Characterization of single-wall carbon nanotubes by N2 adsorption

N₂ adsorption isotherms at 77 K of single-wall carbon nanotubes (SWNTs), multi-wall carbon nanotubes (MWNTs), and mixtures of these carbon nanotubes (CNTs) were analyzed for differences in their pore size distributions (PSDs). The PSDs, calculated in the microporous region by the Horvath–Kawazoe method and in the mesoporous region by the BJH method, are in agreement with the structures of both types of CNTs deduced from high-resolution transmission electron microscopy. A characteristic peak in the microporous region in the PSD of SWNTs is not present in the PSDs of MWNTs and impurities such as amorphous carbon, metal residues of catalysts, etc. The evaluation of this peak is proposed as a convenient tool for the quantitative characterization of SWNT purity in carbon nanotube-containing samples.     

Synthesis of carbon nanotubes by microwave plasma-enhanced hot filament chemical vapor deposition

A combined system of microwave plasma-enhanced chemical vapor deposition (MPECVD) and hot filament CVD (HFCVD) has been developed for the growth of various carbon nanotubes, where the source gas (methane) can be decomposed independently through microwave plasma and hot tungsten filament. It is found that microwave plasma provides more efficiently carbon sources for the growth of carbon nanotubes (CNTs). By the help of microwave plasma, long CNTs array with length of 0.3 mm and high-density single-walled carbon nanotubes (SWNTs) have been grown by thermal CVD and hot filament CVD, respectively. Raman spectra of the SWNTs reveal high crystalline as well as narrow diameter distribution.     

Thionine-mediated chemistry of carbon nanotubes

Thionine can be employed as a kind of useful functional molecule for the non-covalent functionalization of carbon nanotubes, as it shows a strong interaction with either SWNTs or MWNTs. Attachment of thionine molecules onto the sidewalls of carbon nanotubes would improve the solubility and lower the thermal stability of original carbon nanotubes. More importantly, it may functionalize the surface of carbon nanotubes with rich NH₂ groups and therefore open up more opportunities for the surface chemistry of carbon nanotubes. It has been proved that through the modification of small thionine molecules, other kinds of species such as cytochrome C and TiO₂ nanoparticles could be easily and selectively introduced onto the surface of carbon nanotubes. With this approach, SWNTs or MWNTs can be tailored with desired functional structures and properties.     

Materials science of carbon nanotubes: fabrication,integration, and properties of macroscopic structures of carbon nanotubes

In this Account, we summarize some of our recent studies on the materials properties of the carbon nanotubes (CNTs). The focus is on single-wall carbon nanotubes (SWNTs). We describe experiments on synthesis of SWNTs with controlled molecular structures and assembly of functional macroscopic structures. In addition, we present results on the electron field emission properties of macroscopic CNT cathodes.     

Transparent conductive film based on carbon nanotubes and PEDOT composites

Single-walled nanotubes (SWNTs), thin multiwalled carbon nanotubes (t-MWNTs) and multiwalled carbon nanotubes (MWNTs) were treated with H₂SO₄–HNO₃ acid solution, under different chemical conditions. The acid-treated CNTs were dispersed in DI water and in poly (3,4-ethylenedioxythiophene) (PEDOT) solution. Furthermore, the finely dispersed CNTs/PEDOT solutions were employed to a simple method of bar coating to obtain the transparent conductive films on the glass and polyethylene terephthalate (PET) film. A sheet resistance of 247 Ω/sq and a transmission of 84.7% were obtained at a concentration of the acid-treated CNTs of 0.01 wt.%.     

Synthesis of well-organised carbon nanotube membranes from non-degradable plastic bags with tuneable molecular transport: Towards nanotechnological recycling

This study presents a nanotechnological approach to convert commercially available and non-degradable grocery plastic bags into well-organised carbon nanotube membranes with tuneable molecular transport properties. In this nanotechnological process, plastic bags are used as a carbon source while carbon nanotubes (CNTs) are produced by a catalyst/solvent-free chemical vapour deposition (CVD) approach. Furthermore, CNTs are grown inside nanoporous anodic alumina membranes (NAAMs) featuring hexagonally arranged nanopores, which enable the control over the nanotubes’ organisation and geometry. The transport performance of the resulting CNTs–NAAMs is tested by several dye molecules with positive, negative and neutral charge. These results demonstrate the ability of these membranes to selectively tune molecular transport as a function of the interaction between molecules and inner surface of CNTs. This study proves that an environmentally non-degradable wastematerial as commercial plastic bags can be directly used to produce such sophisticated nanodevices as CNTs membranes.     

New hybrid system: Poly(ethylene glycol) hydrogel with covalently bonded pegylated nanotubes

Hydrogels containing carbon nanotubes (CNTs) are expected to be promising conjugates because they might show a synergic combination of properties from both materials. Most of the hybrid materials containing CNTs only entrap them physically, and the covalent attachment has not been properly addressed yet. In this study, single‐walled carbon nanotubes (SWNTs) were successfully incorporated into a poly(ethylene glycol) (PEG) hydrogel by covalent bonds to form a hybrid material. For this purpose, SWNTs were functionalized with poly(ethylene glycol) methacrylate (PEGMA) to obtain water‐soluble pegylated SWNTs (SWNT–PEGMA). These functionalized SWNTs were covalently bonded through their PEG moieties to a PEG hydrogel. The hybrid network was obtained from the crosslinking reaction of poly(ethylene glycol) diacrylate prepolymer and the SWNT–PEGMA by dual photo‐UV and thermal initiations. The mechanical and swelling properties of the new hybrid material were studied. In addition, the material and lixiviates were analyzed to elucidate any kind of SWNT release and to evaluate a possible in vitro cytotoxic effect. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Carbon nanotube induced polymer crystallization: The formation of nanohybrid shish-kebabs

Carbon nanotubes (CNTs) have attracted tremendous attention in recent years because of their superb optical, electronic and mechanical properties. In this article, we aim to discuss CNT-induced polymer crystallization with the focus on the newly discovered nanohybrid shish-kebab (NHSK) structure, wherein the CNT serves as the shish and polymer crystals are the kebabs. Polyethylene (PE) and Nylon 6,6 were successfully decorated on single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs), and vapor grown carbon nanofibers (CNFs). The formation mechanism was attributed to “size-dependent soft epitaxy”. Polymer CNT nanocomposites (PCNs) containing PE, Nylon 6,6 were prepared using a solution blending technique. Both pristine CNTs and NHSKs were used as the precursors for the PCN preparation. The impact of CNTs on the polymer crystallization behavior will be discussed. Furthermore, four different polymers were decorated on CNTs using the physical vapor deposition method, forming a two-dimensional NHSK structure. These NHSKs represent a new type of nanoscale architecture. A variety of possible applications will be discussed.     

Effect of temperature on the selection of semiconducting single walled carbon nanotubes using Poly(3-dodecylthiophene-2,5-diyl)

We report on the investigation of the temperature effect on the selective dispersion of single-walled carbon nanotubes (SWNTs) by Poly(3-dodecylthiophene-2,5-diyl) wrapping. The interaction mechanism between polymer chains and SWNTs is studied by controlling the polymer aggregation via variation of the processing temperature. Optical absorption and photoluminescence measurements including time resolved photoluminescence spectroscopy are employed to study the degree of interaction between the polymer in different aggregation states and the carbon nanotubes. At low processing temperatures, results are consistent with the planarization of the polymer chains and with SWNTs working as seeds for polymer aggregation. The formation of small clusters due to the inter-digitation of alkyl tails between neighboring polymer-wrapped SWNTs allows the formation of the SWNT bundles, as experimentally evidenced and investigated by molecular dynamics simulations. The interaction between the tubes within the bundles, which is reflected in the variation of the photoluminescence dynamics of the polymer, can be suppressed by warming up the sample.     

Synthesis and characterization of polyaniline derivatives and related carbon nanotubes nanocomposites - Study of optical properties and band gap calculation

Poly(o-methylaniline) (POTO), poly(o-methoxyaniline) (POAS), poly(2,5-dimethylaniline) (PDMA), poly(2,5-dimethoxyaniline) (PDOA), and nanocomposite based on multi-walled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs) embedded in these conducting polymers, were synthesized by oxidative polymerization. We used the Langmuir-Schaefer (LS) technique to fabricate films at the air-water interface and performed the doping process on the undoped films by dipping the substrates in 1 M hydrochloric acid (HCl) aqueous solution. We recorded UV-vis spectra for both the undoped and doped forms and calculated the related band gaps by using the Tauc equation. Experimental data showed the substituents affected the final oxidation ratio of the polymer chains and the presence of carbon nanotubes (CNTs) in the medium of reaction changed the properties in relation of the kind and number of substituents along the aromatic ring. The study of UV-vis spectra of the undoped nanocomposites and the calculated band gaps highlighted that the conducting polymer chains simply wrapped up around CNTs with no strong interaction. Both the kind and number of substituents along the aromatic rings strongly affected the protonation process, since their capability of “tuning” the formation of the polaronic state. The presence of CNTs in the polymer matrix showed no appreciable influence in the chemical properties of the doped nanocomposites with respect to the pure conducting polymers.     

Ion-exchange adsorption of copper(II) ions on functionalized single-wall carbon nanotubes immobilized on a glassy carbon electrode

The cation-exchange property of oxidatively treated carbon nanotubes (CNTs) is newly reported. Single-wall carbon nanotubes (SWNTs), which were oxidatively treated, were immobilized on a glassy carbon surface and, on this CNT-modified electrode, Cu(II) ions were spontaneously adsorbed and their redox waves electrochemically measured. It is suggested that the adsorption of the cationic Cu(II) ions occurs by their electrostatic interaction with the negatively charged carboxylic anions on the CNTs after the ion-exchange with protons. The surface coverage of the adsorbed Cu(II) ions depending on the dipping time, the amount of immobilized CNTs, and the Cu(II) concentration was estimated from the electrochemical chronocoulometric measurements. The effect of the ionic strength on the adsorption of the Cu(II) ions was investigated and the adsorption strengths of various alkali metal cations and protons were compared. It is hoped that this new cation-exchange property of CNT-modified electrodes may extend their range of electrochemical applications.     

Poly[ethylene‐co‐(acrylic acid)]‐based nanocomposites: Thermal and mechanical properties and their structural characteristics studied by Raman spectroscopy

Nanocomposites containing carbon nanotubes (CNTs) as nanofillers and poly[ethylene‐co‐(acrylic acid)] (PEAA) or a polymer miscible mixture of PEAA and poly(2‐ethyl‐2‐oxazoline) (PEOx) as a matrix were prepared by the solution‐evaporation method with minimal damage to nanotubes. CNTs were prepared by chemical vapor deposition (CVD) with ethanol as the source of carbon. Raman spectroscopy confirmed the presence of single walled carbon nanotubes (SWNTs). High resolution transmission electron microscopy (HRTEM) showed the formation of multi walled carbon nanotubes (MWNTs). Thermal and mechanical properties of the nanocomposites were studied by analyzing samples containing different amounts of CNTs. The degree of crystallinity (X_c) of the PEAA‐based nanocomposite containing a smaller amount of CNTs was larger (X_c = 17.0%) than both the one of pure PEAA (X_c = 14.6 %) and PEAA‐based nanocomposite containing higher amounts of CNTs (X_c = 15.0%). The Young's modulus, ultimate stress, deformation at break, and toughness obtained from unidirectional tensile tests of the CNTs (1 wt%)‐PEAA nanocomposite were higher than both the one of pure PEAA and CNTs (5 wt%)‐PEAA nanocomposite. When a polymer mixture of PEAA/PEOx (containing 80 wt% of PEAA) was used as a matrix, a better mechanical response was also detected for nanocomposite containing 1 wt% CNTs. The nanocomposites containing small amounts of CNTs prepared here have potential to be used as coatings of metal or glass surfaces expecting a better mechanical performance than the one of pure matrix. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Confined adamantane molecules assembled to one dimension in carbon nanotubes

We have encapsulated adamantane (C₁₀H₁₆) in single- and multi-walled carbon nanotubes. Adamantane is a high symmetry cage like molecule with point group symmetry T_d and can be considered as a hydrogen-terminated diamond fragment. We confirmed and identified the successful filling by high resolution transmission electron microscopy, ¹³C nuclear magnetic resonance, infrared and Raman spectroscopy. ¹³C nuclear magnetic resonance of the adamantane filled nanotubes reveals that the adamantane molecules stop rotating after encapsulation. A blue-shift of the Raman active radial breathing modes of the carbon nanotubes supports this and suggests a significant interaction between encapsulated adamantane molecules and the single wall nanotubes. The encapsulated adamantane molecules exhibit red shifted infrared C–H vibration modes which we assign to a slight elongation of the C–H bonds. We observe both a nanotube diameter dependence of the adamantane filling ratio and a release rate of adamantane from the CNTs that depends on the CNT diameters.     

Role of systemic T-cells and histopathological aspects after subcutaneous implantation of various carbon nanotubes in mice

We have evaluated the biological responses to four different types of carbon nanotubes (CNTs), by measuring CD4⁺ and CD8⁺ T-cells in peripheral blood, and by the histopathological study on tissues surrounding subcutaneously implanted CNTs for up to 3 months. All mice survived, and no large changes in their weights were observed within our experimental period. After 1 week, only single-walled carbon nanotubes (SWNTs) activated major histocompatibility complex (MHC) class I pathway of antigen-antibody response system (higher CD4⁺/CD8⁺ value), resulting in the appearance of an edematous aspect. After 2 weeks, significantly high values in CD4⁺ and CD4⁺/CD8⁺ without change in CD8⁺ signified an activated MHC class II for all samples. It is worth noting that the toxicological response of CNTs was absolutely lower than that of asbestos. As a result, we envisaged that our result (relatively low toxicity of CNTs) will spur the mass-production, as well widespread application of CNTs in the near future.     

Synthesis and Characterization of Novel Hybrids of Tris[3-(trimethoxysilyl)propyl] Isocyanurate (TTPI) Capped Palladium Nanoparticles and Single-Walled Carbon Nanotubes

The conjugation of nanoparticles to carbon nanotubes (CNTs) involves various steps including premodification of the nanotubes, which is known to be a very tedious process and sometimes leads to a mixture of products. In this regard, a direct route to generate such conjugates is a worthwhile endeavor. In this paper, we report a novel, mild, one-pot, approach to a controlled and direct coordination of Pd nanoparticles (Pd NPs) onto the surface of single walled carbon nanotubes (SWNTs), without any pre-modification of the SWNTs surface. We also present detailed characterization of the SWNT-Pd NP hybrid systems using High Resolution Transmission Electron Microscopy (HRTEM), Energy Dispersive X-ray Spectroscopy (EDS), Mid-Infrared Spectroscopy (Mid-IR) and UV-Visible Spectroscopy (UV–vis) along with the stability studies of the nanoconjugates.     

Catalyst effect of metal cations on pyrolysis of hydrocarbon molecules and formation of carbon nanotubes in the channels of AlPO4-5 crystals

Ultra-small single-walled carbon nanotubes (SWNTs) with diameter of 0.4 nm were fabricated in the channels of AlPO₄-5 crystals by pyrolyzing hydrocarbon molecules. In order to improve the structural quality of the SWNTs, we introduced Br?nsted acid sites onto the channel walls by incorporating metal cations (Mn, Mg, Co, and Si) into AlPO₄-5 framework. The Br?nsted acid sites play an important catalytic role in the carbonization of hydrocarbon molecules (tripropylamine) in the AlPO₄-5 channels, and favor the formation of SWNTs, as revealed by the significant decrease in formation energy of the nanotubes. The experimental results agree well with the predictions of first-principles calculations.     

Catalyst effect of metal cations on pyrolysis of hydrocarbon molecules and formation of carbon nanotubes in the channels of AlPO4-5 crystals

Ultra-small single-walled carbon nanotubes (SWNTs) with diameter of 0.4 nm were fabricated in the channels of AlPO₄-5 crystals by pyrolyzing hydrocarbon molecules. In order to improve the structural quality of the SWNTs, we introduced Brønsted acid sites onto the channel walls by incorporating metal cations (Mn, Mg, Co, and Si) into AlPO₄-5 framework. The Brønsted acid sites play an important catalytic role in the carbonization of hydrocarbon molecules (tripropylamine) in the AlPO₄-5 channels, and favor the formation of SWNTs, as revealed by the significant decrease in formation energy of the nanotubes. The experimental results agree well with the predictions of first-principles calculations.     

Ferrocene-filled single-walled carbon nanotubes

Ferrocene molecules are successfully introduced into the inner hollow space of Single-walled carbon nanotubes (SWNTs) to get ferrocene-filled SWNTs (Fc@SWNTs). This nanohybrid material was carefully characterized by high resolution microscopy, FTIR spectrum, and Cyclic voltammetry (CV). This new material may not only act as air stable n-type field-effect transistors based on nanotubes, but it may also be employed as building blocks for various devices based on the redox activity of ferrocene. What’s more, upon high temperature annealing, the encapsulated ferrocene molecules will decompose and change into interior tubes, forming double-walled carbon nanotubes (DWNTs). This provides convincing evidence that ferrocene molecules are inserted into the hollow cavities SWNTs. This result also presented a controllable way to synthesize DWNTs.     

Influence of carbon nanotubes with different functional groups on the morphology and properties of PPO/PA6 blends

Carbon nanotubes with different functional groups were prepared and then incorporated into the poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6) blend via melt blending. The influence of different carbon nanotubes on the morphology and properties of the blend was studied. The results show that addition of pristine CNTs, CNTs‐OH, CNTs‐NH₂ leads to the evolution of the phase structure of PPO/PA6 (mass ratio: 60/40) blend from sea‐island to cocontinuous, whereas incorporation of CNTs‐COOH does not change the blend morphology due to serious aggregation of the carbon nanotubes. Incorporating different CNTs into PPO/PA6 blend increases the tensile modulus and storage modulus of the blends, whereas decreases slightly the tensile strength. At the same time, the glass transition temperatures (T_g) of PA6 and PPO are enhanced. ΔT_g, the gap between the T_g of PA6 and PPO, decreases with the addition of carbon nanotubes due to the stronger interaction of carbon nanotubes with PA6 than PPO. A similar tendency was found in the storage modulus (G′) and complex viscosity (η*) of the composites. The dispersion state of different carbon nanotubes and their interaction with polymer components are different, which causes the different confinement effect to the macromolecular chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ionic peapods from carbon nanotubes and phosphotungstic acid

Using a mild wet-chemical route, cage-like phosphotungstic acid (HPW) molecules of 1.2 nm diameter were successfully filled into opened carbon nanotubes (CNTs) with cavity diameter of 2 nm. High resolution transmission electron microscope revealed that HPW molecules arrayed in a chain in the tube cavity, forming a new kind of peapod structure. In aqueous solution these unusual peapods showed higher ionic property than the opened nanotubes, with a ζ-potential of −47.5 ± 1.3 mV, and dissolved finely as a stable solution. Raman spectra confirmed the strong interaction between HPW molecules and CNT graphite wall. It could substantially tune the electronic properties of CNTs and thus promote their applications in novel electronic devices.