Synthesis and characterization of polyurethane-grafted single-walled carbon nanotubes via click chemistry

Polyurethane (PU)-grafted carbon nanotubes were synthesized by the coupling of alkyne moiety decorated single walled carbon nanotube (SWCNT) with azide moiety containing PU using Cu(I) catalyzed Huisgen [3 + 2] cycloaddition click chemistry. The azide moiety containing poly(s-caprolactone)diol was synthesized by ring-opening polymerization and further used for PU synthesis. Alkyne-functionalizion of SWCNT was completed by the reaction of p-aminophenyl propargyl ether with SWCNT using a solvent free diazotization procedure. Nuclear magnetic resonance, Fourier transform infrared, and Raman spectroscopic measurements confirmed the functionalization of SWCNT. Scanning electron microscopy and transmission electron microscopy images showed an excellent dispersion of SWCNTs, and specially debundling of SWCNTs could be observed due to polymer assisted dispersion. A quantitative grafting was successfully achieved even at high content of functional groups.     

Fabrication and characterization of recyclable carbon nanotube/polyvinyl butyral composite fiber

A surface-draw method to fabricate recyclable carbon nanotube/polyvinyl butyral (CNT/PVB) composite fibers is reported. This method is effective for both single-walled carbon nanotube (SWCNT) and multi-walled carbon nanotube. The CNT mass content of CNT/PVB composite fibers can vary from 0 to 80 wt.%, which is higher than most CNT/polymer composites reported to date. The diameter of the composite fibers can be controlled in the range of 10-100 μm, with essentially unlimited draw length. The composite fibers with 7.4 wt.% SWCNTs showed optimal tensile properties. Compared with pure PVB fibers, the tensile strength, failure strain, and elastic modulus of the composite fiber have improved about 127%, 27%, and 73%, respectively. In addition, SWCNT/PVB composites with 66.7 wt.% SWCNTs have the highest conductivity of 42.9 S m⁻¹. More importantly, the major benefit is the “greenness” of the method, which involves environment friendly ethanol-water solvent with no functionalization of the nanotube required, and only simple apparatus are needed. The CNT/PVB composite fibers obtained can be dissolved in ethanol solution and reformed with the surface draw method without any additional treatment; and the material properties after recycle is comparable to those fabricated in the first round.     

Synthesis and characterization of ZnO nanowires for nanosensor applications

In this paper we report the synthesis of ZnO nanowires via chemical vapor deposition (CVD) at 650 °C. It will be shown that these nanowires are suitable for sensing applications. ZnO nanowires were grown with diameters ranging from 50 to 200 nm depending on the substrate position in a CVD synthesis reactor and the growth regimes. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Raman spectroscopy (RS) have been used to characterize the ZnO nanowires. To investigate the suitability of the CVD synthesized ZnO nanowires for gas sensing applications, a single ZnO nanowire device (50 nm in diameter) was fabricated using a focused ion beam (FIB). The response to H₂ of a gas nanosensor based on an individual ZnO nanowire is also reported.     

The incorporation of single-walled carbon nanotubes into polymerized high internal phase emulsions to create conductive foams with a low percolation threshold

New methods for the incorporation of single-walled carbon nanotubes (SWCNTs) into styrene-divinylbenzene-based high internal phase emulsions (HIPEs) are addressed with specific attention to minimizing the SWCNT loading while maintaining a high level of conductivity of the final polyHIPE–SWCNT composites. Stable HIPEs were achieved using sodium dodecyl sulfate-stabilized SWCNTs, thus eliminating the necessity of SWCNT functionalization. PolyHIPE–SWCNT composites were made with water: oil ratios (vol/vol) of 75:25 and of 84:16. The percolation threshold was determined to be 0.2 and 0.1 wt%, respectively. These threshold values are lower than that obtained for non-porous, polystyrene–SWCNT composites made by means of a latex-based route followed by melt-processing.     

Synthesis of carbon micro-rods via a solvothermal route

Novel carbon micro-rods with regular and uniform shape have been synthesized in high yield by magnesium acetate and n-butyl alcohol as the precursors via a solvothermal route. The resulting products were characterized by combined techniques including X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) and Raman spectroscopy. The carbon micro-rods exhibit diameters ranging from 500 nm to 1 μm and up to 5-10 μm in length. We have found that the optimal reaction conditions for the growth of the carbon micro-rods were 500 °C and 12 h.     

Low substrate temperature synthesis of carbon nanowalls by ultrasonic spray pyrolysis

In this paper, we report the synthesis of two-dimensional wall like carbon nanostructures (i.e. carbon nanowalls) by ultrasonic spray pyrolysis of ethanol and fullerene mixture. At higher temperature carbon nanofibers were formed on the substrate placed at the center of the reactor tube, whereas carbon nanowalls were observed on the substrate placed downstream of the tube below 100 °C. Spaces between the nanowalls changed with distance of the substrates from the furnace. Qualitative analysis of materials was performed using scanning electron microscopy, transmission electron microscopy and Raman spectroscopy.     

A parametric study of single-wall carbon nanotube growth by laser ablation

Results of a parametric study of carbon nanotube production by the double-pulse laser oven process are presented. The effect of various operating parameters on the production of single-wall carbon nanotubes (SWCNTs) is estimated by characterizing the nanotube material using analytical techniques, including scanning electron microscopy, transmission electron microscopy, thermo gravimetric analysis and Raman spectroscopy. The study included changing the sequence of the laser pulses, laser energy, pulse separation, type of buffer gas used, operating pressure, flow rate, inner tube diameter, as well as its material, and oven temperature. It was found that the material quality and quantity improve with deviation from normal operation parameters such as laser energy density higher than 1.5 J/cm2, pressure lower than 67 kPa, and flow rates higher than 100 sccm. Use of helium produced mainly small diameter tubes and a lower yield. The diameter of SWCNTs decreases with decreasing oven temperature and lower flow rates.     

Synthesis of single-walled carbon nanotubes by induction thermal plasma

The production of high quality single-walled carbon nanotubes (SWCNTs) on a bulk scale has been an issue of considerable interest. Recently, it has been demonstrated that high quality SWCNTs can be continuously synthesized on large scale by using induction thermal plasma technology. In this process, the high energy density of the thermal plasma is employed to generate dense vapor-phase precursors for the synthesis of SWCNTs. With the current reactor system, a carbon soot product which contains approximately 40 wt% of SWCNTs can be continuously synthesized at the high production rate of ∼100 g/h. In this article, our recent research efforts to achieve major advances in this technology are presented. Firstly, the processing parameters involved are examined systematically in order to evaluate their individual influences on the SWCNT synthesis. Based on these results, the appropriate operating conditions of the induction thermal plasma process for an effective synthesis of SWCNTs are discussed. A characterization study has also been performed on the SWCNTs produced under the optimum processing conditions. Finally, a mathematical model of the process currently under development is described. The model will help us to better understand the synthesis of SWCNTs in the induction plasma process.      

Passive mode locking of ceramic Nd: YAG using (7, 5) semiconducting single walled carbon nanotubes

Passive mode-locking of a ceramic Nd: YAG laser was demonstrated using highly purified single walled carbon nanotubes (SWCNTs) as the saturable absorber (SA). Poly [(9,9-dihexylfluorenyl-2,7-diyl)-co-(9,10-an-thracene)] or PFO was used to extract a purified sample of semiconducting SWCNTs that consisted of mainly (7, 5) nanotubes (∼80% of the SWCNT ensemble). The pulses had a near Fourier transform-limited pulse width of about 8.3 ps in a non-dispersion compensated setup. In addition, Z-scan investigations revealed that SWCNT SA had a saturation intensity of about 1.7 MW cm⁻² with a modulation depth of about 6% and a non-saturable loss of about 5.5%.     

Growth of single and double walled carbon nanotubes over Co/V/MgO catalysts

High quality single walled carbon nanotubes (SWCNTs) and double walled carbon nanotubes (DWCNTs) were synthesized on Co/V/MgO catalysts by catalytic decomposition of CH₄ in H₂. Raman spectroscopy data revealed that the diameters of as-prepared SWCNTs are 1.28 and 0.73 nm. The diameter value of DWCNTs from Raman analysis also showed a narrow diameter distribution. Using field emission transmission electron microscopy (TEM), it was found that the diameter of carbon nanotubes can be controlled mainly by adjusting the molar ratio of Co–V versus the MgO support. The structure properties of catalysts were examined by X-ray diffraction (XRD). The formation of C₇V₈ may play an important role in preserving carbon in the catalyst particle and favoring the dissociation balance of CH₄.     

Mechanical and electrical properties of carbon nanotube/poly(phenylene sulphide) composites incorporating polyetherimide and inorganic fullerene-like nanoparticles

The mechanical and electrical properties of single-walled carbon nanotube (SWCNT) reinforced poly(phenylene sulphide) (PPS) composites prepared by melt-extrusion have been evaluated. The wrapping of SWCNTs in polyetherimide (PEI) and the addition of inorganic fullerene-like tungsten disulfide (IF-WS₂) nanoparticles provided an effective method for dispersing the SWCNTs, leading to enhanced properties of the resulting hybrid composites. Mechanical tests demonstrated significant enhancements in stiffness, strength and toughness by the addition of both nanofillers, and the Young’s modulus of the hybrid composites was fairly well predicted by two-phase modelling. The electrical conductivity of PPS improved dramatically at low SWCNT content (0.1-0.5 wt%). At higher concentrations, the replacement of part of the SWCNTs with IF-WS₂ maintained the level of conductivity of the composites. Overall, the hybrids possess superior performance than composites reinforced solely with wrapped or non-wrapped SWCNTs, and their properties can be tailored by modifying the SWCNT/IF-WS₂ ratio.     

Direct‐Patterning SWCNTs Using Dip Pen Nanolithography for SWCNT/Silicon Solar Cells

Dip pen nanolithography (DPN) is used to pattern single‐walled carbon nanotube (SWCNT) lines between the n‐type Si and SWCNT film in SWCNT/Si solar cells. The SWCNT ink composition, loading, and DPN pretreatment are optimized to improve patterning. This improved DPN technique is then used to successfully pattern >1 mm long SWCNT lines consistently. This is a 20‐fold increase in the previously reported direct‐patterning of SWCNT lines using the DPN technique, and demonstrates the scalability of the technique to pattern larger areas. The degree of the uniformity of SWCNTs in these lines is further characterized by Raman spectroscopy and scanning electron microscopy. The patterned SWCNT lines are used as thin conductive pathways in SWCNT/Si solar cells, similar to front contact electrodes. The critical parameters of these solar cells are measured and compared to control cells without SWCNT lines. The addition of SWCNT lines increases power conversion efficiency by 40% (relative). Importantly, the SWCNT lines reduce average series resistance by 44%, and consequently increase average fill factor by 24%.     

Field emission characteristics of an individual carbon nanotube inside a field emission-scanning electron microscope

Field emission (FE) properties of individual single-walled carbon nanotubes (SWCNT) were investigated inside a field emission-scanning electron microscopy. The individual SWCNT turned on a voltage of 23 V defined to produce a current of 10 pA, and was saturated at around 43 V and 880 nA. The FE characteristic of individual SWCNT also followed a conventional Fowler-Nordheim (F-N) theory in which a single linear slope in the F-N plots is measured below their limit of current level corresponding to the saturation regime of emission current. Energy-dispersive X-ray spectroscopy analysis showed that carbon atoms were deposited on the anode surface by the local heating of SWCNT tip during the FE processes and indicated about atomic 83% of carbon atoms. The carbon atoms were newly found to be evaporated and deposited on the anode surface during the FE process such that it was assumed that the degradation of FE was caused by evaporation and deposition of carbon atoms during the FE process.     

Synthesis of carbon nanotubes at low temperature by filament assisted atmospheric CVD and their field emission characteristics

Multiwalled carbon nanotubes (MWNTs) were synthesized using a hot filament assisted chemical vapor deposition (CVD) at the atmospheric pressure at a substrate temperature of 550 °C. The size of nanotubes was controlled by changing the size of catalyst particles. The structure and composition of these nanotubes were investigated using scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The electron field emission current of MWNTs was also measured. It was found that the nanotubes with smaller the diameter had higher the emission current levels though synthesis conditions except catalyst particles were the same. These as-grown MWNTs had emission current densities of 6.5 mA/cm² and 2.5 mA/cm² at 1 V/μm for 5-8 nm and 20 nm size carbon nanotube samples, respectively. The results indicated that the MWNTs synthesized had low emission threshold voltages and high emission current levels that are favorable properties for field emission-based display device applications.     

Sonochemical preparation of silica nanorods for gene delivery using single-walled carbon nanotubes as templates

Silica nanorods were fabricated with single-walled carbon nanotubes (SWCNTs) via ultrasound. The diameter of the resulting SWCNT-silica particles ranged from 60 to 70 nm. The morphology of this composite material was investigated via scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The individual SWCNTs are uniformly coated with silica and formed a unique nanocomposite material. The important role of ultrasound and the mechanism of silica layer formation on SWCNTs were explained via the hydrolysis of the silica source and the adsorption of the siloxane groups on the SWCNT surfaces under ultrasound irradiation. The amino-functionalized silica nanorods were demonstrated as non-viral vectors for gene delivery.     

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.     

Zeolite Nanosheets Stabilize Catalyst Particles to Promote the Growth of Thermodynamically Unfavorable,Small‐Diameter Carbon Nanotubes

A challenge in the synthesis of single‐wall carbon nanotubes (SWCNTs) is the lack of control over the formation and evolution of catalyst nanoparticles and the lack of control over their size or chirality. Here, zeolite MFI nanosheets (MFI‐Ns) are used to keep cobalt (Co) nanoparticles stable during prolonged annealing conditions. Environmental transmission electron microscopy (ETEM) shows that the MFI‐Ns can influence the size and shape of nanoparticles via particle/support registry, which leads to the preferential docking of nanoparticles to four or fewer pores and to the regulation of the SWCNT synthesis products. The resulting SWCNT population exhibits a narrow diameter distribution and SWCNTs of nearly all chiral angles, including sub‐nm zigzag (ZZ) and near‐ZZ tubes. Theoretical simulations reveal that the growth of these unfavorable tubes from unsupported catalysts leads to the rapid encapsulation of catalyst nanoparticles bearing them; their presence in the growth products suggests that the MFI‐Ns prevent nanoparticle encapsulation and prologue ZZ and near‐ZZ SWCNT growth. These results thus present a path forward for controlling nanoparticle formation and evolution, for achieving size‐ and shape‐selectivity at high temperature, and for controlling SWCNT synthesis.     

The Impact of Carbon Nanotube Length and Diameter on their Global Alignment by Dead-End Filtration

Dead-end filtration has proven to effectively prepare macroscopically (3.8 cm²) aligned thin films from solutionbased single-wall carbon nanotubes (SWCNTs). However, to make this technique broadly applicable, the role of SWCNT length and diameter must be understood. To date, most groups report the alignment of unsorted, large diameter (≈1.4 nm) SWCNTs, but systematic studies on their small diameter are rare (≈0.78 nm). In this work, films with an area of A = 3.81 cm² and a thickness of ≈40 nm are prepared from length-sorted fractions comprising of small and large diameter SWCNTs, respectively. The alignment is characterized by cross-polarized microscopy, scanning electron microscopy, absorption and Raman spectroscopy. For the longest fractions (L_avg = 952 nm ± 431 nm, Δ = 1.58 and L_avg = 667 nm ± 246 nm, Δ = 1.55), the 2D order parameter, S2D, values of ≈0.6 and ≈0.76 are reported for the small and large diameter SWCNTs over an area of A = 625 µm², respectively. A comparison of Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory calculations with the aligned domain size is then used to propose a law identifying the required length of a carbon nanotube with a given diameter and zeta potential.     

Comparative analysis of electronic properties of tin,gallium, and bismuth chalcogenide-filled single-walled carbon nanotubes

In the present work, the channels of single-walled carbon nanotubes (SWCNTs) were filled with tin sulfide (SnS), gallium telluride (GaTe), and bismuth selenide (Bi₂Se₃). The successful encapsulation of the compounds was proven by high-resolution transmission electron microscopy. The electronic properties of the filled SWCNTs were studied by optical absorption spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the embedded metal chalcogenides have different influence on the electronic properties of the nanotubes. The incorporation of tin sulfide into the SWCNTs does not result in sufficient changes in the electronic structure of SWCNTs, except for a minor influence on metallic nanotubes. The filling of SWCNTs with gallium telluride causes the charge transfer from the SWCNT walls to the encapsulated compound due to acceptor doping of the nanotubes. The insertion of bismuth selenide inside the SWCNT channels does not lead to the modification of the electronic properties of nanotubes.     

Tailoring the diameter of single-walled carbon nanotubes for optical applications

Single-walled carbon nanotubes (SWCNTs) with specific diameters are required for various applications particularly in electronics and photonics, since the diameter is an essential characteristic determining their electronic and optical properties. In this work, the selective growth of SWCNTs with a certain mean diameter is achieved by the addition of appropriate amounts of CO₂ mixed with the carbon source (CO) into the aerosol (floating catalyst) chemical vapor deposition reactor. The noticeable shift of the peaks in the absorption spectra reveals that the mean diameters of the as-deposited SWCNTs are efficiently altered from 1.2 to 1.9 nm with increasing CO₂ concentration. It is believed that CO₂ acts as an etching agent and can selectively etch small diameter tubes due to their highly curved carbon surfaces. Polymer-free as-deposited SWCNT films with the desired diameters are used as saturable absorbers after stamping onto a highly reflecting Ag-mirror using a simple dry-transfer technique. Sub-picosecond mode-locked fiber laser operations at ∼1.56 μm and ∼2 μm are demonstrated, showing improvements in the performance after the optimization of the SWCNT properties.