载银多壁碳纳米管抗菌剂结构与性能的研究

以多壁碳纳米管(MWNTs)为载体,通过化学吸附的方法制备载银多壁碳纳米管(Ag/MWNTs)抗菌剂.用SEM、TEM、FT-IR、XRD对其表观形貌、结构进行了表征.结果表明,银离子(Ag+)被吸附到MWNTs的表面,通过抑菌环实验表明,Ag/MWNTs对大肠杆菌和金黄色葡萄球菌都有很好的抗菌效果.     

TEMPO氧化纤维素纳米纤丝对多壁碳纳米管分散性的影响

以竹粉为原料,采用2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）氧化法通过改变NaClO的添加量制备出不同羧基含量及形态的纤维素纳米纤丝（CNFs）,并将制备的CNFs作为分散剂对多壁碳纳米管（MWCNTs）进行分散处理,得到不同分散浓度的CNFs/MWCNTs悬浮液,采用Beer-Lambert定律对MWCNTs的分散量进行测定,并采用原子力显微镜（AFM）、激光粒度分析仪（LPSA）等手段评价了不同羧基含量及形态的CNFs对MWCNTs的分散效果。结果表明:随着NaClO添加量的增加,CNFs的横截面直径逐渐变小,羧基含量逐渐增加,同时,CNFs对MWCNTs的分散量逐渐增大;当CNFs的羧基含量从0.635 mmol/g增加到1.646 mmol/g时,对MWCNTs的分散量从19%增加到39%;不同CNFs/MWCNTs悬浮液中的粒度分布系数（PDI）值均小于0.3,且不同悬浮液的Zeta电位绝对值均高于30 mV,表明不同羧基含量的CNFs均能对MWCNTs有较好的分散效果;同时,随着羧基含量的增加,CNFs对MWCNTs的分散效果越好,CNFs/MWCNTs复合薄膜的抗拉应力逐渐增大,而且电阻率逐渐降低,当CNFs羧基含量为1.646 mmol/L时,CNFs/MWCNTs复合薄膜抗拉应力达到了91 MPa,薄膜电阻率低至0.1460 Ωcm。      

酯化法制备苯乙烯基功能化多壁碳纳米管的研究

采用羧酸盐与卤化物酯化法,制备了苯乙烯基功能化的多壁碳纳米管(MWCNTs),并用红外光谱(FTIR)、拉曼光谱(Raman)、透射电镜(TEM)以及热重分析(TGA)对样品进行了表征.结果表明苯乙烯基以共价键接枝到MWCNTs的表面,且MWCNTs整体结构没有出现明显破坏;TGA结果显示苯乙烯基接枝率高达36%;分散性试验结果表明,样品能较好地溶于甲苯和THF等有机溶剂中.     

The effect of multi-walled carbon nanotubes/hydroxyapatite nanocomposites on biocompatibility

In the present study, multi-walled carbon nanotubes/hydroxyapatite (MWCNTs/HA) nanocomposites with various MWCNT contents were manufactured by sol-gel processing. The MWCNTs/HA powder was characterized using field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman analysis. The results show that the MWCNTs were fully covered with HA nanoparticles and help forming the crystallized hydroxyapatite. In addition, in vitro tests highlighted the excellent biocompatibility of the MWCNTs/HA composite.     

Fabrication of humidity sensors by multi-walled carbon nanotubes

Humidity sensors have multi-walled carbon nanotubes (MWNTs) as the sensing material is demonstrated. The sensor was fabricated on a silicon dioxide coated silicon wafer with metal electrodes. MWNTs were deposited and interlinked with the electrodes by means of the dielectrophoresis technique. The sensing device has the function of a hygrometer when measuring resistance variations to the local relative humidity percentage (RH%) through MWNTs. By measuring the MWNT resistances, we find that higher RH% results in a decrease of conductivity. The results indicate that electron transports in MWNTs are affected by water molecules adsorption on the outermost nanotube surface. A miniature thermocouple sensor was also fabricated and integrated with the humidity sensor. This allowed us to simultaneously sense environmental humidity and temperature. Hence, accurate humidity measurements were achieved with this prototype by calibrating the electrical resistance and temperature levels to carry out the tests with the humidity percentages.     

Capillary effect of multi-walled carbon nanotubes suspension in composite processing

Carbon nanotubes (CNTs) do have the potential to improve the interlaminar shear strength (ILSS) of composites if they can be successfully integrated into the matrix as it infuses into the fiber preform. The infusion under capillary action of Multi-Walled Carbon Nanotubes (MWNT)/Epoxy suspension with tubes of length 0.3 approximately 1 microm in glass fiber bundles containing pores of the order of 5 nm approximately100 microm was investigated. The influence of parameters such as suspension concentration, viscosity, porous media architecture, surface tension and contact angle were explored. It was found that filtering of the suspension is a major challenge for uniform infusion for concentrations beyond 0.5% MWNT by weight. This is even truer for fiber bundles that are compacted. Hence for successful manufacturing, new infusion techniques that rely on fabrics of high permeability will have to be developed to fabricate such nanocomposites.     

Electrical characterization of multi-walled carbon nanotubes

Electrical characteristics of multi-walled carbon nanotubes (MWNTs) grown by chemical vapor deposition have been investigated as a function of the bias voltage, nanotubes length and temperature, in 2 and 4 terminal configurations. Nanotubes were deposited over metal electrodes using ac dielectrophoresis method. For better contacts between the nanotubes and electrodes, Ni and Pd films were deposited by an electroless deposition technique. Differential conductance was found to rise considerably with bias, and this effect was more pronounced for Ni. Using 2 and 4 terminal configurations, electrical resistance measurements for individual MWNTs were performed, and the results were interpreted using the model of nanotube as a resistive transmission line, where current at low bias flows mainly through the two outermost shells.     

Removal of vanadium from wastewater by multi-walled carbon nanotubes

Nitric acid heating reflux modified multi-walled carbon nanotubes (HMWCNTs) were used for the removal of vanadium(V) in aqueous solution. The removal rate of vanadium(V) decreased with the increase of the initial vanadium(V) concentration and the solution pH, and increased with the increase of reaction time, HMWCNTs amount and solution temperature. The adsorption equilibrium and dynamic kinetics fitted the Langmuir adsorption isotherm and pseudo-second order models. The results obtained by scanning electron micrography and Fourier transform infrared spectroscopy analysis revealed that the hydroxyl and carboxyl functional groups are mainly responsible for the vanadium adsorption. This study showed that the HMWCNTs proved to be a considerable adsorbent for the removal of vanadium from wastewater.     

两亲性嵌段共聚物改性的多壁碳纳米管的制备

通过对碳纳米管进行表面改性制得具有引发ATRP反应活性的碳纳米管(MWNT-Br),以MWNT-Br作引发剂经过两次ATRP反应将聚乙烯基吡咯烷酮(PVP)和聚甲基丙烯酸特丁酯(PtBMA)先后接枝到多壁碳纳米管表面制得两亲性嵌段共聚物接枝的碳纳米管(MWNT-PVP-b-PtBMA),用红外光谱、热失重和透射电镜对两亲性碳纳米管进行了表征.并考察了修饰前弱亲油性的纯碳纳米管、酸化后亲水性的碳纳米管和修饰后两亲性碳纳米管这3种碳纳米管在水和氯仿形成的两相体系中的分散情况,观察到所制备的两亲性碳纳米管能够均匀分散在油水两相界面上.     

Influence of ozone on N-doped multi-walled carbon nanotubes

Nitrogen-doped multi-walled carbon nanotubes (N-MWCNT) were selectively grown on oxidised silicon substrate by means of catalytic chemical vapour deposition with decomposition of acetonitrile in the presence of ferrocene (FeCp₂) at 900°C. The synthesised N-MWCNT film was initially treated with continuous ozone flow for various time periods and characterised by means of scanning electron microscopy and Raman spectroscopy. The electrochemical response of ozone-treated N-MWCNT film towards ferrocyanide/ferricyanide, [Fe(CN)₆]^3?/4? redox couple was investigated by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy. The results were compared with those obtained for untreated N-MWCNT film. The findings reveal the occurrence of structural defects on surface of ozone-treated N-MWCNT film due to oxidation of nanotubes. Furthermore, the handling of N-MWCNT film with ozone increases the barrier for interfacial electron transfer and slows down the kinetics of redox reaction occurring on this particular electrode.     

The effect of acidic treatment on the lithium storage capacity of multi-walled carbon nanotubes

In this research, multi-walled carbon nanotubes (MWCNTs) were modified by nitric acidic treatment to improve their electrochemical performance. The electrochemical performance of MWCNTs was evaluated by charge and discharge cycles. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectrum analysis techniques were used to characterize the samples. The closed tip or cap structures of pristine MWCNT were opened and the nanotubes were chopped after acidic treatment, which is beneficial to improve the lithium ion insertion/extraction into/from MWCNTs and lithium storage capacity. The graphite crystallinity of acid treated MWCNTs reduced slightly and disordered carbon structures were introduced at the surface of MWCNTs, which led to the large initial irreversible capacity.     

多壁碳纳米管吸附异甘草苷的热力学研究

多壁碳纳米管可选择性地吸附结构相似的两种黄酮类化合物甘草苷和异甘草苷,研究了异甘草苷被多壁碳纳米管吸附的吸附热力学特征。结果表明:多壁碳纳米管吸附异甘草苷的量随着异甘草苷浓度的增加而增加,随着温度升高而降低。异甘草苷的吸附过程符合Freundlich方程。其ΔH0和ΔG0值表明该吸附反应是自发进行的放热反应。     

Mechanism of Pt loading on multi-walled carbon nanotubes

Microwave treatment of multi-walled carbon nanotubes (MWCNTs) with nitric acid (HNO3) and 0.2 M sodium chlorate (NaClO3) can generate and enhance defects on the surfaces of MWCNTs. These defects are the important sites to load Pt nanoparticles (NPs). We investigated the defect induced Raman spectra and observed a decrease in the R-values (D-band/G-band peak ratio) and a slight up-shift of the both peaks as the amount of loaded Pt NPs increased. Using the Brunauer-Emmett-Teller (BET) method, we observed that the pore size distribution and the pore volume changed according to the amount of Pt NPs loaded. Fewer micropores and mesopores were observed on MWCNTs loaded with Pt NPs. Based on the pore size distribution calculated from the BET results, Pt NPs loaded mainly on pores/defects with a size of 2-8 nm. Transmission electron microscopy and Raman spectroscopy results confirmed that most well-crystallized Pt NPs loaded on the surface defect sites and pores spontaneously through the exchange of electrons between Pt and C atoms.     

Grafting of polystyrene on nitrogen-doped multi-walled carbon nanotubes

Polymer grafting of polystyrene (PS) on nitrogen-doped multiwall carbon nanotubes (CNx) was successfully obtained by a "grafting from" technique. The production method involves the immobilization of initiators, using wet chemistry, onto the nanotube surface, followed by an in situ surface-initiated polymerization. The polymer-grafting carbon nanotubes synthesis includes the free radical functionalization of CNx and the "controlled/living" Nitroxide Mediated Radical Polymerization (NMRP). The obtained products were studied using several microscopic techniques as scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS). The characterization also includes thermogravimetric analysis (TGA), Raman spectroscopy, infrared spectroscopy, and electron spin resonance (ESR), among others. The analyzed samples were also compared with solutions fabricated by physical blending of the polymer and CNx nanotubes. These results indicate that the nanotube radical functionalization, the chemical grafting, and the polymerization reaction were obtained over CNx when NMRP method was successfully used, giving rise to a uniform PS layer of several nanometers grafted on the outer surface of the CNx nanotubes. Several properties of the PS-grafted CNx nanotubes were also studied. It is shown that the production method leads to a narrower distribution of the external diameters. Moreover, their solubilization in organic solvents is greatly improved. Finally, the dispersion of PS-grafted CNx into a PS matrix is studied to determine the differences in filler dispersion and interfacial adhesion strength, in comparison with nanocomposites elaborated with as-produced CNx.     

Grain size effect on the strengthening behavior of aluminum-based composites containing multi-walled carbon nanotubes

Strengthening efficiency of multi-walled carbon nanotubes (MWCNTs) is investigated for aluminum-based composites with grain sizes ranging from ∼250 to ∼65 nm. The strength of composites is significantly enhanced proportional to an increase of the MWCNT volume. However, the increment differs depending on deformation mode of the matrix. The strengthening efficiency of MWCNTs in ultrafine-grained composites is comparable with that predicted by the discontinuous fiber model, whereas the efficiency becomes half of the theoretical prediction as grain size is reduced below ∼70 nm. For nano-grained aluminum, activities of forest dislocations diminish and dislocations emitted from grain boundaries are dynamically annihilated during the recovery process, providing a weak plastic strain field around MWCNTs. The observation may provide a basic understanding of the strengthening behavior of nano-grained metal matrix composites.     

Stress transfer in multi-walled carbon nanotubes

The interaction and load transfer between the multiple shells of a multi-walled carbon nanotube (MWNT) are the subject of intense research by both analysts and experimentalists. Observations of both lubricated sliding and adhesion between individual shells in MWNT have been observed. While the atomic interactions due to simple separation have been successfully modeled by the Lennard-Jones interaction potential for graphene structures, modeling of the shearing deformation mode has been problematic. In the present work, the authors utilize two approaches in continuum mechanics to examine the shearing transfer between shells in a MWNT subjected to extensional and torsional loading wherein the load is transferred through the outermost shell to interior shells. The first approach follows the earlier developments of the authors wherein imperfect bonding between the shells is governed by a shearing transfer efficiency that varies between perfect bonding and zero shearing traction. The second approach utilizes a classical shear lag model to study the shearing transfer between the shells. A comparison between the shear lag and shear transfer models shows the equivalence of the two approaches for two-shell MWNT and numerical solutions are presented for the shear lag model for multiple layers beyond two. Agreement between the two models for multi-shells is demonstrated by varying an adjustable parameter that depends solely on the MWNT geometry. The simplicity of the shear transfer model as compared to the shear lag model constitutes an important advantage. The fundamental discrepancy between the two models lies in the fact that length dependence is inherent to the shear lag analysis, while according to the shear transfer model, stress transfer does not depend explicitly on length.     

多壁碳纳米管亲水性表面修饰的研究

采用非共价功能化的方法,使用十二烷基苯磺酸钠(SDBS)对多壁碳纳米管(MWNTs)进行表面修饰,获得了亲水性能优良的MWNTs。扫描电镜、原子力显微镜、粒度分析、拉曼光谱、热重分析和紫外-可见光谱等表征测试结果表明,用该方法制备的亲水性MWNTs在水中分散均匀、稳定性好,表面活性剂所占质量分数仅为6%,实验操作过程简单实用。     

多壁碳纳米管改性环氧树脂胶黏剂实验研究

将一种环氧树脂和表面羟基化的多壁碳纳米管(MWCNTs)按照质量比100∶0.1进行配比, 以超声波分散法制备MWCNTs/环氧树脂胶黏剂, 考察了两种硅烷偶联剂KH550和KH560对MWCNTs改性效果的影响。采用FTIR、 DSC、 DMA、 流变仪研究了MWCNTs对胶黏剂固化行为和流变特性的影响, 并结合断口形貌观察, 测试分析了MWCNTs对胶黏剂拉伸剪切强度和冲击强度的影响。结果表明: 硅烷偶联剂能与MWCNTs表面的羟基发生缩合反应, 增强了MWCNTs与环氧树脂基体的亲和性, 从而影响胶黏剂固化反应及黏度-剪切速率曲线; 经KH550改性的MWCNTs明显提高了胶黏剂与金属的界面粘结性, Al-Al拉伸剪切强度较无MWCNTs的胶黏剂提高了46.4%; 添加MWCNTs使胶黏剂的冲击断面更为粗糙, 开裂面积更大; 添加MWCNTs+KH550的胶黏剂冲击强度提高了44.1%, 说明MWCNTs/环氧树脂间界面性能对发挥MWCNTs的增韧效果非常重要。      

Dispersion of functionalized multi-walled carbon nanotubes in multi-walled carbon nanotubes/liquid crystal nanocomposites and their thermal properties

A novel liquid crystal functionalized multi-walled carbon nanotubes (LC-MWNTs)/2-methyl-N,N′-bis(4′-methoxy benzoyloxy)-terephthalamide liquid crystal (LC) nanocomposite (LC-MWNTs/LC) was prepared via solution blend. The dispersion and thermal property of the nanocomposites with different loadings of LC-MWNTs (0.1-1 wt.%) were investigated using SEM, TGA and DSC. The results show that the dispersion of LC-MWNTs in LC matrix is more homogeneous than purified MWNTs. The decomposition temperature of nanocomposites exhibits obvious decrease at first and then increase with increasing concentration of LC-MWNTs, which is lower than that of LC for 0.1-0.4 wt.% LC-MWNT loadings and higher than that of LC for 0.5-1 wt.% LC-MWNT loadings. The addition of LC-MWNTs has little effects on the texture of smectic mesophase. These results illustrate the LC-MWNTs/LC nanocomposites, which have lower melting point and higher decomposition temperature than those of LC by adding adequate amount of LC-MWNTs, show a wide temperature range of mesophase and high thermostability. The increased mesophase temperature region of LC materials will be beneficial to their practical applications.     

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.