聚合物/碳纳米管复合材料纤维的制备和性能

碳纳米管增强聚合物基体复合材料纤维是近几年发展起来的一个新的研究方向。从制备方法的角度对复合材料纤维进行了分类,评述了复合材料纤维的制备方法及其结构和性能研究的最新进展。并对存在的问题及今后的研究方向进行了展望。     

亚麻纤维增强聚乳酸可降解复合材料的制备与性能

将制浆造纸用亚麻短纤维与聚乳酸(PLA)熔融共混,用注塑方法成型亚麻纤维/聚乳酸复合材料试样。通过差示扫描量热实验(DSC)、动态力学性能测试(DMA)、热重分析(TGA)和力学性能测试等方法,研究了聚乳酸和亚麻纤维在不同质量配比下,复合材料热性能、动态力学性能和力学性能的变化规律。随着亚麻纤维的加入,复合材料的结晶度增大,热稳定性增强,储能模量得到提高,力学性能也有了明显变化:纤维含量为20%时,拉伸强度为45.88 MPa,比纯PLA的增加了21%;同时,弯曲模量的增幅达到30%。     

碳纳米管／石英复合粉体的制备

采用表面活性剂和超声辅助的混酸处理工艺对碳纳米管进行了表面修饰，均获得了分散均匀的碳纳米管悬浮水溶液，利用傅立叶红外吸收光谱及Zeta电位等手段对其分散机理进行了分析；采用快速溶胶一凝胶法，制备了多种碳纳米管含量的石英基复合粉体，透射电镜观察显示两种修饰碳纳米管表面的方法都有效提高了碳纳米管在石英基体的分散性，制备出了均匀的碳纳米管／石英复合粉体。     

Lyocell/多壁碳纳米管复合纤维的制备及性能

将多壁碳纳米管(MWCNTs)水悬浮液、N-甲基吗啉-N-氧化物(NMMO)溶液及纤维素共混得到纺丝液,通过干湿法制备了Lyocell/MWCNT复合纤维。采用X-衍射仪(WAXD)、扫描电镜(SEM)、透射电镜(TEM)、强度仪等分析了所得纤维的结构和性能。WAXD图谱显示复合纤维仍然具有纤维素II晶型的结构,同时还保留了MWCNTs的特征衍射峰;二维X衍射结果表明:MWCNTs质量分数为5%的复合纤维中,MWCNTs与纤维轴的取向角为±15.2°,说明复合纤维中MWCNTs基本沿着纤维轴取向。SEM结果显示复合纤维中MWCNTs在Lyocell基体中分布均匀。对纤维的力学性能分析进一步表明:添加适量的MWCNTs可使复合纤维的力学性能提高,MWCNTs质量分数为1%的复合纤维的初始模量和强度分别比Lyocell纤维增加49.4%和15.7%。     

石墨烯/碳纳米管嵌入式纤维传感器对树脂基复合材料原位监测的结构-性能关系对比

基于碳纳米材料的纤维传感技术已成为复合材料原位结构健康监测领域中一项十分有前景的技术。本研究采用两种不同的碳纳米传感元件—碳纳米管(carbon nanotube, CNT)涂层纤维(carbon nanotube coated fibers,CNTF)和还原氧化石墨烯(reduced graphene oxide, RGO)涂层纤维(reduced graphene oxide coated fibers, RGOF),分别制造合成具有自传感特性的复合材料,并比较研究两种嵌入式纤维传感器的传感性能和机理。从两种传感器的压阻效应可看出:RGOF的压阻灵敏度更高,并清晰地展现出从线性至非线性的两阶段压阻行为;而CNTF,则在发生断裂前始终呈现出平稳而有序的电学信号。这种强烈的结构-性能关系,可以用树脂渗透理论加以阐释。对CNTF而言,树脂分子可以渗透到其多孔的网络结构中,形成集成在纤维表面完整的CNT/树脂纳米复合结构。相比之下,具有大横向尺寸和表面一致性的RGO则可形成阻碍树脂渗透的无创网络结构。对实验结果和传感机理的进一步分析与研究表明,CNTF适用于材料的力学状态识别与长期监测,而RGOF则对结构损伤的早期预警更有实用价值。     

碳纳米管及碳纳米管纤维的性能与应用

碳纳米管是由单层或多层石墨片卷曲而成的无缝纳米级管状壳层结构。扼要介绍了碳纳米管、碳纳米管纤维的合成方法及近几年来国内外制备的各种碳纳米管产品。碳纳米管、碳纳米管纤维由于其优良的力学、电学特性可以制成气体吸附体、生物模板、传动装置、增强复合体、催化剂载体、探测器、传感器、纳米反应器等产品，在航空、能源、医药、化学等技术领域广泛应用。     

碳纳米管-铜复合粉的制备

用CVD法制备碳纳米管,将碳纳米管超声分散在硫酸铜水溶液中,经过脱水、氢还原,制得碳纳米管-铜复合粉体。用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)对样品进行了表征。结果表明,碳纳米管在复合粉体中分散均匀,一些碳纳米管与纳米铜粒子结合在一起或被铜包覆。     

静电纺纳米粘土/亚麻复合纳米纤维的制备及表征

利用静电纺丝技术制备了纳米粘土/亚麻落麻复合纳米纤维,其中亚麻落麻纤维溶解在分散有纳米粘土的4-甲基吗啉-N-氧化物(NMMO)/水的混合体系中。探究了纳米粘土和亚麻落麻的浓度、纺丝条件对纺丝工艺的影响。采用光学显微镜、SEM、TEM、FTIR、XRD和TGA测试了复合纳米纤维的微观形貌、结构及热学行为。结果表明:亚麻纤维浓度为1%时,可纺制成丝,且纳米粘土的加入可有效地改善纤维的细度和均匀性;TEM测试结果表明:纳米粘土已成功附着在纳米纤维上,但分散性有待进一步提高;FTIR和XRD结果表明:纳米粘土成功附着在亚麻纤维中,且存在于亚麻纳米纤维和粘土/亚麻复合纳米纤维中的纤维素为纤维素II型结晶;TGA分析表明:纳米粘土的引入可显著提高亚麻纤维的热稳定性。     

柔性可拉伸硅橡胶@多壁碳纳米管/硅橡胶可穿戴应变传感纤维

基于核-壳结构设计,采用简便、低成本的浸涂-固化法制得柔性、可拉伸、高灵敏且稳定的聚二甲基硅氧烷硅橡胶@多壁碳纳米管/聚二甲基硅氧烷硅橡胶(PDMS@MWCNTs/PDMS)压阻式应变传感纤维。通过FTIR、XRD、TG、TEM对硅烷偶联剂改性多壁碳纳米管(MWCNTs-KH570)的化学结构、热稳定性和微观形貌进行了分析,深入研究了核-壳结构与MWCNTs-KH570质量分数对PDMS@MWCNTs/PDMS复合纤维导电性能、传感性能及力学性能的影响规律与机制。结果表明:羟基化MWCNTs(MWCNTs—OH)表面接枝KH570使其在壳层PDMS基体中具有良好的分散性和界面相互作用;核-壳结构的设计使PDMS@MWCNTs/PDMS复合纤维在低填充下具有高电导率和传感性能;PDMS@MWCNTs/PDMS复合纤维的导电性能与传感性能随着MWCNTs-KH570质量分数增加而提高,且在人体关节运动监测中表现出良好的可重复性和工作稳定性。      

表面接枝聚丙烯腈的碳纳米管/聚丙烯腈初生复合纤维的制备

碳纳米管(CNTs)被修饰后表面接枝上聚丙烯腈(PAN),采用溶液聚合法合成复合纺丝液,并利用湿法纺丝技术制备PAN/CNTs初生复合纤维。采用FT-IR,HRTEM,TG等方法分析CNTs表面修饰前后状况,用XRD和SEM分析接枝CNTs对PAN初生纤维结构的影响。结果表明:CNTs表面成功接枝上PAN,二者之间具有较强的相互作用力,接枝CNTs的加入使PAN初生纤维的结晶度从36.92%提高到38.81%,晶粒尺寸从4.40nm增大到4.89nm,初生复合纤维的断面结构更加细化。     

碳纤维/棉纤维/聚吡咯柔性复合材料的制备及性能研究

柔性超级电容器作为一种储能器件,具有功率密度高、充电时间短、循环寿命长、比电容高等优点,可满足可穿戴器件的需求,而柔性电极材料是决定柔性超级电容器发展的关键因素,它决定着电容器的主要性能指标。采用混纺的方法制备了碳纤维含量为20%(质量分数)的碳纤维/棉纤维混纺纱线,然后通过电化学沉积法在碳纤维/棉纤维混纺纱线上生长聚吡咯颗粒,成功制备了20%(质量分数)碳纤维/棉纤维/聚吡咯柔性复合材料。利用扫描电子显微镜、拉曼光谱分析仪和电化学工作站研究了复合材料的形貌、聚吡咯沉积情况以及复合材料的电容性能。结果表明,20%(质量分数)碳纤维/棉纤维/聚吡咯柔性复合材料中,聚吡咯颗粒直径为30~60 nm,且沉积均匀,化学活性较高;在1.02 mA/cm^2电流密度下,复合材料的最大比电容达到1.28 F/cm^2,其高比电容归因于电极的独特结构;复合材料具有良好的柔韧性、机械稳定性和充放电循环寿命,其经过6000次弯曲循环后,电容保持率仍有80%以上,可以用作柔性可穿戴超级电容器的电极材料。     

含碳纳米管的新型抗静电纤维的制备和性能

将多壁碳纳米管分散在自制的抗静电载体PR-86中制备出新型、高效和耐久的抗静电母粒．抗静电母粒的添加量仅为0．5％就可以制备出性能优良的“基体-微纤”型抗静电PP纤维．该纤维的抗静电机理为异极性大分子放电机理．多壁碳纳米管的存在增强了微纤相的极化程度和抗静电母粒的抗静电效果．抗静电纤维的抗静电性具有耐久性．抗静电母粒对纤维的性能基本上没有影响．     

Cerium oxide dispersed multi walled carbon nanotubes as cathode material for flexible field emitters

Nanomaterials based electron sources are omnipresent in modern flat panel displays. Multi walled carbon nanotubes (MWNT) are the well studied electron emitter among the carbon materials. Since the surface modification of MWNT with low work function materials would have a positive impact on the field emission property of MWNT, cerium oxide (CeO2) nanoparticles dispersed multi walled carbon nanotubes (CeO2/MWNT) were synthesized by catalytic chemical vapour deposition followed by chemical reduction and its field emission property was investigated. The high-purity MWNT as well as CeO2/MWNT showed crystalline structure conformed by X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Further characterisation was done with Raman spectroscopy, UV-Visible absorption spectra and Fourier transform IR spectroscopy (FT-IR). The morphology and structural details of CeO2/MWNT composite was probed by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX). The direct evidence of the formation of CeO2/MWNT composites was given by transmission electron microscopy (TEM). The synthesized sample was coated over a flexible carbon paper using spin coating technique. The experiment was performed under a vacuum of 1 x 10(-6) Torr and Fowler-Nordheim equation was used to analyse the data. The turn-on voltage for the cerium oxide dispersed MWNT was found for a current density of 10 microA/cm2. The emission current density from the CeO2 nanoparticles dispersed MWNT reached 0.2 mA/cm2 at a reasonable bias field of 2.58 V/microm. The results were compared with those of pure MWNT and pure CeO2 nanoparticles with literature values.     

DNA-decorated carbon nanotubes for chemical sensing

We demonstrate a new, versatile class of nanoscale chemical sensors based on single-stranded DNA (ss-DNA) as the chemical recognition site and single-walled carbon nanotube field effect transistors (swCN-FETs) as the electronic read-out component. swCN-FETs with a nanoscale coating of ss-DNA respond to gas odors that do not cause a detectable conductivity change in bare devices. Responses of ss-DNA/swCN-FETs differ in sign and magnitude for different gases and can be tuned by choosing the base sequence of the ss-DNA. ss-DNA/swCN-FET sensors detect a variety of odors, with rapid response and recovery times on the scale of seconds. The sensor surface is self-regenerating: samples maintain a constant response with no need for sensor refreshing through at least 50 gas exposure cycles. This remarkable set of attributes makes sensors based on ss-DNA decorated nanotubes very promising for "electronic nose" and "electronic tongue" applications ranging from homeland security to disease diagnosis.     

Hydrogen sensing properties of multi-walled carbon nanotubes

The hydrogen sensing properties of multi-walled carbon nanotubes (MWNTs) synthesized by a hot filament CVD process are reported in this paper. The MWNTs were synthesized by a hot filament assisted chemical vapor deposition method using cobalt oxide nanoparticles as the catalyst on SiO₂ surfaces. The MWNTs were characterized with Raman spectroscopy and scanning electron microscopy. Two-terminal test devices were fabricated by depositing a layer of MWNTs between prefabricated gold electrodes on SiO₂ surfaces. The diameter of these MWNTs was in the 5–8 nm range. The sensitivity of carbon nanotubes was measured for different gas concentrations at different temperatures. It was found that the MWNTs were sensitive to H₂ in low temperature regions of 140–350 °C and had a maximum sensitivity (80%) at 230 °C. No sensitivity was observed at a temperature lower than 140 °C or higher than 400 °C. Though bare MWNTs are not sensitive to H₂ at room temperature, they exhibited very good sensing characteristics in the 140–300 °C range.     

Temperature sensing using individual single-walled carbon nanotubes

Molecular dynamics simulations and quantum transport theory are employed to study the temperature-dependent electrical properties of individual (12,0) zigzag and (5,5) armchair carbon nanotubes deposited on silicon substrates. The results demonstrate that the magnitude of the leakage current depends on the length of the nanotube. Furthermore, the leakage current is generated periodically along the length of the nanotube. Finally, the results indicate that given an appropriate value of the applied bias voltage, the induced current varies linearly with the temperature over specific temperature ranges. As a result, the temperature can be inversely derived from the measured current signal. Overall, the results show that the (12,0) zigzag and (5,5) armchair carbon nanotubes are suitable for temperature sensing applications over temperature ranges of 200-420?K and 300-440?K, respectively.     

Preparation and modification of carbon nanotubes

Carbon nanotubes (CNTs) were prepared by the catalytic decomposition of methane at 680 °C for 120 min, using nickel oxide–silica binary aerogels as the catalyst. The morphological structure of CNTs was investigated by transmission electron microscopy (TEM), X-ray Diffraction (XRD) and Raman spectroscopy. The results revealed that CNTs with diameter 40–60 nm showed high quality, uniform diameter and high length/diameter ratio, the wall structure of CNTs was similar with that of highly oriented pyrolytic graphite (HOPG), and some metal catalyst particles were encapsulated at the tip of CNTs. Different methods were compared to modify CNTs. Investigated by TEM, XRD, Raman spectroscopy and nitrogen adsorption/desorption for modified CNTs, it was confirmed that after modification treatment by immersion in diluted HNO₃ solution with ultrasonic and then milling by ball at a high velocity, the metal catalyst particles at the tip of CNTs disappeared, the unique cylinder wall structure remained, the CNT length became short, the cap at the tip of nanotube was opened, and thus the internal surface area could be effectively used, leading to the increase of the specific surface area and pore volume. This technique is relatively simple and effective for modifying CNTs which can be scaled up for industrial applications.