Reactor scale modeling of multi-walled carbon nanotube growth

As the mechanisms of carbon nanotube (CNT) growth becomes known, it becomes important to understand how to implement this knowledge into reactor scale models to optimize CNT growth. In past work, we have reported fundamental mechanisms and competing deposition regimes that dictate single wall carbon nanotube growth. In this study, we will further explore the growth of carbon nanotubes with multiple walls. A tube flow chemical vapor deposition reactor is simulated using the commercial software package COMSOL, and considered the growth of single- and multi-walled carbon nanotubes. It was found that the limiting reaction processes for multi-walled carbon nanotubes change at different temperatures than the single walled carbon nanotubes and it was shown that the reactions directly governing CNT growth are a limiting process over certain parameters. This work shows that the optimum conditions for CNT growth are dependent on temperature, chemical concentration, and the number of nanotube walls. Optimal reactor conditions have been identified as defined by (1) a critical inlet methane concentration that results in hydrogen abstraction limited versus hydrocarbon adsorption limited reaction kinetic regime, and (2) activation energy of reaction for a given reactor temperature and inlet methane concentration. Successful optimization of a CNT growth processes requires taking all of those variables into account.     

Investigation of the Morphological and Mechanical Properties of Polyethylene Terephthalate (PET)/Ethylene Propylene Diene Rubber (EPDM) Blends in the Presence of Multi-Walled Carbon Nanotubes

In this study the blends of polyethylene terephthalate (PET)/ethylene propylene diene rubber (EPDM) in the presence of multi-walled carbon nanotubes (MWCNT) (1 and 3?wt %) were prepared by melt compounding in an internal mixer. Mechanical and morphological properties of the nanocomposites were investigated. The thermal behaviors of the PET/EPDM nanocomposites were also investigated, by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results of the mechanical tests showed that the tensile strength, elastic modulus and the hardness of the blends were increased with increasing CNT, while the impact strength and elongation at break decreased. The DSC and TGA results showed an increase of melting temperature (T_m) and degradation temperature of the nanocomposites with the addition of the carbon nanotubes, because the carbon nanotubes serve both as nucleating agents to increase T_m and prevent the composite from degradation to increase the thermal stability. The microstructure of the composites was evaluated through field emission scanning electron microscopy (FESEM) and the results showed a good distribution of the MWCNT within the polymer blend.     

Electrical, dielectric and surface wetting properties of multi-walled carbon nanotubes/nylon-6 nanocomposites

This paper reports that the multi-walled carbon nanotubes(MWCNT)/nylon-6 (PA6) nanocomposites with different MWCNT loadingshave been prepared by a simple melt-compounding method. Theelectrical, dielectric, and surface wetting properties of theCNT/PA6 composites have been studied. The temperature dependence ofthe conductivity of the CNT/PA6 composite with 10.0 wt{\%} CNTloading ($\sigma _{\rm RT} \sim 10^{-4}$ S/cm) are measured, andafterwards a charge-energy-limited tunnelling model (ln $\sigma (T)\sim T^{-1/2})$ is found. With increasing CNT weight percentage from0.0 to 10.0 wt%, the dielectric constant of the CNT/PA6composites enhances and the dielectric loss tangent increases twoorders of magnitude. In addition, water contact angles of theCNT/PA6 composites increase and the composites with CNT loadinglarger than 2.0 wt%even become hydrophobic. The obtainedresults indicate that the electrical and surface properties of thecomposites have been significantly enhanced by the embedded carbonnanotubes.     

Highly selective growth of vertically aligned double‐walled carbon nanotubes by a controlled heating method and their electric double‐layer capacitor properties

Vertically aligned double‐walled carbon nanotubes (DWCNTs) with the highest selectivity of 90% were synthesized by a controlled heating method and their electric double‐layer capacitor characteristics were evaluated. DWCNT arrays had a specific capacitance of 83 F/g, which is one of the highest values among CNT arrays in a nonaqueous solution and is almost equivalent to that for single‐walled CNT (SWCNT) arrays reported previously. At the same specific capacitance, DWCNTs with superior structural properties are more promising for practical capacitors than SWCNTs. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Production and characterization of polymer nanocomposite with aligned single wall carbon nanotubes

We reported a simple method to fabricate polymer nanocomposites with single-walled carbon nanotubes (SWNTs) having exceptional alignment and improved mechanical properties. The composite films were fabricated by casting a suspension of single walled carbon nanotubes in a solution of thermoplastic polyurethane and tetrahydrofuran. The orientation as well as dispersion of nanotubes was determined by scanning electron microscopy, transmission electron microscopy and polarized Raman spectroscopy. The macroscopic alignment probably results from solvent-polymer interaction induced orientation of soft segment chain during swelling and moisture curing. The tensile behavior of the aligned nanotube composite film was also studied. At a 0.5 wt.% nanotube loading, a 1.9-fold increase in Young's modulus was achieved.     

Morphology, mechanical, cross-linking, thermal, and tribological properties of nitrile and hydrogenated nitrile rubber/multi-walled carbon nanotubes composites prepared by melt compounding: The effect of acrylonitrile content and hydrogenation

The purpose of this work was to prepare nanocomposites by mixing multi-walled carbon nanotubes (MWCNT) with nitrile and hydrogenated nitrile elastomers (NBR and HNBR). Utilization of transmission electronic microscopy (TEM), scanning electron microscopy (SEM), and small- and wide-angle X-ray scattering techniques (SAXS and WAXS) for advanced morphology observation of conducting filler-reinforced nitrile and hydrogenated nitrile rubber composites is reported. Principal results were increases in hardness (maximally 97 Shore, type A), elastic modulus (maximally 981 MPa), tensile strength (maximally 27.7 MPa), elongation at break (maximally 216%), cross-link density (maximally 7.94 × 10²⁸ m⁻³), density (maximally 1.16 g cm⁻³), and tear strength (11.2 kN m⁻¹), which were clearly visible at particular acrylonitrile contents both for unhydrogenated and hydrogenated polymers due to enhanced distribution of carbon nanotubes (CNT) and their aggregated particles in the applied rubber matrix. Conclusion was that multi-walled carbon nanotubes improved the performance of nitrile and hydrogenated nitrile rubber nanocomposites prepared by melt compounding.     

Influences of Carbon Nanotube Networking on the Conductive,Crystallization, and Thermal Expansion Behaviors of PA610-Based Nanocomposites

The electrical, crystallization and thermal expansion behaviors of polyamide 610 (PA610)/multi-walled carbon nanotube (CNT) nanocomposites prepared by melt mixing were investigated. Electron microscopy (Scanning Electron Microscopy and Transmission Electron Microscopy) revealed that a good dispersion of CNT and CNT network was obtained in the PA610 matrix. Addition of CNT to PA610 matrix led to polymer nanocomposites exhibiting higher electrical conductivity and lower thermal expansion. The network of CNT in the PA610 matrix, which can be tuned by the loading of CNT and the melt isothermal treatment, was found to play an important role in reducing thermal expansion and achieving higher conductivity. Furthermore, it was shown that significant reduction in thermal expansion in PA610/CNT nanocomposites was due to both thermally insensitive CNT and formation of CNT network.     

Synthesis of anatase titania-carbon nanotubes nanocomposites with enhanced photocatalytic activity through a nanocoating-hydrothermal process

Anatase TiO₂ nanoparticles were covalently anchored onto acid-treated multi-walled carbon nanotubes (MWNTs) through a nanocoating-hydrothermal process to obtain TiO₂-MWNTs nanocomposites. The composition and structural properties of the nanocomposites were characterized by XRD, BET, TG, TEM, HRTEM, EDX, XPS, and FTIR, and the formation of ester-bond linkage between TiO₂ nanoparticles and MWNTs was demonstrated. The enhanced photocatalytic activity of TiO₂-MWNTs nanocomposites was probed by photodegradation reaction of methylene blue under visible-light irradiation.     

Rheological and Mechanical Characterization of Multi-Walled Carbon Nanotubes/Polypropylene Nanocomposites

The rheology and morphology of multi-walled carbon nanotube (MWNT)/polypropylene (PP) nanocomposites prepared via melt blending was investigated. The minor phase content of MWNT varied between 0.25 and 8 wt%. From morphological studies using a scanning electron microscopy technique a good dispersion of carbon nanotubes in the PP matrix was observed. The rheological studies were performed by a capillary rheometer, and mechanical properties of the nanocomposites were studied using a tensile and flexural tester. Both PP and its nanocomposites showed non-Newtonian behavior. At low shear rates the addition of MWNT content causes an increase in viscosity; however, viscosity is less sensitive to addition of MWNT content at higher shear rates. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. From this calculation it was concluded that the temperature sensitivity of nanocomposites was increased by increasing of nanotube content. An increase in tensile and flexural moduli and Izod impact strength was also observed by increasing the MWNT content. From rheological and mechanical tests it was concluded that the mechanical and rheological percolation threshold is at 1.5 wt%.     

Effect of carbon nanotubes dispersion on morphology, internal structure and thermal stability of electrospun poly(vinyl alcohol)/carbon nanotubes nanofibers

The current work reports the effect of multi walled carbon nanotubes and single walled carbon nanotubes dispersion on morphological, structural and thermal degradation of electrospun poly(vinyl alcohol) (PVA)/carbon nanotubes (CNTs) dispersed in sodium dodecyl sulfate (SDS) (PVA/CNTs–SDS) composites nanofibers. (PVA/CNTs–SDS) nanocomposites fibers were elaborated using the traditional electrospinning process to disperse and align CNTs into the fibers, especially for low CNTs loading fraction: 0.3 and 0.7 wt%. The morphology of the electrospun fibers was studied using the scanning electronic microscopy. The average diameter of the fibers changes significantly after the incorporation of the CNTs in the PVA. Furthermore, Fourier transform infrared spectroscopy elucidated the effect of CNTs on the crystallization of the PVA which was confirmed by X-ray diffraction analysis. Thermogravimetric analysis showed that the thermal stability of the composite fibers depends on the loading fraction and on the type of carbon nanotubes.     

Comparison of different types of polypyrimidine/CNTs/Pt hybrids in fuel cell catalysis

In this paper, we mainly studied the preparation of platinum-containing composite materials with carbon nanotubes wrapped by polypyrimidine-conjugated polymers and the performance of the composites. The polymer-based carbon nanotubes/Pt catalysts were prepared successfully and confirmed by infrared spectroscopy, XPS, XRD, and TEM images. The performance of polypyrimidine/multi-walled carbon nanotubes (MWCNTs)/Pt and polypyrimidine/double-walled carbon nanotubes (DWCNTs)/Pt was compared with the polypyrimidine/single-walled carbon nanotubes (SWCNTs)/Pt. The amount of the loaded Pt on the polypyrimidine/MWCNTs and polypyrimidine/DWCNTs was calculated to be 50.5 wt% and 52.7 wt% respectively. The effective specific surface area of the polypyrimidine/MWCNTs/Pt (45.7 m²/g) and polypyrimidine/DWCNTs/Pt (42.47 m²/g) was observed by electrochemical cyclic voltammetry. These studies strongly imply that the MWCNTs were better candidates than DWCNTs and SWCNTs in the application of polypyrimidine/CNT materials as catalyst for fuel cells.     

A comparison of the mechanical strength and stiffness of MWNT-PMMA and MWNT-epoxy nanocomposites

The surface of multi-wall carbon nanotubes (MWNTs) was functionalized by covalent linking of long alkyl chains. Such functionalization led to a much better tube dispersion in organic solvents than pristine nanotubes, favored the formation of homogenous nanocomposite films, and yielded good interfacial bonding between the nanotubes and two polymer matrices: a thermo-set (Epon 828/T-403) and a thermoplastic (PMMA). Tensile tests indicated, however, that the reinforcement was greatly affected by the type of polymer matrix used. Relative to pure PMMA, a 32% improvement in tensile modulus and a 28% increase in tensile strength were observed in PMMA-based nanocomposites using 1.0 wt% nanotube filler. Contrasting with this, no improvement in mechanical properties was observed in epoxy-based nanocomposites. The poorer mechanical performance of the latter system can be explained by a decrease of the crosslinking density of the epoxy matrix in the nanocomposites, relative to pure epoxy. Indeed we demonstrate that the presence of nanotubes promotes an increase in the activation energy of the curing reaction in epoxy, and a decrease of the degree of curing.     

Compressive characteristics of single walled carbon nanotube with water interactions investigated by using molecular dynamics simulation

The elastic properties of single walled carbon nanotube (SWCNT) with surrounding water interactions are studied using molecular dynamics simulation technique. The compressive loading characteristic of carbon nanotubes (CNTs) in a fluidic medium such as water is critical for its role in determining the lifetime and stability of CNT based nano-fluidic devices. In this paper, we conducted a comprehensive analysis on the effect of geometry, chirality and density of encapsulated water on the elastic properties of SWCNT. Our studies show that defect density and distribution can strongly impact the compressive resistance of SWCNTs in water. Further studies were conducted on capped SWCNTs with varying densities of encapsulated water, which is necessary to understand the strength of CNT as a potential drug carrier. The results obtained from this paper will help determining the potential applications of CNTs in the field of nano-electromechanical systems (NEMS) such as nano-biological and nano-fluidic devices.     

Probing structural integrity of single walled carbon nanotubes by dynamic and static compression

We report on a first study of single walled carbon nanotubes (SWCNTs) after application of dynamic (shock) compression. The experiments were conducted at 19 GPa and 36 GPa in a recovery assembly. For comparison, an experiment at a static pressure of 36 GPa was performed on the material from the same batch in a diamond anvil cell (DAC). After the high pressure treatment the samples were characterized by Raman spectroscopy and transmission electron microscopy (TEM). After exposure to 19 GPa of shock compression the CNT material exhibited substantial structural damage such as CNT wall disruption, opening of the tube along its axis (“unzipping”) and tube shortening (“cutting”). Dynamic compression to 36 GPa resulted in essentially complete CNT destruction whereas at least a fraction of the nanotubes was recovered after 36 GPa of static compression though severely damaged. The results of these shock wave experiments underline the prospect of using SWCNTs as reinforcing units in material WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Enhanced dielectric permittivity in poly (vinylidene) fluoride/multiwalled carbon nanotubes nanocomposite thin films fabricated by pulsed laser deposition

The fabrication of high quality thin films of poly (vinylidene fluoride) embedded with multiwalled carbon nanotubes using pulsed laser deposition technique is reported. The prepared films were characterized for structural, morphology and dielectric properties. The morphology analysis revealed uniform dispersion of multiwalled carbon nanotubes throughout the polymer matrix. X-ray diffraction results suggested that the poly (vinylidene fluoride) film is in amorphous phase while addition of multiwalled carbon nanotubes showed presence of crystalline peaks in the nanocomposites films. It was interesting to note that the nanocomposite films exhibits significant enhancement of the ferroelectric β-phase as evidenced by the X-ray diffraction and Fourier transform infrared spectroscopy results. The dielectric analysis shows a remarkable enhancement in the dielectric permittivity of nanocomposites with lower loss and conductivity level. The results can be attributed to the formation of minicapacitor network and relatively higher percolation threshold in the nanocomposites.     

Thermal transport of oil and polymer composites filled with carbon nanotubes

We studied the thermal transport properties of multi-walled carbon nanotubes (MWNTs) in polymer and oil matrices. The thermal conductivity of the oils and polymers increased linearly when adding tubes. We observe a particularly high increase in the thermal diffusivity of carbon-nanotube-loaded liquid crystal polymers (6×10⁻⁵ cm²/s wt%), which is due to a spontaneous alignment of the MWNTs. Carbon nanotubes increased the thermal conductivity of oil by a factor of three for 20 wt% loading. We found little or no dependence of the thermal enhancement on the specific flavor of multiwall nanotubes used in the composites. Carbon nanotubes are excellent nanoscale fillers for composites in thermal management application.     

Effect of Morphology and Composition of Organic Montmorillonite on the Structure and Properties of Poly(Butylene Terephthalate) Nanocomposites

The morphology and composition of organic montmorillonites are critical for their dispersion in polymer matrixes. In the current study, the pristine montmorillonite (MMT) was first surface modified with silane and then intercalated using two kinds of intercalating agents in supercritical carbon dioxide (scCO₂). The obtained OMMTs with tunable morphology and composition, together with pristine MMT and commercial MMT, were introduced into poly(butylene terephthalate) (PBT) to investigate the MMTs dispersion in the PBT matrix and the final properties of the PBT/MMT nanocomposites. The structure of the different MMTs and their dispersion in the PBT matrix were characterized by SEM and TEM, respectively. The crystallization behavior, storage moduli and loss factors of the PBT/MMT nanocomposites were also investigated.     

Carbon Nanotube/P(VDF-TrFE) Nano-Composite Characterization by Total Reflection X-Ray Fluorescence

In continuation of our research on carbon nanotube/P(VDF-TrFE) nano-composites [1], total x-ray fluorescence (TXRF) is engaged in a novel characterization of these materials regarding their compositions, purities, and structural analysis. Samples such as single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT), P(VDF-TrFE) copolymer, SWCNT/P(VDF-TrFE), and MWCNT/P(VDF-TrFE) were analyzed by TXRF. The synthetic quartz used as a substrate was analyzed as reference material for the TXRF measurements. The ethanol and the dimethylformamide (DMF) used as solvents for carbon nanotubes and copolymers respectively were also analyzed by TXRF to determine whether they have an influence or not on the TXRF of the previous material. The preliminary results showed that single-walled and multi-walled carbon nanotubes prepared by the arc-discharge method contain catalytic particles such as Fe, Co, and Ni used to obtain SWCNT while there were no metal or impurities in MWCNT. The TXRF spectrum of CNT/P(VDFTrFE) showed the same results as we found previously with background due to the P(VDF-TrFE) copolymer scattered signal. __________ Published in Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 700–702, September–October, 2005.     

Photoabsorption and desorption studies on poly-3-hexylthiophene/multi-walled carbon nanotube composite films

Photon stimulated ion desorption (PSID) and Near-edge X-ray absorption fine structure (NEXAFS) studies have been performed on poly-3-hexylthiophene and nanocomposites thin films made of poly-3-hexylthiophene/multi-walled carbon nanotubes (MWNT) filled with iron/iron-oxide. The experiments were performed at the Brazilian Synchrotron Light Source (LNLS) operating in a single-bunch mode following sulphur K-shell photoexcitation and using time-of-flight mass spectrometry for ion analysis. Both PSID mass spectra show great similarity and exhibit desorption of the polymer fragments only. This result seems to be in accordance with previous morphological studies on these materials, which suggested that the nanotubes are highly dispersed and involved by the polymer. Although similar, the spectra present shifts in the direction of greater time-of-flights in the case of the poly-3-hexylthiophene/multi-walled carbon nanotube composite. This behavior may be related to the donation of electronic charge between the polymer matrix and the carbon nanotubes. In both cases, S⁺ desorption seems to be suppressed, which may be due to the hexyl side-chains. Relative desorption ion yield curves have been determined as a function of the photon energy, which reproduced the photoabsorption spectrum. These results are discussed in terms of the indirect XESD (X-ray induced electron stimulated desorption) process.     

Poly(Butylene Terephthalate)/Single Wall Carbon Nanotubes Composite Nanofibers by Electrospinning

Poly(buthylene terephthalate)(PBT)/single wall carbon nanotubes (SWCNTs) composite nanofibers were prepared by electrospinning. The effect of carbon nanotubes on the morphology, crystallization, and mechanical properties of the electrospun composite nanofibers were investigated by SEM, DSC, and tensile testing, respectively. SEM observations indicated that the presence of SWCNTs resulted in finer nanofibers for lower loading; however, a broader distribution, especially for the higher diameter ranges was found for nanofibers with higher amounts of carbon nanotubes. SWCNTs accelerated crystallization and acted as a nucleating agent; the degree of crystallinity increased with increasing content of SWCNTs, followed by a moderate decrease at higher content. Specific tensile strength and modulus of the PBT/SWCNTs composite nanofibers mats were higher than that of neat PBT nanofibers mat. However, the elongation at break of composite nanofibers mats was lower than that of the neat PBT nanofibers mat.