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.     

Effects of corona discharge on the surface structure, morphology and properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were modified by corona discharge and then heat treated in the air. The influences of corona discharge parameters such as treatment time and processing power were investigated. The results of energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA) indicated the introduction of oxygen-containing functional groups onto the surface of the MWCNTs after heat treatment. The water contact angle tests showed that the hydrophobicity of the MWCNTs was decreased to some extent. The static water contact angle was reduced from 146° to 122° when the time of the corona discharge treatment reached 3 min at the processing power of 200 W. The enhanced thermomechanical and mechanical properties of epoxy nanocomposites filled with the corona discharge treated MWCNTs were observed. The modified MWCNTs conferred better properties on the composites than the pristine MWCNTs because of the improved dispersion of MWCNTs in matrix and the enhanced interfacial interaction between the treated MWCNTs and epoxy.     

Improving the surface properties of multi-walled carbon nanotubes after irradiation with gamma rays

The effects of gamma-irradiation on the modification of the surface and structure of multi-walled carbon nanotubes were studied. Gamma-irradiation affected the graphitization properties of functional groups, and decreased the diameter of multi-walled carbon nanotubes. The irradiated multi-walled carbon nanotubes with the absorbed dose of 100 kGy exhibited a larger specific surface area and microporous volume as compared with the other samples. The Raman spectroscopy and X-ray photoelectron spectroscopy showed that the interaction between the gamma-irradiation and the multi-walled carbon nanotubes with the absorbed dose of 150 kGy destroyed the nanostructure of carbons, leading to the formation of diamond-like structures and carbon oxides. In addition, gamma-irradiation with the absorbed dose of 100 kGy improved multi-walled carbon nanotubes graphitization and surface properties while at higher absorbed dose (150 kGy), it induced damaged structures (sp³ bonds and oxygen compositions).     

Mild hydrothermal treatment to prepare highly dispersed multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) with improved dispersion property have been prepared by a mild and fast hydrothermal treatment. The hydrothermal process avoids using harsh oxidants and organic solvents, which is environmental friendly and greatly decreases the damage to intrinsic structure of MWCNTs. The modified MWCNTs were highly soluble in polar solvents such as water, ethanol and dimethylformamide. Morphological observation by TEM indicated that the diameter and inherent structure were well reserved in modified MWCNTs. X-ray photoelectron spectroscopy and Raman spectroscopy were used to quantify functional groups created on the MWCNT surface, and to determine rational parameters of hydrothermal process.     

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Ba^0.3FeCo³S b^１2，并采用放电等离子烧结法(SPS)制备了Ba^0.3FeCo³Sb^１2／多壁碳纳米管复合材料. 研究了Ba^0.3FeCo³Sb^１2／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Ba^0.3 FeCo³S b^１2基体中；随着碳纳米管添加量的增加，Ba^0.3FeCo3Sb^１2/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Ba^{0.3FeCo3Sb１2/碳纳米管复合材料的最大ZT值达078.}     

Physical properties,thermal stability,and glass transition temperature of multi-walled carbon nanotube/polypyrrole nanocomposites

Polypyrrole (PPy) was synthesized and doped with 1, 2, 4, and 8?wt.% of functionalized multi-wall carbon nanotubes (MWCNTs) by in situ polymerization. TGA/DTA analysis of nanocomposites revealed an increase in thermal stability by increasing the CNTs wt.%. Measurement of electrical resistivity showed a reduction in the resistivity of the composites at all temperatures. The glass transition temperature (T_g) of the samples was measured using electrical resistivity measurements and showed that by increasing the amount of functionalized MWCNTs in PPy, its T_g was increased. Temperature dependence of resistivity of pressed pure PPy showed that by increasing the pelletization pressure, the T_g increased. Also the hardness of nanocomposites was increased by increasing the MWCNTs wt.%.     

Thermal conductivity of multi-walled carbon nanotubes:Molecular dynamics simulations

Heat conduction in single-walled carbon nanotubes(SWCNTs) has been investigated by using various methods, while less work has been focused on multi-walled carbon nanotubes(MWCNTs). The thermal conductivities of the double-walled carbon nanotubes(DWCNTs) with two different temperature control methods are studied by using molecular dynamics(MD) simulations. One case is that the heat baths(HBs) are imposed only on the outer wall, while the other is that the HBs are imposed on both the two walls. The results show that the ratio of the thermal conductivity of DWCNTs in the first case to that in the second case is inversely proportional to the ratio of the cross-sectional area of the DWCNT to that of its outer wall. In order to interpret the results and explore the heat conduction mechanisms, the inter-wall thermal transport of DWCNTs is simulated. Analyses of the temperature profiles of a DWCNT and its two walls in the two cases and the interwall thermal resistance show that in the first case heat is almost transported only along the outer wall, while in the second case a DWCNT behaves like parallel heat transport channels in which heat is transported along each wall independently.This gives a good explanation of our results and presents the heat conduction mechanisms of MWCNTs.     

溶胶-喷雾法制备多壁碳纳米管增强氧化铝基复合材料及性能研究

采用溶胶-喷雾制备了多壁碳纳米管增强氧化铝基球形复合粉体,采用放电等离子真空快速烧结成型.SEM分析测试结果表明,多壁碳纳米管在氧化铝基体中呈网络分布,且主要位于晶界处,少量呈穿晶分布.复合材料性能分析测试结果表明,当多壁碳纳米管的质量分数为0.5%时,复合材料的维氏硬度相对纯的氧化铝提高了32.6%;热扩散系数在不同测试温度下相对纯氧化铝的平均提高幅度为27.2%.此外,当多壁碳纳米管质量分数达到0.5%时复合材料呈导体,根据渗流导电理论拟合得到实验制备复合材料的渗流阈值为0.32 wt.%,说明多壁碳纳米管在氧化铝基体中分散良好.     

Electrochemical and surface characterisation of gold nanoparticle decorated multi-walled carbon nanotubes

A novel type of gold nanoparticle/multi-walled carbon nanotube (AuNP/MWCNT) composite electrodes is presented. The electrochemical reduction of oxygen on these hybrid electrodes was studied using the rotating disk electrode (RDE) method. The AuNP/MWCNT nanocomposites were prepared by sputter deposition of gold in argon atmosphere on MWCNTs followed by heat-treatment of the catalyst at different temperatures. High-resolution scanning electron microscopy (HR-SEM), glancing incidence angle X-ray powder diffraction (GIXRD) and small-angle X-ray scattering (SAXS) techniques were employed to characterise the surface structure and morphology of catalyst materials. Au nanoparticles with diameter around 20 nm were dispersed at the tips and on the sidewalls of nanotubes. Electrochemical measurements were performed to demonstrate the electrocatalytic properties of the composite catalysts towards O₂ reduction in acid media. The successful preparation of AuNP/MWCNT nanocomposites by magnetron sputtering opens up the possibility of making an efficient dispersion of nanoparticles for electrocatalyst design.     

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．     

多壁碳纳米管光限幅特性的研究

用化学气相沉积法制备了多壁碳纳米管,并将其溶解在甲苯溶液中.用波长为1064nm的皮秒脉冲激光测量该样品的透过率,发现了非常明显的光限幅特性.当入射光强较小时,透射光强度随入射光强度的增大而增大,输出与输入为线性关系;随着入射光强的增大,透射光强增长的速度明显变慢,并逐渐趋于饱和.当入射光强度较小时,样品的透过率接近100%;而当入射光强为8GW/cm²时,非线性透过率达到30%.根据三光子吸收理论计算,理论拟合与实验结果非常符合,说明多壁碳纳米管的三光子吸收产生了光限幅效应.实验测 关键词： 多壁碳纳米管 光限幅 三光子吸收     

Comparative study of electrochemical capacitance of multi-walled carbon nanotubes before and after chopping

In the work, short multi-walled carbon nanotubes (S-CNTs) were synthesized by chopping conventional μm-long multi-walled carbon nanotubes (L-CNTs) under ultrasonication in H₂SO₄/HNO₃ mixed acids. A comparative electrochemical investigation performed in 6 M KOH solution demonstrated that a specific capacitance (SC) of ca. 14.6 μF cm⁻² was delivered by the S-CNTs with the specific surface area (SSA) of 207 m² g⁻¹, much larger than that of ca. 10.1 μF cm⁻² for the L-CNTs with the SSA of 223 m² g⁻¹, the reason for which was that S-CNTs with two open ends, due to good ion penetrability, provided more entrances for electrolyte ions to access the inner surface easily through their shorter inner pathway so as to enhance their SSA utilization and geometric SC. The surface structure disruption of S-CNTs, owing to ultrasonication and oxidation during chopping process, deteriorated their electronic conductivity and resulted in an inferior power property in contrast to L-CNTs.     

碳纳米管悬浮液的光限幅特性实验研究

通过超声波降解法制备了多壁碳纳米管的水-表面活性剂悬浮液,测量了其对于1 064 nm,脉宽10 ns Nd:YAG调Q脉冲激光的光限幅曲线。实验发现：入射激光能量密度较低时,出射能量密度随入射能量密度的增加而线性增加;当入射能量密度为160 mJ/cm2时,出射能量不再线性增加并且逐渐趋近于光限幅器的嵌位输出值,约16 mJ,同时,对激光的透过率从71%下降到15%。通过Z扫描和探针光实验以及45°散射角下散射能量、散射率随入射激光能量变化曲线的测量,对碳纳米管悬浮液的光限幅机理进行了研究。结果表明：其限幅机理可能源于碳纳米管吸收激光能量后升华产生的膨胀的碳气泡对入射激光产生的非线性散射;另外,非线性折射对光限幅效果也有一定的作用。     

Kondo效应对磁杂质碳纳米管电输运特性的影响

从碳纳米管中Kondo效应的影响出发, 在有限温度下采用Anderson模型表征碳纳米管/磁杂质系统, 利用Landauer公式对磁杂质碳纳米管的电导和热电势进行研究, 得出和实验结果一致结论. 关键词： Kondo效应 碳纳米管 电输运特性     

Surface modification of multi-walled carbon nanotubes by O2 plasma

The surface modification of multi-walled carbon nanotubes (MWCNTs) by O₂ plasma was carried out in this study. In order to achieve a relatively homogeneous treatment of MWCNTs powder, a rotating barrel fixed between the two discharge electrodes was used. The effect of plasma treatment parameters, such as power, time, and positions of samples (inside and outside the barrel), on the morphology and structure of MWCNTs surface was systematically analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The results showed that the direct discharge (outside the barrel) could result in not only a quick grafting of polar functional groups but also an easy damage of MWCNTs after longer time, particularly under intensive power. It was found that the surface of MWCNTs powder might be changed in three steps—expansion (loosed structure formed), peel off and oxidization with increasing of treatment time during the irradiation. In this way, a complete purification of MWCNTs powder could be finished within 30 min via plasma treatment. Our work suggested that plasma treatment could be a simple and nonpolluting method for a large scale purification of MWCNTs.     

Synthesis, characterization and cytotoxicity of surface amino-functionalized water-dispersible multi-walled carbon nanotubes

Surface functionalization of multi-walled carbon nanotubes (MWCNTs), with amino groups via chemical modification of carboxyl groups introduced on the nanotube surface, using O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (N-HATU) and N,N-diisopropylethylamine (DIEA) is reported. The N-HATU coupling agent provides faster reaction rate and the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. The amines, 1,6-hexanediamine (HDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and 1,4-phenylenediamine (PDA) were used. The resulting materials were characterized with different techniques such as FTIR, XRD, elemental analysis, TGA, TEM, UV-vis spectroscopy and cyclic voltammetry. MWCNTs functionalized with PDA posses the best dispersibility and electron transfer properties in comparison to the others amines. Functionalized MWCNTs, at the concentrations between 1 and 50 μg ml⁻¹, were not cytotoxic for the fibroblast L929 cell line. However, the concentrations of MWCNTs higher of 10 μg ml⁻¹ reduced cell growth and this effect correlated positively with the degree of their uptake by L929 cells.     

Electrical conductivity and dielectric properties of nanofibrillated cellulose thin films from bagasse

Nanocelluloses are potential candidates for applications in flexible electronic due to their unique physical and mechanical properties. However, electrical properties of these materials have not investigated thoroughly to study their electrical properties. In the current work, electrical properties of nanocellulose films prepared from bagasse pulp were studied and compared with those of bagasse pulp fibers. Two kinds of nanocelluloses were used in the current study: microfibrillated cellulose (MFC) and TEMPO‐oxidized nanofibrillated cellulose (NFC). The crystallinity, grain size, and morphology of the different nanocelluloses were studied using X‐ray diffraction and transmission electron microscopy techniques. The dc‐, ac‐ electrical conductivity, dielectric constant ?′, and dielectric loss ?″ of non‐plasticized and glycerol‐plasticized nanocellulose films were studied in the temperature range from 298 to 373 K and in the frequency range from 0.1 KHz to 5 MHz. The results showed that the dc‐ electrical conductivity verifies Arrhenius equation and the activation energies varied in the range of 0.9 to 0.42 eV. Ac‐electrical conductivity increased with frequency and fitted with power law equation, which ensures that the conduction goes through hopping mechanism. The dielectric constant decreased with increasing frequency and increased with increasing temperature, probably due to the free movement of dipole molecular chains within the cellulose fiber. Glycerol‐plasticized NFC (NFC‐G) film had the highest dielectric constant and ac‐electrical conductivity values of 79 800 and 2.80× 10^?3ohm^?1 cm^?1, respectively. The high values of dielectric constant and conductivity of the prepared films support their use in electronic components.     

XPS study of fluorinated carbon multi-walled nanotubes

Arc-produced carbon multi-walled nanotubes (MWNTs) were fluorinated at 420 °C in a flow of diluted F₂ gas containing small admixture of HF gas. Fluorinated materials (F-MWNTs) with 10–55 wt.% fluorine content were studied by XPS. It was shown that fluorination begins at the external layers of nanotubes and the reaction front propagates inside the multi-layer particles in concert with structural deterioration of graphene layers. The C₂F stoichiometry still allows MWNT wall integrity, similar to known for SWNTs. The fluorine contents in the product can noticeably exceed this higher fluorine limit for tube stability. The position of the F 1s line at 688.2 eV does not depend on the fluorine concentration. Nearly covalent C–F bonds dominate the F-MWNT samples, with a small quantity (2–9%) of ionic bonds also present. Fluorinated carbon tends to spatially separate from non-fluorinated carbon.