Evaluations of carbon nanotube field emitters for electron microscopy

Brightness of carbon nanotube (CNT) emitters was already reported elsewhere. However, brightness of electron emitter is affected by a virtual source size of the emitter, which strongly depends on electron optical configuration around the emitter. In this work, I-V characteristics and brightness of a CNT emitter are measured under a practical field emission electron gun (e-gun) configuration to investigate availability of CNT for electron microscopy. As a result, it is obtained that an emission area of MWNT is smaller than its tip surface area, and the emission area corresponds to a five-membered-ring with 2nd nearest six-membered-rings on the MWNT cap surface. Reduced brightness of MWNT is measured as at least 2.6×10⁹ A/m² sr V. It is concluded that even a thick MWNT has enough brightness under a practical e-gun electrode configuration and suitable for electron microscopy.     

Electronic properties and field emission of carbon nanotube films treated by hydrogen plasma

Large-scale and very even multi-wall carbon nanotube (MWNT) films have been obtained at room temperature by an electrophoresis deposition technique. The characterization, by means of scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and micro-Raman spectroscopy, shows that the MWNTs with hydrogen-plasma (HP) treatment are covered by onion-like nanolumps, and three-dimensional multiple-way-connected nanotube webs are formed. The electronic property of the treated MWNT film is converted from semiconducting to metallic. The field-emission test indicates that the HP-treated MWNT film has a low threshold of 1.1 V/m (at 0.1 A/cm²), a high emission light spot density of about 10⁵ cm^-2, and a stable and suitable emission current. The conversion mechanism of the treated carbon nanotube structure and the reason for the change of the electronic and field-emission characteristics of the MWNT films are discussed. PACS 81.07.De; 82.33.Xj; 85.45.Db     

Modification of interface structure and contact resistance between a carbon nanotube and a gold electrode by local melting

The electrical connection between a multiwalled carbon nanotube (MWNT) and a gold electrode on applying an electric current was studied by performing in situ transmission electron microscopy observations while simultaneous measuring the bias voltage and the electric current. The tip of the MWNT was brought into contact with the gold surface. When a current density of ∼10⁸ A/cm² flowed through the contact, the gold surface started to melt along the surface of the MWNT tip due to Joule heating. At about twice the current density, a drastic change was observed in the structure of the gold surface in the contact region. This structural change increased the contact area between the MWNT tip and gold, which reduced the electrical contact resistance.     

Polystyrene/multi-wall carbon nanotube composites prepared by suspension polymerization and their electrorheological behavior

Polystyrene and polystyrene/multi-wall carbon nanotube composites, PS/MWNT, with MWNT content up to 1 wt.% were prepared in the form of microspheres through in situ suspension polymerization. The morphology of the fraction of 32–64 μm was examined by SEM and TEM microscopy. On the surface of the spheres the presence of MWNT was not observed. The microspheres intersections showed the structure of aggregates of sintered beads a few micrometers in size with heterogeneous interface. No MWNT material was observed inside the beads; it seemed to be situated in the heterogeneous phase of microspheres. Suspensions of PS/MWNT in silicone oil show electrorheological effect, whose intensity strongly depends on MWNT content in composite microspheres.     

Nonlinear properties of polyurethane-urea/multi-wall carbon nanotube composite films

The third-order nonlinear optical properties of polyurethane-urea/multiwalled carbon nanotube composites (PU/MWNT) films with different MWNT concentrations are investigated by the use of the Z-scan technique at a wavelength of 532 nm with a pulse duration of 8 ns. The results reveal that the nonlinear refraction and absorption coefficients are linearly dependent on the MWNT concentration. The negative nonlinear refraction effect is validated from the closed-aperture Z-scan measurements. We find that PU/MWNT films are promising nonlinear optical materials, and the nonlinear coefficients can be controlled.     

Preparation and electrochemistry of one-dimensional nanostructured MnO2/PPy composite for electrochemical capacitor

One-dimensional nanostructured manganese dioxide/polypyrrole (MnO₂/PPy) composite was prepared by in situ chemical oxidation polymerization of pyrrole in the host of inorganic matrix of MnO₂, using complex of methyl orange (MO)/FeCl₃ as a reactive self-degraded soft-template. The morphology and structure of the composite were characterized by infrared spectroscopy (IR) X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the MnO₂/PPy composite consists of α-MnO₂ and PPy with nanotube-like structure. Electrochemical properties of the composite demonstrated the material showed good electrochemical reversibility after 500 charge-discharge cycles in the potential range of −0.4 to 0.6 V, the tube-like nanocomposite has the potential application in electrochemical capacitor.     

Hot nanotubes: stable heating of individual multiwall carbon nanotubes to 2000 k induced by the field-emission current

Field emission (FE) electron spectroscopy from an individual multiwalled carbon nanotube (MWNT) is used to measure quantitatively stable temperatures at the apex, T(A), of up to 2000 K induced by FE currents approximately 1 microA. The high T(A) is due to Joule heating along the length of the MWNT. These measurements also give directly the resistance of the individual MWNT which is shown to decrease with temperature, and explain the phenomenon of FE-induced light emission which was observed simultaneously. The heating permits thermal desorption of the MWNT and, hence, excellent current stability.     

Synthesis and elevated temperature performance of a polypyrrole-sulfur-multi-walled carbon nanotube composite cathode for lithium sulfur batteries

A sulfur-multi-walled carbon nanotube composite (S/MWCNT) was prepared using a two-step procedure of liquid-phase infiltration and melt diffusion. Polypyrrole (PPy) conductive polymer was coated on the surface of the as-prepared S/MWCNT composite by in situ polymerization of pyrrole monomer to obtain PPy/S/MWCNT composite. The composite materials were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The electrochemical performance of the as-prepared cathode material was investigated at 25, 40, and 70 °C at various rates. It was found that temperature has dual effects on the performance of Li/S cells. Increasing the temperature, on one hand, facilitates the lithium ion transport through the cathode and, on the other hand, leads to faster dissolution of active material into the electrolyte. The PPy coating can effectively trap polysulfides in its porous structure, even at elevated temperatures, leading to the improvement of the discharge capacity, the cycle stability, and the coulombic efficiency. The electrochemical impedance spectroscopy (EIS) results reveal that the PPy coating reduces the formation of passive layer on the cathode surface, even at high temperatures, resulting in a better elevated temperature performance. A high reversible capacity of 945 mAh g^?1 was maintained after 50 cycles for the PPy/S/MWCNT composite at 70 °C at a rate of 0.5 C.     

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%.     

Oxygen Diffusion into Multiwalled Carbon Nanotube Doped Polystrene Latex Films Using Fluorescence Technique

This study examines the oxygen diffusion into polystyrene (PS) latex/multiwalled carbon nanotube (MWNT) nanocomposite films (PS/MWNT) consisting of various amounts of MWNT via steady state fluorescence technique (SSF). PS/MWNT films were prepared from the mixture of MWNT and pyrene (P)-labeled PS latexes at various compositions at room temperature. These films were then annealed at 170 °C above glass transition (T_g) temperature of PS. Fluorescence quenching measurements were performed for each film separately to evaluate the effect of MWNT content on oxygen diffusion. The Stern-Volmer equation for fluorescence quenching is combined with Fick’s law for diffusion to derive the mathematical expressions. Diffusion coefficients (D) were produced and found to be increased from 1.1?×?10^?12 to 41?×?10^?12 cm²s^?1 with increasing MWNT content. This increase was explained via the existence of large amounts of pores in composite films which facilitate oxygen penetration into the structure.     

NMR relaxation rate in metallic carbon nanotubes

NMR relaxation rate, T₁⁻¹, of the metallic carbon nanotube is discussed based on Tomonaga–Luttinger-liquid theory. It is found that the Coulomb interaction leads to increase of (T₁T)⁻¹ by a power law with decreasing temperature, T. The dependence on temperature of (T₁T)⁻¹ in the multi-wall nanotube (MWNT) is shown to be strongly suppressed by existence of the metallic shells in the MWNTs.     

Synthesis and characterization of polycaprolactone-grafted carbon nanotubes via click reaction

Polycaprolactone (PCL) was covalently grafted on the surface of carbon nanotubes by a simple click reaction of propargyl-terminated PCL (propargyl-PCL) and carbon nanotubes (CNTs) containing azide groups (MWNT-N₃). Propargyl-PCL was synthesized by the ring-opening polymerization of ε-caprolactone using propargyl alcohol and stannous octoate. MWNT-N₃ was prepared from MWNT having 2-bromoisobutyryl groups (MWNT-Br) with sodium azide by azidation. The melting temperature of propargyl-PCL was shifted to the high temperature in PCL-grafted MWNT. The thermal stability of PCL-grafted MWNT was enhanced as compared to that of propargyl-PCL. PCL was coated on the surface of MWNT with a high density of PCL chains, which showed good solubility of PCL-grafted MWNT in organic solvents. PCL-grafted MWNT was characterized with FT-IR, ¹H NMR, Raman, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy.     

A fluorescence study for the critical behavior of polymethylmethacrylate doped by multiwalled carbon nanotube (PMMA–MWNT) composite bulk gel systems

Polymethylmethacrylate (PMMA) doped by multiwalled carbon nanotube (MWNT) bulk gels were prepared with different amounts of MWNTs varying in the range between 1 and 20 wt%. Free-radical cross-linking copolymerization of PMMA–MWNT composite bulk gels was characterized by the steady-state fluorescence technique. Ethylene glycol dimethacrylate (EGDM) and pyrene (P _y ) were introduced as cross linker and fluorescence probe, respectively. Changes in the viscosity of the pregel solutions due to glass formation dramatically increased the P _y fluorescent intensities, which were used to study the glass transition of PMMA–MWNT composite gels for various MWNT contents. The fluorescence intensity of P _y is proportional to the average size of the glassy regions below and to the strength of the infinite network above the glass transition point. Observations around the glass transition point show that there are three regimes for MWNT concentration in which the gel fraction exponent, β, and the weight average degree of polymerization exponent, γ, differ drastically from percolation results, given in three dimensions as β=0.41 and γ=1.80.     

Synthesis and Properties of Polyacrylamide-Based Conducting Gels with Enhanced Mechanical Strength

A nanocomposite conducting hydrogel, polyacrylamide/MWNT/clay (abbreviated as PAM/MWNT/clay), prepared through in situ free radical aqueous polymerization and crosslinked by both clay, as a functional physical crosslinker, and N,N′-methylenebisacrylamide (MBA) as a chemical crosslinker, is reported. The morphology of the gels was characterized by scanning electron microscopy (SEM). The mechanical properties and electrical conductivity were also studied. The results show that the prepared hydrogels had the expected chemical components, with a highly porous structure, and the gels also showed high mechanical strength. The mechanical strength and electrical conductivity value increased with increasing content of multi-walled nanotube (MWNT), and decreased with increasing content of water.     

Thermal stability of HfO2 nanotube arrays

Thermal stability of highly ordered hafnium oxide (HfO₂) nanotube arrays prepared through an electrochemical anodization method in the presence of ammonium fluoride is investigated in a temperature range of room temperature to 900 °C in flowing argon atmosphere. The formation of the HfO₂ nanotube arrays was monitored by current density transient characteristics during anodization of hafnium metal foil. Morphologies of the as-grown and post-annealed HfO₂ nanotube arrays were analyzed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Although monoclinic HfO₂ is thermally stable up to 2000 K in bulk, the morphology of HfO₂ nanotube arrays degraded at 900 °C. A detailed X-ray photoelectron spectroscopy (XPS) study revealed that the thermal treatment significantly impacted the composition and the chemical environment of the core elements (Hf and O), as well as F content coming from the electrolyte. Possible reasons for the degradation of the nanotube at high temperature were discussed based on XPS study and possible future improvements have also been suggested. Moreover, dielectric measurements were carried out on both the as-grown amorphous film and 500 °C post-annealed crystalline film. This study will help us to understand the temperature impact on the morphology of nanotube arrays, which is important to its further applications at elevated temperatures.     

Electrical characterization of PVA-based nanocomposite electrolyte nanofibre mats doped with a multiwalled carbon nanotube

An attempt has been made to prepare and characterise ammonium thiocyanate (NH₄SCN) salt and a multiwall carbon nanotube (MWNT)-doped polyvinyl alcohol-based nanofibre mats using an electrospinning process. The X-ray diffraction result shows an improvement in the amorphous nature of composite electrolyte fibre mats with increasing concentrations of the MWNT filler. The DSC behaviour of these nanofibre mat exhibits better thermal response upon dispersal of the filler. Composite electrolyte nanofibre mat doped with 6 wt% MWNT shows optimum conductivity, viz., 5.8?×?10^?4 Scm^?1. The temperature dependence of the bulk electrical conductivity displays a combination of Arrhenius and Vogel–Tammam–Fulcher nature. Dielectric loss studies have also been used to understand the conduction process in the system. Jonscher power law seems to be obeyed during ac conductivity measurements of the fibre mats.     

Electrical properties of multi-walled carbon nanotube/poly(methyl methacrylate) nanocomposite

Multi-walled carbon nanotube (MWNT) nanocomposites with poly(methyl methacrylate) were prepared via both an in situ bulk polymerization and a suspension polymerization using a radical initiator of 2,2-azobisisobutyronitrile (AIBN). Prior to the synthesis, the MWNT was purified in an acidic solution to remove impurities such as metallic catalysts and amorphous carbons. The AIBN induced PMMA was grafted on the MWNT, which was confirmed by a Fourier transform infrared spectrometer (FT-IR). The composite morphology of the MWNT was observed by scanning electron microscopy (SEM). Electrical characteristics were further examined via both a four-probe method and a rotational rheometer equipped with a high voltage generator.     

Novel Nanocomposites of Polypyrrole Doped with Fullerene C60

This paper reports on the structural, thermal, and dielectric properties of polypyrrole/fullerene C₆₀ nanocomposites synthesized by a interfacial polymerization method. Fourier transform infrared (FT-IR) and ultraviolet-visible (UV-vis) analyses clearly indicated the existence of interactions between polypyrrole (PPy) and the fullerene C₆₀ nanoparticles. Thermal analyses indicated that the extrapolated onset degradation temperature (T_deg) of PPy increased with increasing doping level. Scanning electron microscopy (SEM) images showed that the fullerene C₆₀ changed the morphology of PPy. Dielectric analyses showed a temperature dependent dielectric relaxation behavior. The relaxation time of the nanocomposites with high doping levels tended to increase with increasing temperature. This behavior of the polypyrrole/fullerene C₆₀ nanocomposites indicated that they could be used as a high temperature ultrasonic transducer.     

Synthesis,characterization, conductivity and sensor application study of polypyrrole/silver doped nickel oxide nanocomposites

Conducting polymer composites of polypyrrole (PPy) and silver doped nickel oxide (Ag-NiO) nanocomposites were synthesised by in situ polymerisation of pyrrole with different contents of Ag-NiO nanoparticles. The formation of nanocomposites were studied by Fourier transform infrared (FTIR) and UV–vis spectroscopy, field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and AC and DC conductivity measurements. The sensitivity of ammonia gas through the nanocomposite was analysed with respect to different contents of nanoparticles. Spectroscopic studies showed the shift in the absorption bands of polymer nanocomposite than that of pure PPy indicating the strong interaction between the nanoparticles and polymer chain. FESEM revealed the uniform dispersion of nanoparticles with spherically shaped metal oxide particles in PPy matrix. The XRD pattern indicated a decrease in amorphous domain of PPy with increase in loading of nanoparticles. The higher thermal stability and glass transition temperature of polymer nanocomposites than that of pure PPy were revealed from the TGA and DSC respectively. The dielectric properties, DC and AC conductivity of nanocomposites were much higher than PPy and these electrical properties increases with the loading of nanoparticles. The nanocomposites showed an enhancement in sensitivity towards ammonia gas detection than PPy.     

Carbon nanowire made of a long linear carbon chain inserted inside a multiwalled carbon nanotube

A new type of one-dimensional (1D) carbon structure, carbon nanowires (CNWs), was discovered in the cathode deposits prepared by hydrogen arc discharge evaporation of carbon rods. Observation of high-resolution transmission electron microscopy (HRTEM) indicates that a CNW consists of a multiwalled carbon nanotube (MWNT) with a long 1D linear carbon chain (C chain) inserted into its innermost tube of 0.7 nm in diameter. The characteristic Raman peaks of CNWs appeared at around 1850 cm(-1). Raman scattering and HRTEM studies show the formation of a long linear C chain involving more than 100 carbon atoms inside a MWNT. This novel 1D carbon allotrope has potential applications in nanoelectronics, nanomechanics, and nanomaterials.