Structural modifications and enhanced Raman scattering from multiwalled carbon nanotubes grown on titanium coated silicon single crystals

Multiwalled carbon nanotubes (MWCNTs) were grown on 10 nm iron (Fe) film by microwave plasma enhanced chemical vapor deposition using titanium (Ti) film as an interlayer. The Ti interlayer of thickness 5 nm-20 nm was sandwiched between Fe and silicon (Si) using thermal evaporation. Enhanced Raman response was observed in MWCNTs with increasing Ti interlayer thickness. This was related with the plasmonic effects occurring at the interface of the CNTs and the metallic support in a three layer system (Ti-Fe-CNTs). The increase in the G mode optical strength is attributed to surface enhanced resonance Raman scattering. Moreover, the increase in the D-mode and 2D-mode intensity is explained on the basis of double resonance effects. The crystallinity in the samples was calculated using I_D/I_G ratio. It was found that that I_D/I_G ratio decreases in three layer system with increasing Ti interlayer thickness as compared to a two layer (Fe-CNTs) system as reported earlier.     

Vapor sensing performances of PVDF nanocomposites containing titanium dioxide nanotubes decorated multi-walled carbon nanotubes

Inorganic nanocarbon hybrid materials are good alternatives for superior electrochemical performance and specific capacitance to their traditional counterparts. Nanocarbons act as a good template for the growth of metal nanoparticles on it and their hybrid combinations enhance the charge transport and rate capability of electrochemical materials without sacrificing the specific capacity. In this study, titanium dioxide nanotubes (TNT) are synthesized hydrothermally in the presence of multi-walled carbon nanotubes (MWCNT) where the latter acts as base template material for the metal oxide nanotube growth. The MWCNT–TNT hybrid material possesses very high dielectric strength and this is used to enhance the dielectric property of the polymer polyvinyledene fluoride (PVDF). Solution mixing was used to prepare the PVDF/MWCNT–TNT nanocomposites by varying the filler concentrations from 0.5 to 2.5 wt%. Excellent vapor sensing was noticed for the PVDF nanocomposites with different rate of response towards commonly used laboratory solvents. The composites and the fillers were characterized for its morphology and structural properties using scanning and transmission electron microscopy, X-ray diffraction studies and infrared spectroscopy. Vapor sensing was measured as relative resistance variations against the solvent vapors, and the dielectric properties of the composites were measured at room temperature during the frequency 10²–10⁷ Hz. Experimental results revealed the influence of filler synergy on the properties of PVDF and the enhancement in the solvent vapor detectability and dielectric properties reflects the ability of these composite films in flexible vapor sensors and in energy storage.     

Multi-scale electrical response of silicon nitride/multi-walled carbon nanotubes composites

Dense silicon nitride (Si₃N₄) composites with various amounts (0-8.6 vol%) of multi-walled carbon nanotubes (MWCNTs) are electrically characterised by combining macroscopic dc-ac and nanoscale conductive scanning force microscopy (C-SFM) measurements. In this way, a coherent picture of the dominant charge transport mechanisms in Si₃N₄/MWCNTs composites is presented. A raise of more than 10 orders of magnitude in the electrical dc conductivity compared to the blank specimen is measured for MWCNTs contents above 0.9 vol%. Semiconductor and metallic-like behaviours are observed depending on both the temperature and the MWCNTs content. Macroscopic measurements are further supported at the nanoscale by means of C-SFM. The metallic-type conduction is associated to charge transporting along the nanotube shells, whereas the semiconductor behaviour is linked to hopping conduction across nanotube-nanotube contacts and across intrinsic defect clusters within the nanotubes.     

Hydroxyapatite growth on multiwall carbon nanotubes grown on titanium fibers from a titanium sheet

Nano-hydroxyapatite (HA) was grown on functionalized multiwalled carbon nanotubes (MWCNTs) deposited on TiO₂ nanofibers (NFs) that were hydrothermally grown on Ti metal sheets. The HA was electrochemically grown on the MWCNTs/TiO₂ porous layer. It was found that the HA grows on the MWCNTs/TiO₂ NFs in the form of dense coating with nanorice grain-shaped. The incorporation of MWCNTs between HA and TiO₂ NFs has led to higher adhesion strength as measured by micro-scratching test indicating the benefit of MWCNTs on the improving the bonding strength of HA layer. The obtained coatings exhibit excellent corrosion resistance in simulated body fluid. It is expected that this simple route for preparing the new HA/MWCNTs/TiO₂/Ti-layered structure might be used not only in the biomedical field, but also in catalysis and biological sensing among others.     

Biocompatibility of immobilized aligned carbon nanotubes

In vivo host responses to an electrode-like array of aligned carbon nanotubes (ACNTs) embedded within a biopolymer sheet are reported. This biocompatibility study assesses the suitability of immobilized carbon nanotubes for bionic devices. Inflammatory responses and foreign-body histiocytic reactions are not substantially elevated when compared to negative controls following 12 weeks implantation. A fibrous capsule isolates the implanted ACNTs from the surrounding muscle tissue. Filamentous nanotube fragments are engulfed by macrophages, and globular debris is incorporated into the fibrous capsule with no further reaction. Scattered leukocytes are observed, adherent to the ACNT surface. These data indicate that there is a minimal local foreign-body response to immobilized ACNTs, that detached fragments are phagocytosed into an inert material, and that ACNTs do not attract high levels of surface fouling. Collectively, these results suggest that immobilized nanotube structures should be considered for further investigation as bionic components.     

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.     

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。     

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.     

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.     

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.     

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.     

Free-standing array of multi-walled carbon nanotubes on silicon (111) by a field-inducing self-assembly process

In this paper, the authors bring forward a novel method named as the field-inducing self-assembly process in which free-standing MWCNTs array can be assembled perpendicularly on silicon (111) wafer. The density of free-standing MWCNTs array is controllable by adjusting the DC voltage from 0 V to 40 V. Preferential MWCNTs array is obtained by the condensation reaction between carboxylic group of MWCNTs end and hydroxyl group of silicon electrode surface under a low DC field. And the MWCNTs array can exhibit excellent field emission property.     

多壁碳纳米管/氧化石墨烯/硅橡胶复合薄膜湿敏性能研究

采用化学修饰的多壁碳纳米管(o-MWCNTs)与Hummers法制备的氧化石墨烯(GO)超声混合,加入室温硫化硅橡胶(RTV),利用溶液共混法制备具有湿敏特性的o-MWCNTs/GO/RTV复合薄膜。借助于透射电子显微镜(TEM)、红外吸收光谱(FT-IR)等分析手段分别对化学修饰的多壁碳纳米管及氧化石墨烯进行表征,并对基于o-MWCNTs/GO/RTV的复合薄膜的湿敏性能及湿敏机理进行了探讨。结果表明,混酸处理后的碳纳米管端口打开,侧壁和开端处产生羧基和羟基等官能团,有利于水分子的吸附,同时也有利于与GO表面的基团作用,形成三维的纳微米结构,提高了碳纳米管与硅橡胶基体的相容性,使所制备的o-MWCNTs/GO/RTV复合薄膜灵敏度提高。当相对湿度在23%~87%的范围,m(GO)∶m(o-MWCNTs)=1∶3时,o-MWCNTs/GO/RTV复合薄膜的湿滞为5%RH,灵敏度为0.3152/%RH,响应时间和恢复时间分别为4和27 s。     

多壁纳米碳管的制备与表面改性处理

以Co-MCM-41作催化剂,采用化学气相沉积(CVD)法催化热解无水乙醇制备纳米碳管(CNTs),然后将纳米碳管在120℃下用浓硝酸回流,进行纯化及表面酸氧化改性处理。通过XRD、FT-IR、TEM、N2吸附-脱附和Raman光谱等分析手段对酸处理前后的纳米碳管进行了表征。结果表明制备出品质较好、管径均匀、管壁较厚、顶端开口的多壁纳米碳管。浓硝酸氧化处理后在纳米碳管的表面存在羧基和羟基等官能团。     

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.     

Effect of growth temperature on the CVD grown Fe filled multi-walled carbon nanotubes using a modified photoresist

Fe filled carbon nanotubes were synthesized by atmospheric pressure chemical vapor deposition using a simple mixture of iron(III) acetylacetonate (Fe(acac)₃) with a conventional photoresist and the effect of growth temperature (550-950 °C) on Fe filled nanotubes has been studied. Scanning electron microscopy results show that, as the growth temperature increases from 550 to 950 °C, the average diameter of the nanotubes increases while their number density decreases. High resolution transmission electron microscopy along with energy dispersive X-ray investigation shows that the nanotubes have a multi-walled structure with partial Fe filling for all growth temperatures. The graphitic nature of the nanotubes was observed via X-ray diffraction pattern. Raman analysis demonstrates that the degree of graphitization of the carbon nanotubes depends upon the growth temperature.     

多壁碳纳米管的表面功能化及分散性研究

多壁碳纳米管(MWCNTs)分别经混合、强酸氧化浸泡和酰氯化处理后,再与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的衍生物(DHDOPO)进行接枝反应得到表面功能化的MWCNTs。利用傅里叶变换红外光谱仪(FT-IR)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、热重分析仪(TGA)、紫外-可见分光光度仪(UV-Vis)和沉降实验等分别表征改性前后MWCNTs的结构和表面形态,估算DHDOPO在MWCNTs表面的相对接枝率,研究改性前后MWCNTs在乙醇中的分散性。结果表明,MWCNTs经混合强酸氧化后表面出现羧基;DHDOPO在MWCNTs上的相对接枝率为51%;混合强酸氧化和表面接枝DHDOPO的MWCNTs在无水乙醇中具有良好的分散性。     

Attachment of functionalized single-walled carbon nanotubes (SWNTs) to silicon surfaces

Single-walled carbon nanotubes (SWNTs) were functionalized by direct fluorination and subsequent reaction with 6-aminohexanoic acid for water-soluble carboxylic acid functionalized SWNTs (AHA-SWNTs). Both of the compounds were used as precursors to attach SWNTs to APTES coated silicon surfaces. AHA-SWNTs in aqueous solution were reacted with APTES self-assembled monolayers (SAMs) with coupling reagents N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) and N-hydroxysuccinimide (NHS). The surface coverage is a function of concentration of AHA-SWNTs, solvent and coupling method. While for the fluorinated SWNTs (F-SWNTs), direct addition of F-SWNTs to preformed APTES SAMs at 90 degrees C shows essentially no reaction, in contrast to the one-pot reaction of F-SWNTs with APTES molecules in the presence of SWNTs on a silicon substrate. This reaction route provides a convenient method to attach SWNTs to silicon surfaces.     

载铜多壁碳纳米管的抗菌活性研究

采用溶胶-凝胶法在多壁碳纳米管(MWCNTs)表面负载纳米铜,制备复合抗菌材料MWCNTsCu。X射线能量色散谱(EDS)、透射电子显微镜(TEM)表征结果表明,纳米铜成功地负载在MWCNTs表面,纳米铜分散良好。以大肠杆菌为目标,评价了MWCNTs-Cu对水中细菌的抗菌活性,探讨了其抗菌机理。研究结果表明,MWCNTs-Cu对大肠杆菌表现出很强的抗菌性,其中,MWCNTs对大肠杆菌有强吸附性,纳米铜起主要杀菌作用。