nanotubes. The observed microwave-induced effects may potentially lead to a convenient scheme for demetalization of single-walled carbon nanotube mixtures.     

功能光学纳米Ag薄膜的制备及其光学特性研究

对以热蒸发法制备的超薄Ag薄膜,扫描电子显微镜结果显示其呈纳米尺度的颗粒状,由透射谱测量发现其具有表面等离子体激元特征.检测到不同条件制备纳米Ag薄膜的表面等离子体共振吸收峰的位移规律,且纳米Ag材料具有选择性的透过、反射特性.通过不同的制备条件,得到了在长波范围内透过率超过90％、在表面等离子体共振峰值位置处反射率接近50％且峰位可调的光学薄膜材料.这种薄膜材料有望成为应用在薄膜太阳电池中间层中具有潜在性光管理功能的光学薄膜材料. 关键词： 热蒸发 纳米Ag薄膜 表面等离子体激元 光管理     

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．     

单壁碳纳米管在场发射显示器中的应用研究

采用丝网印刷法将利用电弧放电法制备的单壁碳纳米管印刷在玻璃板上作为场发射显示器阴极材料，利用荧光粉阳极测试了其发光亮度，并研究其场发射性能.实验结果表明，单壁碳纳米管作为场发射显示器阴极材料具有较低的开启电场和较大的场发射电流密度，显示出良好的场发射特性.     

Magnetoadsorptive Particles Enabling the Centrifugation‐Free,Preparative‐Scale Separation,and Sorting of Single‐Walled Carbon Nanotubes

A novel magnetic composition of the high surface area particles with amide chemical functionality, Sephacryl S‐200, is reported enabling the preparative‐scale (1 L, ≈5–10 mg) separation of metallic and semiconducting single‐walled carbon nanotubes (SWNT) from completely unpurified and uncentrifuged nanotube stocks. Sephacryl S‐200 has previously been utilized in separating semiconducting SWNT (s‐SWNT) on the laboratory scale. Significantly, use of these magnetic derivative particles in absorptive separation of SWNT allows the unprecedented and industrially scalable purification of both metallic SWNT (m‐SWNT) as well as s‐SWNT directly from uncentrifuged, ultrasonicated surfactant‐based SWNT solutions by simple and scalable magnetic separation. These particles also allowed for the systematic study on the effect of SWNT–polymer interaction time on the resulting SWNT “payloads.” Ultimately, high ‐purity m‐SWNT and s‐SWNT products are independently achieved by controlling the SWNT–polymer interaction time and relative concentrations, as well as SWNT sonication conditions. Furthermore, by controlling these factors, single‐chirality (6,5) s‐SWNT can be isolated with 92% purity directly from unpurified stocks. Thermogravimetric analysis indicates a total process SWNT yield of 1.2% and 1.7% for m‐SWNT and s‐SWNT, respectively. These results demonstrate the potential for a preparative method for separating carbon nanotubes based on electronic properties.     

Raman spectroscopy and field-emission properties of CVD-grown carbon-nanotube films

Carbon-nanotube films are very efficient cathodes for field-emission devices. This study presents a comprehensive comparison between structural, spectroscopic and field-emission properties of films of aligned and non-aligned multi-wall nanotubes (MWNTs) which are grown by thermal chemical vapour deposition. Three types of films are investigated: vertically aligned MWNTs with clean and coated nanotube side walls as well as non-aligned MWNT films. Raman spectra taken on the aligned MWNT films consist of many lines of first-, second- and third-order signals. Several lines are reported here for the first time for MWNTs. The presence of the surface coating leads to a decrease and broadening of the higher-order signals as well as an increase in the disorder-induced contributions in the first-order regime. The aligned MWNT films have excellent field-emission properties with very high emission current densities and low turn-on and threshold fields. The presence of a surface coating has no impact on the efficiency of the field-emission process. Films of non-aligned MWNTs show considerably reduced electron-emission current densities and larger critical fields. Received: 25 April 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

Influence of chirality on the thermal conductivity of single-walled carbon nanotubes

The influence of chirality on the thermal conductivity of single-walled carbon nanotubes(SWNTs) is discussed in this paper, using a non-equilibrium molecular dynamics(NEMD) method. The tube lengths of the SWNTs studied here are 20, 50, and 100 nm, respectively, and at each length the relationship between chiral angle and thermal conductivity of a SWNT is revealed. We find that if the tube length is relatively short, the influence of chirality on the thermal conductivity of a SWNT is more obvious and that a SWNT with a larger chiral angle has a greater thermal conductivity. Moreover, the thermal conductivity of a zigzag SWNT is smaller than that of an armchair one. As the tube length becomes longer, the thermal conductivity increases while the influence of chirality on the thermal conductivity decreases.