Horizontally aligned single-walled carbon nanotube field emitters fabricated on vertically aligned multi-walled carbon nanotube electrode arrays

Vertically aligned multi-walled carbon nanotube (MWCNT) arrays were fabricated on an anodic aluminum oxide membrane bonded to a Si wafer. After obtaining a protruding tip for the MWCNTs by etching away some oxide, they were used as electrodes in the fabrication of carbon nanotube field emitters. Long single-walled carbon nanotubes (SWCNTs) were spin coated on the MWCNT arrays of uniform height. Clean SWCNTs were suspended by attaching them to the tips of the vertically aligned MWCNT arrays. The spin coated SWCNTs function as emitters, while the MWCNT arrays function as electrodes. The field emission was greatly improved by coating gold on the MWCNT arrays and annealing at 400 °C. Our field emitter exhibits good field emission properties such as a low turn-on field (1.4 V/μm), high current density (122 mA/cm²), and good stability (55 h for 10% degradation of current density from 400 μA/cm²).     

Friction and adhesion properties of vertically aligned multi-walled carbon nanotube arrays and fluoro-nanodiamond films

Sliding friction and adhesion properties of vertically aligned multi-walled carbon nanotube (VAMWCNT) arrays and fluoro-nanodiamond (F-ND) films on glass substrate have been quantitatively investigated in current study using atomic force microscopy. It was found that VAMWCNT arrays result in lower friction compared to F-ND films. Friction forces were also found to be consistently higher in nitrogen environment than in ambient environment for both samples and a surface chemistry based hypothesis was proposed. However, no apparent dependence of relative humidity was found on adhesion forces for both F-ND and VAMWCNT samples, indicating lack of correlation between nanoscale adhesion and friction. The implications from current study for designing movable components in micro- and nanoelectromechanical system devices were also discussed.     

Electrical and piezoresistive properties of multi-walled carbon nanotube/polymer composite films aligned by an electric field

Aligned multi-walled carbon nanotube (MWCNT)/polymer composite films are prepared by solution casting in the presence of an alternating electric field. Application of 7 kV/m at a frequency of 60 Hz to the polymer composite melt induces MWCNT alignment in the direction of the applied field, which is maintained after polymer crystallization. The electrical conductivity and piezoresistive response of electric-field-aligned and randomly oriented 0.1–0.75 wt% MWCNT/polysulfone films are evaluated. Electrical conductivity is 3–5 orders of magnitude higher for composites with electric-field-aligned MWCNTs than for randomly oriented composites. MWCNT alignment inside the polymer matrix also increases the film piezoresistive sensitivity, enhancing the strain sensing capabilities of the composite film.     

Frictional behaviour of vertically aligned carbon nanotube films

Vertically aligned CNT films were grown on polycrystalline β-SiC wafers by the surface decomposition method. Their frictional behaviours were investigated by AFM at the nanometer scales. Compared with DLC film and silicon wafers, they demonstrate an extremely low friction coefficient at the nanometer scale about 0.03-0.04. The effect of the surface topography on the friction coefficient is obvious for the aligned CNT film sliding at the nanometer scale. This implies that the excellent tribological properties of the vertically aligned CNT films, combined with their small dimensions and structural perfection, might lead to significant improvement of the performance of nano-devices.     

Temperature dependent piezoresistive effect of multi-walled carbon nanotube films

The temperature dependence of piezoresistive effect on multi-walled carbon nanotube (MWNT) films is investigated. The gauge factor for pristine MWNT films and chemically treated MWNT films at 500 microstrain was found to be 46 and 75, respectively, at room temperature, but increased rapidly with temperature, exceeding that of polycrystalline silicon (30) at 35 °C. These findings suggest that the performance of carbon nanotube-based sensors may be significantly superior to that of polycrystalline silicon.     

Densified aligned carbon nanotube films via vapor phase infiltration of carbon

We report a simple way to produce fully densified aligned carbon nanotube (ACNT) films. The simultaneous growth of nanotubes and densification of the ACNT films by carbon infiltration in the interstitial spaces between nanotubes are accomplished in a single step by the combination of the chemical vapor deposition and chemical vapor infiltration processes. Scanning electron microscope analysis and microbalance measurements showed that after infiltration, the diameters of nanotubes and bulk density of the ACNT films are increased by an order of magnitude (and hence the porosity of the ACNT films is decreased). Transmission electron microscope and Raman scattering analysis showed that after densification, the nanotubes are conformally coated by partially graphitized pyrolytic carbon. The compressive modulus of the densified ACNT films could be increased by three orders of magnitude compared to the pristine ACNT films. Electrical properties are also measured for the densified films showing marked differences with the ACNT films. The property enhanced densified ACNT films constitute a new form of carbon-carbon nanocomposites and could find applications as multifunctional nanocomposites.     

Covalent functionalization of multi-walled carbon nanotube surfaces by conjugated polyfluorenes

The outer surface of multi-walled carbon nanotubes (MWCNTs) was successfully modified with 7-bromo-9,9-dioctylfluorene-2-carbaldehyde by using 1,3-dipolar cycloaddition of azomethine reaction to introduce bromo functional groups. The peripheral bromo functional groups can be used to further react with AB-type monomers through Suzuki polycondensation to afford the PF-functionalized MWCNTs, which are of a cable-like structure. Through covalent connection to MWCNTs, the fluorescence of polyfluorenes was completely quenched by the MWCNTs, indicating a fast photo-induced electron transfer from polyfluorenes to MWCNTs.     

Catalytic activity of ultrathin Pt films on aligned carbon nanotube arrays

Uniform ultrathin Pt films were electrodeposited onto an aligned array of carbon nanotubes (CNTs) for high-area chemically stable methanol fuel cell anodes. Electrochemical treatment of the graphitic CNT surfaces by diazoniumbenzoic acid allowed for uniform Pt electroplating. The mass activity of the Pt thin film can reach 400 A/g at a scan rate of 20 mV/s and in a solution of 1 M CH₃OH/0.5 M H₂SO₄. A programmed pulse potential at 0 V was also seen to nearly eliminate the effects of carbon monoxide poisoning. The mass activity of Pt for methanol oxidation can be maintained at 300 A/g for more than 3000 s, which is 19 times of that under a constant potential of 0.7 V (vs. Ag/AgCl).     

Development of microreactors made of vertically aligned carbon nanotube films

Microreactors consisting of multiwalled carbon nanotube (CNT) microchannels have been developed. Vertically aligned CNT films with negative pattern shapes of microchannels are grown on silicon oxide films, providing CNT microchannels. Polymethyl methacrylate plates are placed on the CNT microchannels for the flow experiments. Since CNTs are hydrophobic and the silicon oxide film is hydrophilic, fluids can flow in the silicon oxide regions in the CNT microreactors. Fermat’s spiral and Y-junction type multiwalled CNT microreactors were synthesized.     

Terahertz time-domain spectroscopy characterization of vertically aligned carbon nanotube films

Terahertz time-domain spectroscopy measurements were made for vertically aligned multi-walled carbon nanotube (VACNT) films. We obtained the frequency dependent complex permittivity and conductivity (on the assumption that permeability μ = 1) of several samples exhibiting Drude behaviour for lossy metals. The obtained material properties of VACNT films provide information for potential microwave and terahertz applications.     

An evaluation of cell proliferation and adhesion on vertically-aligned multi-walled carbon nanotube films

Biocompatibility tests were performed on vertically-aligned multi-walled carbon nanotube (MWCNT) films produced by microwave plasma chemical vapor deposition on titanium substrates with iron (Fe) and nickel (Ni) as catalysts. The cell adhesion and morphology of L-929 mouse fibroblast cells were studied by high resolution scanning electron microscopy, after up to 7 days incubation periods. Cell viability and proliferation were evaluated by two “in vitro” tests: (1) 2-(4,5-dimethyl-2-thiazolyl)-3,5-diphenyl-2H-tetrazolium bromide (MTT), and (2) lactate dehydrogenase (LDH) assays. Low level of bioavailable Fe and Ni was determined by inductively coupled plasma optical emission spectrometry. Neither functionalization nor purification of MWCNT films was necessary to obtain good response to the biocompatibility tests. Efficient cell growth and non-toxicity suggest the use MWCNTs in tissue regeneration. The MWCNT films stimulated the cell growth, showing a proliferation 20% higher than on Ti.     

Impact of molecular mass on the elastic modulus of thin polystyrene films

Surface wrinkling was used to determine the elastic modulus at ambient temperature of polystyrene (PS) films of varying thickness and relative molecular mass (M_n). A range of M_n from 1.2 kg/mol to 990 kg/mol was examined to determine if the molecular size impacts the mechanical properties at the nanoscale. Ultrathin films exhibited a decrease in modulus for all molecular masses studied here compared to the bulk value. For M_n > 3.2 kg/mol, the fractional change in modulus was statistically independent of molecular mass and the modulus began to deviate from the bulk as the thickness is decreased below ≈50 nm. An order of magnitude decrease in the elastic modulus was found when the film thickness was ≈15 nm, irrespective of M_n. However, an increase in the length scale for nanoconfinement was observed as the molecular mass was decreased below this threshold. The modulus of thin PS films with a molecular mass of 1.2 kg/mol deviated from bulk behavior when the film thickness was decreased below ≈100 nm. This result illustrates that the modulus of thin PS films does not scale with molecular size. Rather, the quench depth into the glass appears to correlate well with the length scale at which the modulus of the films deviates from the bulk, in agreement with molecular simulations from de Pablo and coworkers [31] and recent experimental work [35].     

Electrical properties of annealed MPCVD grown vertically aligned carbon nanotube films

Vertically aligned multiwalled carbon nanotubes (MWNTs) were grown on silicon substrate at a low temperature (<520 °C) using microwave plasma-enhanced chemical vapor deposition (MPCVD). From the Raman spectra, it was found that the I_D/I_G ratio of MWNTs decreased after annealing, indicating that more graphenes were formed by the annealing process. Nevertheless, a strong Si signal was found in Raman spectra after annealing at a high-temperature (600 °C). From X-ray photoelectron spectroscopy (XPS) analysis it was observed that the ratio of the oxygen to carbon (O/C) signal intensity was from 0.15 to 1.88 for the increasing annealed temperatures of MWNTs, and a Si signal was found nearby the surface of MWNTs after annealing at 600 °C. Moreover, from the I–V measurement, the less symmetric I–V characteristic was found for the metal/MWNTs/metal (MIM) sandwich structure of unannealed MWNTs. After 300 °C annealing process, the positive current was increase and the negative current was decrease. It was conjectured that the MWNTs could obtain more graphenes structure by the 300 °C annealing process. Moreover, the I–V trace of the sample annealed by 600 °C exhibited rapid current descent, indicating the oxygenated and partly silicided phenomena might cover outer graphite layer of MWNTs. The equivalent circuit for the MIM sandwich structure could be represented as two Schottky barrier diodes in a back-to-back configuration. From the data fitting, it was found that the Schottky barrier height (_B0) decreased and the current density (J) increased from unannealing to 300 °C annealing temperature. However, the Schottky barrier height (_B0) was increased from 300 to 600 °C annealing temperature. Comparison with the XPS, this may due to the oxygenated and partly silicided phenomenon on the surface of the MWNTs.     

Nucleation and aligned growth of multi-wall carbon nanotube films during thermal CVD

The development during early growth of a multi-wall carbon nanotube film by thermal CVD with acetylene (C₂H₂) and hydrogen at 750 °C has been characterized in detail by cross-section transmission electron microscopy. The studies provide information on the nanotube growth mechanisms and the complex catalyst transformations that are essential for the onset of different growth stages. An initial random growth catalysed by supported particles is followed by aerosol growth of aligned tubes. This results in a two-layered film structure, where a film of aligned nanotubes is lifting up an initially formed nanotube network from the substrate.     

Mechanical, electrical, piezoelectric and electro-active behavior of aligned multi-walled carbon nanotube/cellulose composites

Multi-walled carbon nanotubes (MWCNTs) were covalently grafted to cellulose to make an MWCNT/cellulose (M/C) composite. Aligned M/C composite was obtained by mechanical stretching process. The stretching effect was demonstrated by observing morphology as well as measuring mechanical, electrical and piezoelectric properties of the M/C composite. The influence of aligned MWCNTs on the actuator performance of the M/C composite was evaluated in terms of bending displacement and resonance frequency depending on the stretching ratio and environmental humidity level. The aligned MWCNTs contributed to remarkably enhancing the mechanical and piezoelectric properties, but also improving actuator performance of the M/C composite.     

Processing and properties of aligned multi-walled carbon nanotube/aluminoborosilicate glass composites made by sol-gel processing

We describe a novel sol-gel based approach for producing aluminoborosilicate glass composites containing continuous, aligned carbon nanotubes. The process involves the production of aligned carbon nanotubes (ACNT) via aerosol chemical vapour deposition (CVD), followed by infiltration of the ACNT with aluminoborosilicate sol. The advantages of this process are three fold: (1) aerosol CVD is an efficient method of producing clean, aligned arrays of CNTs, (2) sol-gel chemistry provides a simple route to infiltration of the ACNTs, and (3) carbon nanotube (CNT) agglomeration problems associated with CNT composites are circumvented. ACNTs (carpets) with heights of up to 4.4 mm were grown with areas of 10 mm × 20 mm for composite fabrication. The composite showed extensive pullout of the CNTs on a fracture surface and improved thermal and electrical conductivities of 16 Wm⁻¹ K⁻¹ and 5-8 × 10² S m⁻¹ respectively compared with only 1.2 W m⁻¹ K⁻¹ and 10⁻¹³ S m⁻¹ for the monolithic glass.     

Melt processing and mechanical property characterization of multi-walled carbon nanotube/high density polyethylene (MWNT/HDPE) composite films

High density polyethylene (HDPE) was used as the matrix material for a carbon nanotube (CNT) polymer composites. This combination of composite constituents has not been previously reported in the literature. Multi-wall carbon nanotube (MWNT)/HDPE composite films were fabricated using the melt processing method. The composite films with 0, 1, 3 and 5% nanotube content by weight were analyzed under SEM and TEM to observe nanotube dispersion. The mechanical properties of the films were measured by small punch test. Results show increases in the stiffness, peak load and work to failure for the composite films with increasing MWNT content.