Complete elimination of metal catalysts from single wall carbon nanotubes

The complete removal of entrapped metallic impurities (i.e. Ni and Co) incorporated within single wall carbon nanotubes (SWNTs) has been a long-standing issue. A sonication-mediated treatment of as-obtained SWNT soot in a 1:1 mixture of aqueous hydrofluoric and nitric acids resulted in the complete elimination of these impurities as shown by energy dispersive X-ray analysis (EDAX). Contact angle measurements indicated that the wetting of SWNTs is enhanced in the presence of HF. The presence of HNO₃ and surfactant was found essential in removing the catalyst due to SWNT etching of end-caps/defects and providing better dispersion, respectively. Moreover, Raman spectroscopy indicated that the structural purity of the SWNTs is not compromised by the HF/HNO₃ purification treatment.     

Phonons in single wall carbon nanotube bundles

We review recent and original results on the vibrational properties of single wall carbon nanotubes (SWNT). We especially focus on calculations and experiments performed on nanotube bundles. So far, the main technique for probing the dynamics has been Raman spectroscopy. Here, we discuss: (i) the relation between frequency of the A_1g radial breathing mode and nanotube diameter, (ii) the origin of resonance and the consequences on the profile and intensity of the Raman lines, and (iii) the assignment and resonant behaviour of the Raman lines between 700 and 1000 cm⁻¹. Recently, inelastic neutron scattering techniques (INS) were shown to be effective tools to probe the vibrational density of states of SWNT. We review the INS results and focus on the study of low frequency excitations, especially libration-twist modes and acoustic modes. Both Raman and INS results are analysed in the light of calculations performed in a valence force field model taking into account van der Waals intertubes interactions in the bundles.     

Synthesis and Raman characterization of boron-doped single-walled carbon nanotubes

A systematic study was carried out to dope single-walled carbon nanotube (SWNT) bundles with varying amounts of boron using the pulsed laser vaporization technique. Targets containing boron concentrations ranging from 0.5 to 10 at.% boron were prepared by mixing elemental boron with carbon paste and the Co/Ni catalysts. The laser-generated products that were obtained from these targets were characterized by high resolution transmission electron microscopy, electron energy loss spectroscopy (EELS), thermoelectric power (TEP) measurements, and Raman scattering experiments. Electron microscopy and Raman studies revealed that the presence of various levels of boron concentration in the target strongly affected the products that were prepared. SWNTs were found in the products prepared from targets containing up through 3 at.% boron, and high resolution EELS estimated that less than 0.05-0.1 at.% boron is present in the SWNT lattice. The absence of SWNT bundles in the products derived from targets containing more than 3 at.% boron implies that the presence of excess boron in the carbon plume severely inhibits the carbon nanotube growth. The overall effect of the boron incorporation primarily leads to: (i) a systematic increase in intensity of the disorder-induced band (D-band) upon boron doping, with increasing D-band intensity observed for higher doping levels, (ii) a systematic downshift in the G′-band frequency due the relatively weaker C-B bond, and (iii) a non-linear variation in the RBM and G′-band intensities which is attributed to shifts in resonance conditions in the doped tubes. Resonant Raman spectroscopy thus provides large changes in the intensity of prominent features even when the dopant concentration is below the detectable limit of EELS (0.05-0.1 at.%). Thermoelectric power data also provide complementary evidence for the presence of a small boron concentration in the SWNT lattice which transforms the SWNTs into a permanently p-type material.     

Microscopic mechanism of reinforcement in single-wall carbon nanotube/polypropylene nanocomposite

We analyzed mechanical properties and structure of polypropylene fibers with different concentrations of single-wall carbon nanotubes (SWNTs) and draw down ratios (DDR). Tensile tests show a three times increase in the Young's modulus with addition of only 1 wt% SWNT, and much diminished increase of modulus with further increase in SWNT concentration. Microscopic study of the mechanism of reinforcement by SWNT included Raman spectroscopy and wide-angle X-ray diffraction (WAXD). The results show linear transfer of the applied stress from the polymer matrix to SWNT. Analysis of WAXD data demonstrates formation of a β-crystal phase in polypropylene matrix under the strain.     

Carbon nanotubes as Raman sensors of vulcanization in natural rubber

A method has been developed to synthesize composites with cross-linked natural rubber (NR) and dispersed single-wall carbon nanotubes (SWNT). The mechanical response of the NR samples was observed to change as a function of the amount of sulfur used for cross-linking, based on the number density of cross-links resulting from the vulcanization process. The relationship between SWNTs D^∗ wavenumber shift and the amount of sulfur have been obtained by means of Raman spectroscopy. The cross-link densities of the NR and SWNT/NR samples have been calculated from uniaxial stress-strain measurements, and plotted as the function of the amount of added sulfur. Comparison of the results from mechanical measurements and Raman spectroscopic measurements showed that SWNT Raman sensors are sensitive to the cross-link density in natural rubber and can be used to evaluate the cross-linking process of rubbery materials.     

Co-synthesis, purification and characterization of single- and multi-walled carbon nanotubes using the electric arc method

We report the simultaneous synthesis of single-walled (SWNT) and multi-walled (MWNT) carbon nanotubes using the electric arc method. Two distinct deposits are formed when an electric arc is struck between a Co/Ni impregnated carbon electrode (anode) and a graphite electrode (cathode). The cobweb-like deposit harvested from the walls of the growth chamber (chamber deposit) contained SWNT bundles while the MWNTs were present in the deposit formed at the tip of the cathode (cathode deposit). Energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and Raman spectroscopy of each deposit confirmed the presence of respective carbon nanotubes along with carbonaceous impurities. A systematic purification procedure for separating SWNT bundles from the rest of the impurities is discussed. The optimal yield of purified SWNT bundles is ∼25 wt.% of the as-prepared chamber deposit.     

Crystallization and orientation studies in polypropylene/single wall carbon nanotube composite

Crystallization behavior of melt-blended polypropylene (PP)/single wall carbon nanotube (SWNT) composites has been studied using optical microscopy and differential scanning calorimetry. Polypropylene containing 0.8 wt% SWNT exhibits faster crystallization rate as compared to pure polypropylene. PP/SWNT fibers have been spun using typical polypropylene melt spinning conditions. The PP crystallite orientation and the SWNT alignment in the fibers have been studied using X-ray diffraction and polarized Raman spectroscopy, respectively.     

Conductivity and mechanical properties of well-dispersed single-wall carbon nanotube/polystyrene composite

The morphologies, electrical and mechanical properties and structure of polystyrene (PS) composites with varying concentrations of single-wall carbon nanotubes (SWNT) are analyzed. Using Raman spectroscopy and electron microscopy, we demonstrate that initial thermal annealing of SWNT significantly improves their dispersion in PS. In dielectric measurements, the annealed SWNT/PS composites show higher electrical conductivity and a lower percolation threshold (less than 0.3 wt%) than the raw SWNT/PS composites, which provides further evidence of good dispersion of the annealed SWNT in PS. Raman spectra of composites under tension show good transfer of an applied stress from the polymer matrix to SWNT. However, mechanical moduli of the annealed SWNT/PS composites are only increased slightly. The reason for this discrepancy remains unclear.     

Single wall carbon nanotube templated oriented crystallization of poly(vinyl alcohol)

Shearing of poly(vinyl alcohol) (PVA)/single wall carbon nanotube (SWNT) dispersions result in the formation of self-assembled oriented PVA/SWNT fibers or ribbons, while PVA solution results in the formation of unoriented fibers. Diameter/width and length of these self-assembled fibers was 5-45 μm and 0.5-3 mm, respectively. High-resolution transmission electron micrographs showed well resolved PVA (200) lattice with molecules oriented parallel to the nanotube axis. Nanotube orientation in the self-assembled fibers was also determined from Raman spectroscopy. PVA fibers exhibited about 48% crystallinity, while crystallinity in PVA/SWNT fibers was 84% as determined by wide angle X-ray diffraction. PVA and carbon nanotubes were at an angle of 25-40° to the self-assembled fiber axis. In comparison to PVA, PVA/SWNT samples exhibited significantly enhanced electron beam radiation resistance. This study shows that single wall carbon nanotubes not only nucleate polymer crystallization, but also act as a template for polymer orientation.     

Analysis of the cure reaction of carbon nanotubes/epoxy resin composites through thermal analysis and Raman spectroscopy

The effect of the incorporation of single‐walled carbon nanotubes (SWNTs) onto a diglycidyl ether of bisphenol A‐based (DGEBA) epoxy resin cure reaction was investigated by thermal analysis and Raman spectroscopy. The results of the investigation show that SWNTs act as a strong catalyst. A shift of the exothermic reaction peak to lower temperatures is, in fact, observed in the presence of SWNTs. Moreover, these effects are already noticeable at the lowest SWNT content investigated (5%) with slight further effects at higher concentrations, suggesting a saturation of the catalyzing action at the higher concentrations studied. The curves obtained under isothermal conditions confirm the results obtained in nonisothermal tests showing that the cure reaction takes less time with respect to the neat epoxy. The thermal degradation of cured DGEBA and DGEBA/SWNT composites was examined by thermogravimetry, showing a faster thermal degradation for DGEBA–SWNT composites. Raman spectroscopy was successfully applied to demonstrate that the observed changes in the cure reaction of the composites lead to a different residual strain on the SWNT bundles following a different intercalation of the epoxy matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 452–458, 2003     

Single-wall carbon nanotubes with diameters approaching 6 nm obtained by laser vaporization

Single-wall carbon nanotubes (SWNTs) with large diameters from 2 to 5.6 nm were prepared by pulsed laser vaporization of carbon rods doped with Co, Ni and FeS in an atmosphere of Ar:H₂. The SWNT material was characterized by SEM, HRTEM, Raman, IR, UV-VIS-NIR absorption spectroscopy and thermogravimetric analysis.     

Well-dispersed single-walled carbon nanotube/polyaniline composite films

Single-walled carbon nanotube (SWNT)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dissolved SWNTs. The results of atomic force microscopy (AFM) and UV-Vis adsorption spectroscopy show that aniline can be used to solubilize SWNTs via formation of donor-acceptor complexes. The electrochemical deposition of SWNT-aniline solutions have been investigated by cyclic voltammetry. The results show that SWNT-based aniline solutions exhibit a drastic increase in peak current within the potential scanning region. The doping effect of SWNTs on PANI films was investigated by electrochemistry and FTIR spectroscopy. The results indicate that the enhanced electroactivity and conductivity of the SWNT/PANI composite films may be due to the strong interaction between SWNTs and PANI, which facilitates the effective degree of electron delocalization.     

Interfacial in situ polymerization of single wall carbon nanotube/nylon 6,6 nanocomposites

An interfacial polymerization method for nylon 6,6 was adapted to produce nanocomposites with single wall carbon nanotubes (SWNT) via in situ polymerization. SWNT were incorporated in purified, functionalized or surfactant stabilized forms. The functionalization of SWNT was characterized by FTIR, Raman spectroscopy and TGA and the SWNT dispersion was characterized by optical microscopy before and after the in situ polymerization. SWNT functionalization and surfactant stabilization improved the nanotube dispersion in solvents but only functionalized SWNT showed a good dispersion in composites, whereas purified and surfactant stabilized SWNT resulted in poor dispersion and nanotube agglomeration. Weak shear flow induced SWNT flocculation in these nanocomposites. The electrical and mechanical properties of the SWNT/nylon nanocomposites are briefly discussed in terms of SWNT loading, dispersion, length and type of functionalization.     

Electrochemical potential control of isolated single-walled carbon nanotubes on gold electrode

Spectral features of Raman scattering of isolated single-walled carbon nanotubes (SWNT) on gold surface in aqueous solution was investigated under electrochemical potential control. Spectrum of the radial breathing mode of SWNT was dependent upon the electrode potential. Change in the intensity of the spectrum was reversible. Distinct difference in the potential dependence was observed at SWNT with different diameter. Absolute potential of the Fermi level of individual tubes was estimated from the potential dependence. Observations suggest that the work function of the tube becomes larger in a manner inversely proportional to the diameter of SWNT. Linewidth of the spectrum also showed potential dependence at the metallic tubes. Characteristics of the spectral changes induced by electrochemical doping were correlated to the difference in electronic density of individual SWNT with distinct diameter and chirality.     

Magnetic field alignment and electrical properties of solution cast PET-carbon nanotube composite films

Single-wall carbon nanotubes (SWNTs) were dispersed in a polyethylene terephthalate (PET) matrix by solution blending and then cast onto a glass substrate to create flexible films. Various SWNT loading concentrations were implemented (0.5, 1.0, and 3.0 wt%), and the processing method was repeated to produce films in the presence of magnetic fields (3.0 and 9.4 T). Alignment of the SWNTs in the PET matrix was characterized by Raman spectroscopy. Impedance spectroscopy was utilized to study the electrical behavior of the nanocomposites. It was concluded that SWNT concentration and dispersion are the key variables for improving electrical conductivity, while alignment plays a secondary role. Interestingly, it appears that a magnetic field may prove to be a novel method for improving the dispersion of unmodified SWNTs by disrupting van der Waals interactions.     

The effect of the cobalt loading on the growth of single wall carbon nanotubes by CO disproportionation on Co-MCM-41 catalysts

Highly ordered MCM-41 mesoporous molecular sieves in which silicon was isomorphously substituted with 0.5-4 wt.% cobalt were synthesized using an alkyl template with a 16 carbon atoms alkyl chain length. These materials were used as catalysts for the synthesis of uniform diameter single wall carbon nanotubes (SWNT) by CO disproportionation (Boudouard reaction). The SWNT synthesis conditions were identical for all Co-MCM-41 samples, and consisted of pre-reduction of the Co-MCM-41 catalyst in hydrogen at 500 °C for 30 min followed by reaction with pure CO at 800 °C and 6 atm for 1 h (conditions previously optimized for 1 wt.% Co-MCM-41). The SWNT grown in the Co-MCM-41 catalysts were characterized by TGA, multi-excitation energy Raman spectroscopy and TEM. The state of the catalyst and the size of the metallic cobalt clusters formed in Co-MCM-41 during the SWNT synthesis were characterized by X-ray absorption spectroscopy. The mechanism controlling the diameter distribution of the SWNT produced is related to the size uniformity of the cobalt clusters nucleated in the Co-MCM-41 catalytic template: the SWNT growth selectivity and size uniformity is influenced by the cobalt concentration in the framework. If the cobalt is not initially strongly stabilized in the MCM-41 framework during template synthesis, the catalyst produces SWNT with a wider diameter distribution. Co-MCM-41 catalysts with up to 3 wt.% cobalt can be used to grow SWNT with a diameter distribution similar to that obtained with 1 wt.% Co-MCM-41, but at yields greater by a factor of approximately 2.4.     

An effective surfactant-free isolation procedure for single-wall carbon nanotubes

An optimised isolation procedure of single-wall carbon nanotubes (SWNTs) from a SWNT soot without using any surfactant is reported. Amorphous carbon and small graphitic particles were washed away with N-methyl-2-pyrrolidone (NMP) and acetone. A large amount of graphite-coated metal particles were removed with the oxidation of the SWNT material with HNO₃ (6.5 and 4 M) and by washing the oxidised SWNT material with a mixture of methanol (MeOH) and deionised water. The isolated material was investigated with transmission electron microscopy (TEM) and Raman scattering (647.1 and 532 nm). An elemental analysis of the content of Co and Ni in the SWNT samples isolated at different steps of the isolation procedure was performed. On the basis of the TEM images and elemental analysis it was estimated that the purified material contains more than 75 wt.% of SWNTs.     

Stabilization and carbonization of gel spun polyacrylonitrile/single wall carbon nanotube composite fibers

Gel spun polyacrylonitrile (PAN) and PAN/single wall carbon nanotube (SWNT) composite fibers have been stabilized in air and subsequently carbonized in argon at 1100 °C. Differential scanning calorimetry (DSC) and infrared spectroscopy suggests that the presence of single wall carbon nanotube affects PAN stabilization. Carbonized PAN/SWNT fibers exhibited 10-30 nm diameter fibrils embedded in brittle carbon matrix, while the control PAN carbonized under the same conditions exhibited brittle fracture with no fibrils. High resolution transmission electron microscopy and Raman spectroscopy suggest the existence of well developed graphitic regions in carbonized PAN/SWNT and mostly disordered carbon in carbonized PAN. Tensile modulus and strength of the carbonized fibers were as high as 250 N/tex and 1.8 N/tex for the composite fibers and 168 N/tex and 1.1 N/tex for the control PAN based carbon fibers, respectively. The addition of 1 wt% carbon nanotubes enhanced the carbon fiber modulus by 49% and strength by 64%.     

Molecularly imprinted polymers integrated with surface enhanced Raman spectroscopy: Innovative chemosensors in food science

Determination of trace levels of compounds in agri‐foods are challenging due to the complexity of the agricultural and food matrices. A specific and complete separation and enrichment of the target compound is sometimes more important than the development of detection tools. Raman spectroscopy and its derivative, surface enhanced Raman spectroscopy (SERS), have been widely used for the detection of specific food components due to their unique ability to record “fingerprinting” features of each molecule. However, Raman spectroscopy/SERS records the spectral signatures of all the food components, demonstrating that a pre‐separation of the target compound is critical. Molecularly imprinted polymers (MIPs), defined as “artificial antibodies”, have been constructed and integrated with Raman spectroscopy/SERS for an accurate and reliable separation and detection of target compounds in agri‐foods with minimum interference from food matrices. Compared to other separation elements (e.g., antibody, aptamer etc.) that can be integrated with Raman spectroscopy/SERS for sensing, MIPs do not contribute to spectral signature, can be reused multiple times and are more resistant to environmental factors, demonstrating the potential to be used for in‐field and on‐line screening of food safety and quality.     

Electrical transport properties of small diameter single-walled carbon nanotubes aligned on ST-cut quartz substrates

A method is introduced to isolate and measure the electrical transport properties of individual single-walled carbon nanotubes (SWNTs) aligned on an ST-cut quartz, from room temperature down to 2 K. The diameter and chirality of the measured SWNTs are accurately defined from Raman spectroscopy and atomic force microscopy (AFM). A significant up-shift in the G-band of the resonance Raman spectra of the SWNTs is observed, which increases with increasing SWNTs diameter, and indicates a strong interaction with the quartz substrate. A semiconducting SWNT, with diameter 0.84 nm, shows Tomonaga-Luttinger liquid and Coulomb blockade behaviors at low temperatures. Another semiconducting SWNT, with a thinner diameter of 0.68 nm, exhibits a transition from the semiconducting state to an insulating state at low temperatures. These results elucidate some of the electrical properties of SWNTs in this unique configuration and help pave the way towards prospective device applications.