Synthesis and characterization of functionalized carbon nanotubes with different wetting behaviors and their influence on the wetting properties of carbon nanotubes/polymethylmethacrylate coatings

The synthesis and characterization of hydrophobic functionalized multi-wall carbon nanotubes (MWCNTs) were investigated and their influence on the wetting properties of organic coatings and composites was studied. Functionalization was performed using oxidation, 1,3-dipolar cycloaddition, and silanization. Silanization was conducted using three hydrophobic silane precursors: 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, and triethoxyoctylsilane. Functionalization was directly confirmed and characterized by Fourier transform infrared spectroscopy, thermal gravimetric analysis, and scanning electron microscopy. The water contact angle of the functionalized MWCNTs was 40–142° for different surface functionalities and the functionalized MWCNTs were incorporated into an acidic solution of polymethylmethacrylate. The effect of surface functionality and the concentration of the functionalized MWCNTs on the wetting properties of these composites were studied by measuring the water contact angle. Under optimum conditions, composite surfaces with water contact angles greater than 110° were obtained. Atomic force microscopy was used to determine the topography of the surface and energy dispersion spectroscopy was used to determine the distribution of the functionalized MWCNTs in the composite film. It was shown that the hydrophobic functionalized MWCNTs migrated to the surface; this was more pronounced for the more hydrophobic MWCNTs.     

Synthesis and characterisation of carbon nanotubes grown on silica fibres by injection CVD

Carbon nanotube grafted primary reinforcing fibres are under development for a new generation of hierarchical composites. Pure and nitrogen-doped multi-walled carbon nanotubes (MWCNTs) were grown on silica fibres using the injection chemical vapour deposition method. The morphology and size of the nanotubes were controlled by varying the growth time. The surface structure of the silica fibres after the grafting process was studied by electron microscopy following focused ion beam sectioning; the images confirmed a base growth mechanism and a shallow iron-rich layer. Thermogravimetric analysis indicated a shorter induction period and a faster growth rate for pure rather than nitrogen-doped MWCNTs. Raman characterisation of the grafted MWCNTs showed a decreasing intensity ratio of the D to G modes, moving from the tip to base in both cases; a detailed comparison of different characteristic Raman ratios is provided, using both the peak intensity and the area for the D, G, and G′ signals.     

Functionalized multi‐wall carbon nanotubes/silicone rubber composite as capacitive humidity sensor

Functionalized multi‐wall carbon nanotubes (MWCNTs) treated by mixed acids have been used to develop a capacitive humidity sensor based on MWCNTs/silicone rubber (SR) composite film. The MWCNTs/SR composites were prepared through conventional solution processed method. The micrographs of MWCNTs/SR composites were observed by transmission electron microscopy (TEM) and scanning electron microscope. The FT‐IR spectra demonstrated the successfully grafting of ? OH groups on the treated MWCNTs. The sensing properties of the composite at different relative humidity (RH) and frequency were characterized and linear sensing responses of the MWCNTs/SR composites to RH were observed. The treated MWCNTs/SR composite film (Tr‐film) had higher sensitivity than that of the untreated MWCNTs/SR composite film (Un‐film). Experimental data indicate that the Tr‐film exhibits an excellent long‐term stability, small hysteresis, and fine reproducibility. The response and recovery time of the Tr‐film were 30 and 27 s, respectively. Thereby, such Tr‐film had potential applications as humidity sensors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40342.     

Multi-walled carbon nanotube/polyimide composite film fabricated through electrophoretic deposition

Multi-walled carbon nanotube (MWCNT)/polyimide composite films were fabricated through electrophoretic deposition (EPD) of MWCNT-polyamic acid colloidal suspension which was derived from carboxylated-MWCNTs and poly(pyromellitic dianhydride-co-4,4′-oxydianiline) (PMDA-ODA). Under electric field, both negatively charged MWCNTs and PMDA-ODA colloid particles migrate onto a positively charged anode simultaneously, and are converted to a coherent MWCNT/polyimide composite film in the ensuing imidization reaction. Uniform dispersion of MWCNTs in the composite film was observed using transmission electron microscopy. The thickness of the prepared composite film can be tuned by varying processing conditions such as deposition time and anode conductivity. The electrical conductivity of the composite film increased with increasing the concentration of MWCNTs in EPD suspension. The mechanical reinforcement of polyimide using MWCNTs was evaluated by tensile testing and nanoindentation testing.     

Functionalization of multi-walled carbon nanotubes with various 4-substituted benzoic acids in mild polyphosphoric acid/phosphorous pentoxide

Functionalization of multi-walled carbon nanotubes (MWCNTs) with various 4-substituted benzoic acids (BAcs) was conducted by using “direct” Friedel-Crafts acylation in mild polyphosphoric acid/phosphorous pentoxide. The degree of functionalization was studied using thermogravimetric analysis, elemental analysis, infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy. The overall evidence indicated that the MWCNTs had remained structurally intact as a result of the reaction. The more reactive BAcs showed that the larger arylcarbonyl moieties were covalently attached onto the surface of MWCNTs. The resultant functionalized MWCNTs (F-MWCNTs) formed bundles with average diameters of 40-70 nm depending on the polarity of the surface groups. The diameter dimensions of bundles were closely related to surface polarities of F-MWCNTs. The solubility/dispersibility and thermal properties of F-MWCNTs were also greatly influenced by the nature of the substituted groups.     

Surface modification of multiwalled carbon nanotubes via gliding arc plasma for the reinforcement of polypropylene

To increase the applicability of multiwalled carbon nanotubes (MWCNTs), functional groups were generated on the generally inert surface of MWCNTs using gliding arc (GA) plasma. MWCNTs were modified using plasma polymerization with styrene (St) as monomer. The surface compositional and structural changes that occur on MWCNTs were investigated using FT‐IR, Raman spectroscopy, BET surface area, and elemental analysis. Dispersion of the treated MWCNTs in different solvents was evaluated. Transmission electron microscopy images showed that the plasma‐treated MWCNTs had a better dispersion than the untreated ones in nonpolar solvents. Subsequently, MWCNTs‐reinforced polypropylene (PP) composites were prepared by internal batch mixing with the addition of 1.0 wt % MWCNTs. The morphology of MWCNTs/PP nanocomposites was studied through scanning electron microscopy. Observations of SEM images showed that the plasma‐treated MWCNTs had a better dispersion than the untreated MWCNTs either on the composite fracture surfaces or inside the PP matrix. Moreover, the mechanical tests showed that the tensile strength and elongation at break were improved with the addition of polystyrene‐grafted MWCNTs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of alumina/carbon nanotubes composites by chemical precipitation

Continuous alumina coating on multi-walled carbon nanotubes (MWCNTs) was successfully prepared by a new method of chemical precipitation using aluminum nitrate and ammonia as starting materials. Structure and morphology of the alumina/multi-walled carbon nanotubes (Al₂O₃/MWCNTs) composites were characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), infrared spectra (IR), thermo gravimetric analysis (TG), differential thermal analysis (DTA) and N₂ adsorption–desorption. The results show that polyvinyl alcohol (PVA) modification on the surface of MWCNTs contributes to form continuous alumina coating, γ-Al₂O₃ layers with thickness of 1–3 nm cover the surface of MWCNTs and the original structure of MWCNTs is retained during the coating process.     

Synthesis and third-order nonlinear optical properties of a multiwalled carbon nanotube-organically modified silicate nanohybrid gel glass

We report the synthesis and characterization of multiwalled carbon nanotube (MWCNT)-organically modified silicate (ORMOSIL) nanohybrid gel glass, in which the incorporated MWCNTs are covalently bonded to the silica network. The structural properties of the 3-aminopropyltriethoxysilane functionalized MWCNTs and MWCNT-ORMOSIL nanohybrid gel glass are comprehensively characterized using spectroscopic and electron microscopy techniques. We find that the agglomeration of incorporated MWCNTs is effectively restrained and that the MWCNTs are dispersed homogeneously and individually in the gel glass matrix. Compared with the mother MWCNT suspension, the resultant nanohybrid gel glasses demonstrate sustained nonlinear optical properties at both 532 and 1064 nm laser wavelengths.     

Formation and Yield of Multi-Walled Carbon Nanotubes Synthesized via Chemical Vapour Deposition Routes Using Different Metal-Based Catalysts of FeCoNiAl,CoNiAl and FeNiAl-LDH

Multi-walled carbon nanotubes (MWCNTs) were prepared via chemical vapor deposition (CVD) using a series of different catalysts, derived from FeCoNiAl, CoNiAl and FeNiAl layered double hydroxides (LDHs). Catalyst-active particles were obtained by calcination of LDHs at 800 °C for 5 h. Nitrogen and hexane were used as the carrier gas and carbon source respectively, for preparation of MWCNTs using CVD methods at 800 °C. MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a quartz tube. The materials were subsequently characterized through X-ray diffraction, Fourier transform infrared spectroscopy, surface area analysis, field emission scanning electron microscopy and transmission electron microscopy. It was determined that size and yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs.     

Field emission properties of Cu/multiwalled carbon nanotube composite films fabricated by an electrodeposition technique

Composite films of Cu and multiwalled carbon nanotubes (MWCNTs) were fabricated by an electrodeposition technique, and their field emission properties were examined. Commercially available MWCNTs with various diameters (60–150 nm) were used. The microstructure of the composite films was analyzed by scanning electron microscopy and the field emission properties were measured using a diode-type system. Cu/MWCNT composite films with homogeneous dispersion of MWCNTs were fabricated using each type of MWCNT. Bare MWCNTs were present on the surface of the composite films and the ends of the protruding tips were fixed by the deposited copper matrix. The composite films produced clear emission currents and the corresponding Fowler–Nordheim (F–N) plots showed that these were field emission currents. The turn-on electric field tended to decrease with decreasing MWCNT diameter. A light-emitting device incorporating the Cu/MWCNT composite film as a field emitter was fabricated, and its light-emitting properties were investigated. Light emission with a brightness of around 100 cd m^?2 was observed for approximately 100 h.     

Fabrication of silica nanoparticles on the surface of functionalized multi-walled carbon nanotubes

A method for the preparation of a hybrid material consisting of various size silica nanoparticles attached to multi-walled carbon nanotubes (MWCNTs) is proposed. Poly (acrylic acid) oligomer was first reacted with hydroxyl groups on acid-treated MWCNTs leading to a grafted encapsulation of the MWCNTs. These were subsequently reacted with 3-aminopropyltriethoxysilane (APTES) resulting sub-grafting of APTES on the MWCNTs. Such MWCNTs (siloxane-MWCNTs) were further hydrolyzed to make MWCNTs indirectly bearing Si–OH groups. Finally, a bud-like MWCNT/silica hybrid was obtained by forming a number of silica nanoparticles from Si–OH groups on the surface of MWCNTs by introducing siloxane-MWCNTs into a solution of tetraethyl orthosilicate, ammonia, and ethanol. The average size of the silica nanoparticles on the surface of the MWCNTs could be controlled by adjusting the concentration of ammonia and the reaction time.     

Preparation of an ultraviolet‐curable water‐borne poly(urethane acrylate)/silica dispersion and properties of its hybrid film

An organic–inorganic hybrid material was prepared through the addition of nanometer fumed silica partly modified by dimethyl dichlorosilane into a water‐borne poly(urethane acrylate) (PUA) anionomer. A PUA/silica hybrid film was made via ultraviolet curing. The mechanical properties of the hybrid film were studied. The tensile strength, elongation at break, pendulum hardness and the glass‐transition temperature of the hybrid material increased with increasing content of silica. Scanning electron microscopy showed an asymmetrical distribution of modified silica in PUA. Atomic force microscopy demonstrated that silica particles could make the surface of the film smooth. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1347–1352, 2004     

The effect of silica nanoparticles and carbon nanotubes on the toughness of a thermosetting epoxy polymer

Silica nanoparticles and multiwalled carbon nanotubes (MWCNTs) have been incorporated into an anhydride‐cured epoxy resin to form “hybrid” nanocomposites. A good dispersion of the silica nanoparticles was found to occur, even at relatively high concentrations of the nanoparticles. However, in contrast, the MWCNTs were not so well dispersed but relatively agglomerated. The glass transition temperature of the epoxy polymer was 145°C and was not significantly affected by the addition of the silica nanoparticles or the MWCNTs. The Young's modulus was increased by the addition of the silica nanoparticles, but the addition of up to 0.18 wt % MWCNTs had no further significant effect. The addition of both MWCNTs and silica nanoparticles led to a significant improvement in the fracture toughness of these polymeric nanocomposites. For example, the fracture toughness was increased from 0.69 MPam^1/2 for the unmodified epoxy polymer to 1.03 MPam^1/2 for the hybrid nanocomposite containing both 0.18 wt % MWCNTs and 6.0 wt % silica nanoparticles; the fracture energy was also increased from 133 to 204 J/m². The mechanisms responsible for the enhancements in the measured toughness were identified by observing the fracture surfaces using field‐emission gun scanning electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Evaluation of structural,optical and dielectric properties of MWCNT-BaTiO3/silica ceramic nanocomposites

In this research, MWCNT-BaTiO₃/silica nano-composites were synthesized and analyzed at different MWCNTs loadings (2, 4, 6, and 8% wt). Utilizing the different concentrations of MWCNTs, the optical responses of MWCNT-BaTiO₃/silica nanocomposite were investigated. For this purpose, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy were used. Using the Kramers-Kronig method, the refractive index and dielectric coefficient of MWCNT-BaTiO₃/silica nanocomposites were analyzed. Results clearly revealed that the higher incorporation of MWCNTs in nanocomposites led to more strong responses in the real parts of both refractive index and dielectric coefficient. Finally, the transversal (TO)/longitudinal (LO) phonon frequencies shifted to the blue wavenumbers by decreasing the amount of MWCNTs in MWCNT-BaTiO₃/silica nanocomposite.     

Functionalization of multi-wall carbon nanotubes to reduce the coefficient of the friction and improve the wear resistance of multi-wall carbon nanotube/epoxy composites

Functionalization of multi-wall carbon nanotubes (MWCNTs) was achieved by grafting carboxyl groups and amino groups. Fourier transform infrared spectroscopy was used to detect the changes produced by functional groups on the surface of the MWCNTs. Three different MWCNTs were incorporated into epoxy resin and the friction and wear behavior of MWCNT/epoxy composites was investigated using a M-2000 wear testing machine at different sliding speeds under different applied loads. Scanning electron microscopy was used to observe the worn surfaces of the samples. The results indicated that the functional groups had been grafted on the surface of MWCNTs. Compared with neat epoxy, the composites with MWCNTs showed a lower friction coefficient and wear rate, and the wear rate decreased with the increase of MWCNT loading. Combining epoxy resin with MWCNTs is an efficient method to improve the wear resistance and decrease the coefficient of friction.     

Self-assembling of multi-walled carbon nanotubes on a porous carbon surface by catalyst-free chemical vapor deposition

Synthesis of carbon nanotubes (CNTs) by catalyst-free chemical vapor deposition (CFCVD) is one of the most important challenges in nanotube science. Self-assembling multi-walled CNTs (MWCNTs) were produced on a porous carbon surface using carbon black (CB) as a substrate, at 800 °C by the decomposition of diluted ethylene. MWCNTs with an outer-diameter distribution of 20–80 nm, examined by scanning and transmission electron microscopy, could be self-assembled on pore structures of CB surface by CFCVD.     

Ag nanocrystal as a promoter for carbon nanotube-based room-temperature gas sensors

We have investigated the room-temperature sensing enhancement of Ag nanoparticles (NPs) for multiwalled carbon nanotube (MWCNT)-based gas sensors using electrical measurements, in situ infrared (IR) microspectroscopy, and density functional theory (DFT) calculations. Multiple hybrid nanosensors with structures of MWCNTs/SnO(2)/Ag and MWCNTs/Ag have been synthesized using a process that combines a simple mini-arc plasma with electrostatic force directed assembly, and characterized by electron microscopy techniques. Ag NPs were found to enhance the sensing behavior through the "electronic sensitization" mechanism. In contrast to sensors based on bare MWCNTs and MWCNTs/SnO(2), sensors with Ag NPs show not only higher sensitivity and faster response to NO(2) but also significantly enhanced sensitivity to NH(3). Our DFT calculations indicate that the increased sensitivity to NO(2) is attributed to the formation of a NO(3) complex with oxygen on the Ag surface accompanying a charge rearrangement and a net electron transfer from the hybrid to NO(2). The significant response to NH(3) is predicted to arise because NH(3) is attracted to hollow sites on the oxidized Ag surface with the H atoms pointing towards Ag atoms and electron donation from H to the hybrid sensor.     

Synthesis of mesoporous Si/SiC with three-dimensional structure derived from C/silicalite-1 via magnesiothermic reduction

C/silicalite-1 composites were successfully synthesized by using industrial silica sol as silica source and multiwalled carbon nanotube (MWCNTs) as carbon source under hydrothermal method. Then, C/silicalite-1 composites were transformed into mesoporous Si/SiC through magnesiothermal reduction at relatively low temperature (650 °C). The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and Brunauer–Emmett–Teller analysis (BET). The XRD patterns and TEM micrographs exhibit that C/silicalite-1 composites are transformed into Si/SiC. The SEM images exhibit that Si/SiC keeps the three-dimensional structure of silicalite-1. BET analysis shows that the specific surface areas and mesoporous distribution of Si/SiC are 274 m²/g and 4.69 nm, respectively.     

Functionalization of multi-walled carbon nanotubes with perfluoropolyether peroxide to produce superhydrophobic properties

Multi-walled carbon nanotubes (MWCNTs) have been functionalized through perfluoropolyether (PFPE) radicals obtained by thermal decomposition of linear PFPE peroxide. The reactivity of MWCNTs with PFPE peroxide has been compared with the direct fluorination of MWCNTs using elemental fluorine in mild conditions. The experimental results indicated that the functionalization with PFPE peroxide and the direct fluorination with elemental fluorine were suitable techniques to modify and control the physical-chemical properties of MWCNTs. After the introduction of PFPE chains on the MWCNT surface, the wettability of MWCNTs changed from hydrophilic to superhydrophobic, because the low surface energy properties of PFPE were transferred to the MWCNT surface. However, the linkage of PFPE chains weakly influenced the electrical properties of conductive MWCNTs. The amount of PFPE chains linked to the carbon nanotubes, the PFPE fluids obtained by homocoupling side-reactions and the decomposed portion of PFPE have been evaluated by mass balance. The modified MWCNTs have been characterized by X-ray photoelectron spectroscopy, thermal gravimetric analysis, X-ray diffraction, scanning electron microscopy, contact angle and surface area measurements. The effects of the chemical treatment on the conductive properties of MWCNTs have been studied by resistivity measurements at different applied pressures.     

Dispersion of carbon nanotubes in low pH aqueous solutions by means of alumina-coated silica nanoparticles

A novel noncovalent and inorganic method was used to disperse multiwalled carbon nanotubes (MWCNTs) in aqueous solutions through alumina-coated silica (ACS) nanoparticle halos. MWCNTs were directly dispersed into a highly charged ACS nanoparticle aqueous solution without functionalization of their surfaces. The dispersed MWCNTs were characterized by transmission electron microscopy and atomic force microscopy. Raman spectroscopy of MWCNTs prepared from dispersion in the ACS solution revealed reduced bundling compared to the corresponding untreated MWCNTs. The characteristic Raman peak at about 1570 cm⁻¹, corresponding to the G band, shifted to a higher wavenumber with a narrower peak. It was possible to disperse up to 20 mg/mL of MWCNTs in a 1 wt% ACS nanoparticle aqueous solution at pH 2. This homogeneous MWCNT-ACS aqueous solution was stable for weeks after ultrasonication.