Self-assembly of carbon nanotube films from room temperature ionic liquids

A novel method for the assembly of thin, uniform transparent and conductive films of single-walled carbon nanotubes (SWCNTs) on glass substrates is described. This process involves the initial transfer of a temporary suspension of SWCNTs in room temperature ionic liquid to the surface of water and the subsequent transfer of the SWCNT film onto a glass substrate. The average sheet resistance of the films was determined by four point probe measurements to be 1.52 and 4.13 kΩ/sq, with an average optical transparency of 50% and 63%, respectively.     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

离子液体中制备碳纳米管复合材料的研究

与传统的溶剂相比,离子液体作为一种新型的绿色环保溶剂及优良电解质,在碳纳米管复合材料制备中得到了广泛的应用.对近年来利用离子液体合成出的碳纳米管/金属复合材料、碳纳米管/纤维素复合材料、碳纳米管/聚合物复合材料,以及在高分子离子液体、离子液凝胶中制备的碳纳米管复合材料进行了综述,介绍它们的优势及特点.对今后离子液体在碳...     

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.     

Plasma sprayed graphene/carbon nanotube reinforced lanthanum-cerate hybrid composite coating

Lanthanum cerate (LC: La₂Ce₂O₇) is a potential material for thermal barrier coating, whose improved toughness is a crucial necessity for the pathway of its industrialization. Herein, we demonstrated a promising approach to develop graphene/carbon nanotube hybrid composite coating using a large throughput and atmospheric plasma spraying method. Graphene nanoplatelets (GNP: 1 wt %) and carbon nanotube (CNT: 0.5 wt %) reinforced lanthanum cerate (LCGC) hybrid composite coatings were deposited on the Inconel substrate. Addition of 1 wt % GNP and 0.5 wt % CNT in LC matrix has significantly increased its relative density, hardness, and elastic modulus up to 97.2%, 2–3 folds, 3–4 folds, respectively. An impressive improvement of indentation toughness (8.04 ± 0.2 MPa m^0.5) was observed on LCGC coating, which is ～8 times higher comparing the LC coating. The toughening was attributed to the factors: such as the distribution of GNPs and CNTs in the LC matrix, synergistic toughening offered by the GNPs and CNTs; (i) GNP/CNT pull-out, (ii) crack bridging and arresting, (iii) splat sandwiching, mechanical interlocking, etc. Finally, this improved toughness offered an exceptional thermal shock performance up to 1721 cycles at 1800 °C, without any major failure on the coating. Therefore, the GNP and CNT-reinforced LC hybrid composite coating can be recommended to open a path for turbine industries.     

Effects of nanotube size and roof-layer coating on viscoelastic properties of hybrid diamond-like carbon and carbon nanotube composites

Hybrid carbon nanobuffers are developed by exploiting the ultra-hardness and wear-resistant properties of diamond-like carbon (DLC) coatings and the inherent viscoelasticity properties of vertically aligned carbon nanotubes (VACNTs). The viscoelastic properties of carbon nanobuffers incorporating thin-walled and thick-walled CNTs, respectively, are characterized by means of nanoindentation dynamic mechanical analysis tests. It is shown that the thin-walled nanobuffer has a better damping performance than the thick-walled nanobuffer due to its buckling-driven friction and post-buckling behaviors; particularly under large displacements. In addition, it is shown that under large indenter displacements, the VACNT arrays with DLC coatings display the improved stress distributions and enhanced strain energy dissipation performances due to the load transfer on the top of VACNTs. Molecular dynamics (MD) simulations are performed to investigate the roof-layer effect on damping behavior and structural deformation of the coated and uncoated VACNTs under nanoindentation. The results confirm that the VACNT with a DLC coating exhibits the significantly damping characterizations than the non-coated VACNT. Overall, the results presented in this study reveal the potential for tuning the damping performance of CNT-based nanobuffers through a careful control of the CNT size.     

Multifunctional epoxy composites modified with a graphene nanoplatelet/carbon nanotube hybrid

Epoxies are a class of thermoset polymers which find use in high performance applications. However, epoxies are inherently brittle and are poor conductors of electricity, which limits their ability to be employed in functional applications. Carbon nanomaterials have attracted considerable attention as filler materials, due to their combination of outstanding properties. In the present work, an epoxy polymer was modified with a hybrid nanofiller, consisting of graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs) at a mass ratio of 9:1, using three-roll milling. Addition of 1 wt% resulted in an increase of eight orders of magnitude in the electrical conductivity and a 182% increase in the fracture energy, G_IC, of the epoxy. CNTs contributed greatly in the reduction of the percolation threshold, which was 10 times lower than that of conventional GNP/epoxy composites, while the increase in toughness was entirely attributed to the GNPs, predominantly through the mechanism of crack deflection. The toughening contribution of the hybrid nanofiller was theoretically calculated using analytical modeling, which showed excellent agreement between the predicted and experimental values of G_IC.     

Temperature dependence of oxygen diffusion into polymer/carbon nanotube composite films

This study examines the transport properties of polystyrene (PS)/multiwalled carbon nanotube (MWNT) composite films taking into consideration both MWNT composition and temperature, via fluorescence technique. Three different (3, 15, and 40 wt%) MWNT content films were prepared from PS/MWNT mixtures by annealing them at 170°C, above the glass transition temperature of PS for 10 min. The diffusivity of the PS/MWNT composite was determined by performing oxygen (O₂) diffusion measurements within a temperature range of 24 to 70°C for each film and pyrene (P) was used as the fluorescent probe. The diffusion coefficients (D) of oxygen were determined by the fluorescence quenching method assuming Fickian transport. Results indicated that D values are strongly dependent on both temperature and the MWNT content in the film and it was also observed that D coefficients obey Arrhenius behavior, from which diffusion energies were produced and increased along with increases of MWNT content. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Stresses in diamond-like carbon films

Internal stresses have been measured in diamond-like carbon (DLC) films deposited by d.c. plasma assisted chemical vapor deposition from methane, acetylene, or cyclohexane, and in nitrogen containing DLC films deposited from acetylene, or cyclohexane and nitrogen. The total hydrogen content in the films and the fraction of bound hydrogen have been analyzed by forward recoil elastic scattering and Fourier transform infrared spectroscopy respectively. It was found that in pure DLC films the stresses increase with increasing fraction of unbound hydrogen. The highest compressive stresses were obtained in the films deposited from methane and the lowest stresses in films deposited from cyclohexane. In the nitrogen containing DLC films the stresses decrease with increasing nitrogen content in the films. Stresses as low as 0.22 GPa were obtained in the films deposited from cyclohexane and nitrogen at a ratio of 1/15 in the plasma.     

Enhanced field emission properties of a reduced graphene oxide/carbon nanotube hybrid film

A facile vacuum filtration method for the preparation of hybrid films to achieve superior field emission properties from carbon nanotubes (CNTs) using reduced graphene oxide (rGO) as a bi-functional filler has been proposed. In the hybrid films, CNTs serve as electron emitters, while rGO helps to control the density of the CNT-emitters and reduce electrical resistance of the films. Via controlling volumes of CNTs and rGO dispersions, electron field emission properties of the hybrid films can be easily tailored. Higher weight ratio of rGO:CNT results in better electrical properties and the best field emission property is achieved when a rGO:CNT weight ratio of 1:3 is employed. The hybrid film reveals a significant improvement in field emission properties, as compared with the CNT film without adding rGO. Decreases in sheet resistance, turn-on field, and threshold field are attributed to the formation of extended conjugated network between CNTs and rGO in association with the reduction of screening effect through the optimization of density of CNT-emitters. The concept that rGO can be employed to control the density of CNT emitters will be of special interest for field emission enhancement.     

Solution spinning of cellulose carbon nanotube composites using room temperature ionic liquids

Multiwall carbon nanotube (MWCNT)/cellulose composite fibers were processed from solutions in ethyl methylimidazolium acetate (EMIAc). Rheological percolation in MWCNT/Cellulose/EMIAc solution was observed above 0.01 mass fraction of MWCNT, while electrical percolation in oriented fibers was observed above 0.05 mass fraction of MWCNTs with respect to the weight of the cellulose. Cellulose orientation and crystal size were significantly higher in the composite than in the control cellulose fiber. In addition, in the composite fiber, carbon nanotube orientation was higher than cellulose orientation. At 0.05 mass fraction MWCNT, fiber tensile strength increased by about 25%, strain to failure increased by 100%, and modulus essentially remained unchanged. The composite fibers showed lower thermal shrinkage than the control cellulose fiber. The axial electrical conductivity at 0.1 mass fraction MWCNTs in these oriented fibers was more than 3000 S/m.     

One-pot synthesis of MnO2/graphene/carbon nanotube hybrid by chemical method

A branched hybrid of MnO₂/graphene/carbon nanotube (CNT) is generated in a one-pot reaction process by chemical method. Some ultrathin MnO₂/graphene nanosheets, around 5 nm in thickness, are randomly distributed on the CNT surface. Morphology, phase structure, microstructure and vibrational properties of the hybrid were characterized by field emission scanning electron microscope, X-ray diffractometer, high resolution transmission electron microscope and Raman spectrometer. Elemental distribution of the hybrid was determined by energy dispersive X-ray mapping performed in scanning transmission electron microscope mode. The key factor of the formation mechanism is associated with both redox and oxidation–intercalation reactions. Graphene flakes are partly exfoliated from the surface layers of the CNTs, and the redox reaction between KMnO₄ and hydroxyl groups occurs on both sides of these flakes, resulting in the formation of a MnO₂/graphene/CNT hybrid. Brunauer–Emmett–Teller surface area measurements indicate that the hybrid has over four times the specific surface area of the pristine CNTs.     

Engineering graphene/carbon nanotube hybrid for direct electron transfer of glucose oxidase and glucose biosensor

The graphene/carbon nanotube hybrid was designed and implemented by a deoxygenation process for direct electron transfer of glucose oxidase and glucose biosensor. The procedure was analyzed by transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectra, etc. The strategy of structurally engineering one-dimensional carbon nanotube (CNT) and two-dimensional graphene oxide (GO) presented three benefits: (a) a deoxygenation process between GO and acid-CNT was introduced under strongly alkaline condition; (b) GO prevented the irreversible integration of CNT; and (c) CNT hindered the restacking of GO. The RGO interacted with CNT through the van der Waals forces and π–π stacking interaction. The three-dimensional hybrid not only had a high surface area, but also exhibited a good electronic conductivity. A direct electrochemistry of glucose oxidase was obtained on the nanohybrid modified electrode which showed good response for glucose sensing. This study would provide a facile and green method for the preparation of nanohybrid for a wide range of applications including biosensing, super capacitor, and transparent electrode.     

Electro-generated nickel/carbon nanotube composites in ionic liquid

It is reported, for the first time, that compact nickel-multiwalled carbon nanotube (Ni/MWCNT) composites were successfully electrodeposited in choline chloride/urea based deep eutectic solvent (DES) on a copper substrate. Dispersion stability of MWCNTs is excellent in DES nickel chloride solution therefore electrodeposition of Ni/MWCNT composites was easily achieved. MWCNTs were uniformly distributed in the nickel matrix and gave different morphologies and high surface roughness to the coating. Coating with oxygen-functionalized MWCNTs exhibited higher stability and better corrosion resistance than the coating with pristine MWCNTs.     

Frictional properties of diamond-like carbon, glassy carbon and nitrides with femtosecond-laser-induced nanostructure

This paper reports macro and micro frictional properties of DLC, TiN, CrN films and GC substrate of which surfaces are nanostructured with femtosecond (fs) laser pulses. The friction coefficient μ of the nanostructured surface was measured at a usual load with a ball-on-disk friction test machine. The results have shown that carbon materials of DLC and GC provide lower values of μ than TiN and CrN, and μ of DLC and TiN measured with a hardened steel ball decreases with an increase of the laser pulse energy. On the other hand, μ of nanostructured surfaces of thin films monotonously increases with an increase in laser pulse energy, which was measured with a micro-scratch test at an ultralight load of 1.5 mN utilizing a diamond tip. The friction coefficient of the GC substrate irradiated at a low fluence around the ablation threshold has shown a lower value than that of the non-irradiated surface.     

Preparation of graphene/multi-walled carbon nanotube hybrid and its use as photoanodes of dye-sensitized solar cells

This study employed a solution-based method to prepare a 3-D hybrid material comprising graphene and acid-treated multi-walled carbon nanotubes (MWCNTs). The adsorption of MWCNTs on graphene reduces the π–π interaction between graphene sheets resulting from steric hindrance, providing a subsequent reduction in aggregation. Optimal proportions of MWCNTs to graphene (2:1) enabled the even distribution of individual MWCNTs deposited on the surface of the graphene. The hybrid 3-D material was incorporated within a TiO₂ matrix and used as a working electrode in dye-sensitized solar cells (DSSCs). The hybrid material provides a number of advantages over electrodes formed of either MWCNTs or graphene alone, including a greater degree of dye adsorption and lower levels of charge recombination. In this study, DSSCs incorporating 3-D structured hybrid materials demonstrated a conversion efficiency of 6.11%, which is 31% higher than that of conventional TiO₂-based devices.     

Superhydrophobic carbon nanotube/amorphous carbon nanosphere hybrid film

Fabrication of superhydrophobic surfaces has been widely investigated due to their wide range of applications. Here, synthesis of self-assembled aligned carbon nanotubes (ACNT)/amorphous carbon (a-C) nanosphere hybrid film is reported. Carbon plasma produced by FCVA was used to deposit a-C nanospheres on the ACNT films fabricated by PECVD. The superhydrophobic properties of the surface was investigated by static contact angle (CA) measurement. It is found that the surface morphology of the film which depends on the size of the a-C nanospheres, has a great influence on the hydrophobic properties of the surface. The hydrodynamic properties of the surface is discussed in terms of both Cassie and Wenzel mechanisms. The microstructure of the films is also investigated by XPS and HRTEM. It is shown that the bombardment of the CNTs with high energy carbon ions will damage the crystalline structure of the CNT walls as well.     

Synthesis of three-dimensional carbon nanotube/graphene hybrid materials by a two-step chemical vapor deposition process

A three-dimensional carbon nanotube (CNT)/graphene hybrid material was synthesized by a two-step chemical vapor deposition (CVD) process. Due to the separated CVD processes for graphene and CNTs, the structures of the hybrid materials could be easily controlled. It is revealed that graphene film was tightly connected with one end of the CNT arrays, forming “jellyfish” structures. Moreover, our results indicate that the presence of graphene influenced the precipitation and growth rate of CNTs. The precipitation of CNTs was postponed due to the existence of graphene. However, the average growth rate of CNTs in the graphene region for the whole process was faster than that in the region without graphene.     

The influence of addition of carbon nanotube and graphene platelets on characteristics of carbon/basalt fiber reinforced intra-ply hybrid composites

In this study, effects of addition of carbon nanotubes (CNTs) and graphene platelets (GPLs) on characteristics of carbon/basalt fiber reinforced intra-ply hybrid composites were investigated. The composites were fabricated using vacuum assisted resin infusion molding (VARIM) method in two types including bare and 0.1, 0.5 wt.% of GPL and CNT nanoparticles filled hybrid composites. Fabricated normal and multiscale composites were cut by water jet and mechanical properties of specimens were examined by tensile, flexural, SBS experiments. Therefore, the modulus of elasticity, flexural modulus, tensile and flexural strength and ILSS of bare and multiscale composites were compared. Thermomechanical properties of fabricated composites were evaluated by dynamic mechanic analyze (DMA), thermogravimetric analyze ( TGA) and thermal conductivity (TC) tests and storage modulus, loss modulus, damping ratio, glass transition temperature, weight loss and derivative weight loss were compared in fabricated normal and multiscale composites. Similarly, modal properties of fabricated composites such as natural frequency and damping factor were obtained by vibrational tests and compared in fabricated composites. According to the results, the addition of carbon-based nanoparticles improved the characteristics of carbon/basalt fiber intra-ply hybrid composites. The response of composites was directly proportional to the addition ratio of the carbon-based nanoparticles.