Pressureless sintering of carbon nanotube–Al2O3 composites

Alumina ceramics reinforced with 1, 3, or 5 vol.% multi-walled carbon nanotubes (CNTs) were densified by pressureless sintering. Commercial CNTs were purified by acid treatment and then dispersed in water at pH 12. The dispersed CNTs were mixed with Al₂O₃ powder, which was also dispersed in water at pH 12. The mixture was freeze dried to prevent segregation by differential sedimentation during solvent evaporation. Cylindrical pellets were formed by uniaxial pressing and then densified by heating in flowing argon. The resulting pellets had relative densities as high as ～99% after sintering at 1500 °C for 2 h. Higher temperatures or longer times resulted in lower densities and weight loss due to degradation of the CNTs by reaction with the Al₂O₃. A CNT/Al₂O₃ composite containing 1 vol.% CNT had a higher flexure strength (～540 MPa) than pure Al₂O₃ densified under similar conditions (～400 MPa). Improved fracture toughness of CNT–Al₂O₃ composites was attributed to CNT pullout. This study has shown, for the first time, that CNT/Al₂O₃ composites can be densified by pressureless sintering without damage to the CNTs.     

Fabrication and characterization of multiwalled carbon nanotube–loaded interconnected porous nanocomposite scaffolds

Novel nanocomposite porous scaffolds based on poly(?-caprolactone) (PCL) and multiwalled carbon nanotubes (MWCNTs) were manufactured by a compression-molding/polymer-leaching approach utilizing cryomilling for homogeneous dispersion of nanotubes and blending of polymers. Addition of MWCNTs to PCL and PCL/polyglycolide (PGA) blends resulted in significant changes to scaffold morphology compared to control samples despite persistent interconnected porosity. Several structures exhibiting rough and nanotextured surfaces were observed. Mean pore sizes were in the range of ～3–5?µm. The nanocomposites presented good mechanical and water uptake properties. The results of this research provide significant insight into a strategy for producing nanocomposite scaffolds with interconnected porosity.     

Densified multiwalled carbon nanotubes–titanium nitride composites with enhanced thermal properties

Densified multiwalled carbon nanotube (MWNT)–TiN composites with various MWNTs contents were successfully obtained through a spark plasma sintering (SPS) method. The thermal conductivity k was found to increase with the MWNT amount and temperature. In the presence of 5 wt% MWNTs, there was a 97% enhancement in k at 703 K compared with that of TiN. The high thermal conductivity of MWNTs, a good interfacial combination and a homogeneous dispersion of MWNTs are key issues to enhance the thermal conductivity of MWNT–TiN composites.     

Fabrication and microwave absorption properties of magnetite nanoparticle–carbon nanotube–hollow carbon fiber composites

Absorbents with “tree-like” structures, which were composed of hollow porous carbon fibers (HPCFs) acting as “trunk” structures, carbon nanotubes (CNTs) as “branch” structures and magnetite (Fe₃O₄) nanoparticles playing the role of “fruit” structures were prepared by chemical vapor deposition technique and chemical reaction. Microwave reflection loss, permittivity and permeability of Fe₃O₄–CNTs–HPCFs composites were investigated in the frequency range of 2–18 GHz. It was proven that prepared absorbents possessed the excellent electromagnetic wave absorbing performances. The bandwidth with a reflection loss less than −15 dB covers a wide frequency range from 10.2 to 18 GHz with the thickness of 1.5–3.0 mm, and the minimum reflection loss is −50.9 dB at 14.03 GHz with a 2.5 mm thick sample layer. Microwave absorbing mechanism of the Fe₃O₄–CNTs–HPCFs composites is concluded as dielectric polarization and the synergetic interactions exist between Fe₃O₄ and CNTs–HPCFs.     

Resistance–temperature dependence in carbon nanotube fibres

The electrical transport of a carbon nanotube assembly is determined by its morphology and composition. These vary with the assembly production processes and post-process treatments applied. Here, we present the study of the electrical – structural dependence of wire like assemblies of carbon nanotubes i.e. carbon nanotube fibres produced via floating catalyst chemical vapour deposition processes. We propose that the analysis of resistance – temperature characteristics of the fibres provides vast amount of information for the assessment of the quality of the fibres and thus the efficacy of fibre production and post-production processes. To aid qualitative and quantitative analysis of the experimental results we propose a new universal model which allows the fitting of experimental data in the full range of temperatures and a straightforward comparison of the recorded characteristics.     

Carbon nanotube–polyaniline composites

The last decade has seen a growing interest in hybrid electrically conducting nanocomposites. This article aims to provide a detailed overview of the present status of research in carbon nanotube–polyaniline (CNT/PANI) composites, from processing to structural and property evaluations. CNT/PANI are synthesized by electrochemical and chemical processing. When chemical methods are used, the main challenge is to obtain processable CNT/PANI in the emeraldine salt (ES) form composites. Stable dispersions of ES–CNT in organic media are prepared using the post doping method, inverse emulsion polymerization, or ex situ polymerizations. On the contrary, stable water dispersions of CNT/ES are prepared using hydrophilization of a preformed CNT/ES composite, direct synthesis of micelle–CNT hybrid templates, interfacial polymerization, covalent functionalization of CNT with a water soluble polymer, or using electrostatic interactions between two oppositely charged ES and CNT aqueous colloids. Moreover, the strategies for the synthesis of ternary CNT/PANI composites incorporating noble metal nanoparticles, metal oxide, or graphene sheets are also presented and analyzed in depth. Finally, we give a review of potential applications, including chemical sensors, capacitors, fuel cells and electronic devices.     

Toughened carbon nanotube–iron–mullite composites prepared by spark plasma sintering

Carbon nanotube–iron–mullite nanocomposite powders were prepared by a direct method involving a reduction in H₂–CH₄ and without any mechanical mixing step. The carbon nanotubes are mostly double- and few-walled (3–6 walls). Some carbon nanofibers are also observed. The materials were consolidated by spark plasma sintering. Their electrical conductivity is 2.4 S/cm whereas pure mullite is insulating. There is no increase in fracture strength, but the SENB toughness is twice than the one for unreinforced mullite (3.3 vs. 1.6 MPa m^1/2). The mechanisms of carbon nanotube bundle pullout and large-scale crack-bridging have been evidenced.     

Zn based nanoparticle–carbon nanotube hybrid materials: Interaction and charge transfer

The interaction and charge transfer between Zn-based nanoparticles (NPs) and carbon nanotubes (CNTs) is investigated by X-ray Auger and photoelectron spectroscopy. Charge transfer from Zn NPs toward the CNTs is demonstrated by the presence of an additional feature revealed in the C 1s spectrum of CNTs. This charge transfer was found to vanish after thermal oxidation due to the transformation of the metal Zn into ZnO. Photoluminescence (PL) spectroscopy shows that in the samples ZnO(Nps)/CNTs the PL intensity is quenched.     

In situ formation of noble metal nanoparticles on multiwalled carbon nanotubes and its implication in metal–nanotube interactions

A simple method to decorate multiwalled carbon nanotubes (MWCNTs) with Au, Ag and Cu nanoparticles is illustrated. The method consists in directly depositing the selected metals by thermal evaporation on the carbon nanotubes. Comparative measurements carried out on samples that differ in the quantity and type of the deposited metal, reveal that isolated discrete particles form on the nanotube outer wall for all three metals. The CNT-based composites have been investigated by scanning and transmission electron microscopy to determine the size, shape and distribution of the nanoparticles. The results indicate that the quantity of evaporated metal only affects the nanoparticle size and not the average particle density. Particle composition was determined by X-ray photoelectron spectroscopy study. The results are discussed in terms of metal nanoparticle–tube interactions, an important issue for the fundamental and practical applications of similar MWCNT based composites.     

Electrical transport in metal–carbon hybrid multijunction devices

Understanding the factors that influence the structural, mechanical and electrical properties of hybrid metal–carbon multilayer materials and devices are explored in this study by examining the effects of the choice of metal, Cu or Ti, and the number of metal–carbon bilayers. With up to four bilayers, corresponding to ten discrete metal–carbon electrical junctions, lower interfacial stresses and lower electrical resistance are always found in Cu multilayer structures, when compared with Ti containing multilayers. The lower electrical resistance is a result of a copper–carbon interaction which facilitates a carbon sp³ to sp² bonding transformation and is accompanied by a metal-induced transformation of the carbon layer from an amorphous to nanostructured morphology which also aids in conduction. Time-of-flight secondary ion mass spectrometry measurements demonstrate that the two selected metals, Cu and Ti, represent extreme examples in their affinity to bond with carbon with Cu (Ti) representing a weak (strong) affinity metal for bonding. This study shows the importance of the metal–carbon interaction in understanding the mechanical stresses and electrical characteristics in particular, and the wider result of the role played by the relative chemical reactivity of the components in multijunction hybrid semiconductor-based devices in general.     

Sol-gel derived TiO2–carbon composites with adsorption-enhanced photocatalytic activity and gas sensing performance

We report the in-situ sol-gel synthesis of TiO₂–carbon composites (black TiO₂) by carbonization of the gel. With ultra-fine anatase TiO₂ nanoparticles dispersed homogeneously on amorphous carbon, the as-prepared black TiO₂ possesses a BET surface area as high as 145.4 m²/g. Due to the synergy effect of adsorption and photocatalysis, the as-synthesized black TiO₂ is demonstrated to exhibit enhanced photocatalytic activity. The gas sensing properties of black TiO₂ have been rigorously investigated with and without UV illumination at room temperature. It is found that increased adsorption of gas molecules can effectively improve the sensor response. The mechanism of the adsorption-enhanced gas sensing performance of black TiO₂ has been detailedly discussed.     

Electrophoretic deposition of carbon nanotube–ceramic nanocomposites

The purpose of this paper is to present an up-to-date comprehensive overview of current research progress in the development of carbon nanotube (CNT)–ceramic nanocomposites by electrophoretic deposition (EPD). Micron-sized and nanoscale ceramic particles have been combined with CNTs, both multiwalled and single-walled, using EPD for a variety of functional, structural and biomedical applications. Systems reviewed include SiO₂/CNT, TiO₂/CNT, MnO₂/CNT, Fe₃O₄/CNT, hydroxyapatite (HA)/CNT and bioactive glass/CNT. EPD has been shown to be a very convenient method to manipulate and arrange CNTs from well dispersed suspensions onto conductive substrates. CNT–ceramic composite layers of thickness in the range <1–50 μm have been produced. Sequential EPD of layered nanocomposites as well as electrophoretic co-deposition from diphasic suspensions have been investigated. A critical step for the success of EPD is the prior functionalization of CNTs, usually by their treatment in acid solutions, in order to create functional groups on CNT surfaces so that they can be dispersed uniformly in solvents, for example water or organic media. The preparation and characterisation of stable CNT and CNT/ceramic particle suspensions as well as relevant EPD mechanisms are discussed. Key processing stages, including functionalization of CNTs, tailoring zeta potential of CNTs and ceramic particles in suspension as well as specific EPD parameters, such as deposition voltage and time, are discussed in terms of their influence on the quality of the developed CNT/ceramic nanocomposites. The analysis of the literature confirms that EPD is the technique of choice for the development of complex CNT–ceramic nanocomposite layers and coatings of high structural homogeneity and reproducible properties. Potential and realised applications of the resulting CNT–ceramic composite coatings are highlighted, including fuel cell and supercapacitor electrodes, field emission devices, bioelectrodes, photocatalytic films, sensors as well as a wide range of functional, structural and bioactive coatings.     

Hybrid peptide–carbon nanotube dispersions and hydrogels

Scanning probe microscopy (SPM) techniques based on nano-mechanical measurements (topography, adhesion, modulus) and electric force microscopy (EFM) have been used to examine mica surfaces modified with the ionic-complementary peptide EFK8 alone and with EFK8–single-walled carbon nanotube (SWNT) dispersions in water in order to gain a deeper understanding of the interaction between nanotubes and ionic-complementary peptides. Through the use of these techniques, it has been shown for the first time that peptide fibers can be distinguished from SWNTs and peptide-wrapped SWNTs. SPM images reveal features consistent with two types of helical structures: EFK8 fibers wrapped around each other during self-assembly and EFK8 fibers wrapped around SWNTs. In this second structure, EFK8 chains should be oriented with their hydrophobic sides oriented toward the SWNTs and their hydrophilic sides toward the water, thereby enabling the dispersion of the nanotubes in aqueous media. We have also demonstrated the formation of hybrid EFK8–SWNT hydrogels that have potentially superior physical and mechanical properties over those of other hydrogels and opens up new applications for this type of material. To the best of our knowledge, this is the first work reporting the formation of a composite hydrogel made of an ionic-complementary peptide and carbon nanotubes.     

TaB2–SiC–Si multiphase oxidation protective coating for SiC-coated carbon/carbon composites

To improve the oxidation resistance of the carbon/carbon (C/C) composites, a TaB₂–SiC–Si multiphase oxidation protective ceramic coating was prepared on the surface of SiC coated C/C composites by pack cementation. Results showed that the outer multiphase coating was mainly composed of TaB₂, SiC and Si. The multilayer coating is about 200 μm in thickness, which has no penetration crack or big hole. The coating could protect C/C from oxidation for 300 h with only 0.26 × 10^?2 g²/cm² mass loss at 1773 K in air. The formed silicate glass layer containing SiO₂ and tantalum oxides can not only seal the defects in the coating, but also reduce oxygen diffusion rates, thus improving the oxidation resistance.     

Hot pressed hydroxyapatite–carbon fibre composites

Composite samples were obtained from hydroxyapatite powder and carbon fibres by hot pressing at 1100°C and 25 MPa for 15 min in argon atmosphere. Two types of cut carbon fibres produced in a carbonisation process of polyacrylonitrile (PAN) precursor were used both in non-coated or coated form. The coatings of calcium phosphate were applied by sol–gel technique. The highly sintered composite with the best strength properties was obtained from coated carbon fibres with basic character of the surface. The existence of hydroxyl groups on fibre surface makes possible formation of bonds with the calcium phosphate layer formed as a result of polycondensation following the sol–gel procedure.     

Ablation behavior of ZrB2–SiC protective coating for carbon/carbon composites

Ablation behavior of ZrB₂–SiC protective coating for carbon/carbon composites during oxyacetylene flame test at 2500 °C was investigated by analyzing the microstructure differentiation caused by the increasing intensity of ablation from the border to the center of the surface. After ablation, a continuous SiO₂ scale, a porous SiO₂ layer inlaid with fine ZrO₂ nuclei, and a continuous ZrO₂ scale respectively emerged in the border region, the transitional region, and the center region. In order to investigate the ablation microstructure in the initial stage, the sub-layer microstructure was characterized and found to be mainly formed by coral-like structures of ZrO₂, which showed huge difference with the continuous structure of ZrO₂ on the surface layer. A kinetic model concerning the thickness change induced by volatilization and oxidation during ablation was built to explain the different growth mechanisms of the continuous ZrO₂ scale and the coral-like ZrO₂ structure.     

Dielectric relaxation properties of PbTiO3-multiwalled carbon nanotube composites prepared by a sol–gel process

Dielectric composites fabricated by combining multi-walled carbon nanotubes (MWCNT) and PbTiO₃ (PTO) powder were prepared using a sol–gel process. Well-dispersed PTO powder with various volume ratios of MWCNT was compressed to form a pellet, and then silver electrodes were coated on both sides for electrical measurements. The PTO–MWCNT composite with 0.4 vol% MWCNT showed the highest dielectric constant (912 at 1 kHz), which is approximately 25 times larger than that (37 at 1 kHz) of a pure PbTiO₃ pellet. Furthermore, a strong frequency dependence of the dielectric constant in the low frequency range was shown for the PTO–MWCNT composites. Interfacial effects related to dielectric relaxation in composite materials were used to explain an observed increase of the dielectric constant near the percolation threshold.     

Continuous electrodeposition of polypyrrole on carbon nanotube–carbon fiber hybrids as a protective treatment against nanotube dispersion

This paper describes the electrodeposition of nanometer size polypyrrole layers on carbon fibers coated with multi-wall carbon nanotubes. The obtained carbon nanotubes–carbon fiber hybrids are characterized by electrochemistry, electron microscopy, vibrational spectroscopy and thermogravimetry. The electrical properties are measured for various polymerization times and electrolytes. The conductivity is found decrease with increasing polypyrrole thickness, but all the carbon nanotube–carbon fiber hybrids remain more conductive than pristine carbon fibers having a sizing coating. Finally it is shown that polypyrrole acts as a protecting layer against carbon nanotube dispersion when sonicated in ethanol.     

High strength micron size carbon fibers from polyacrylonitrile–carbon nanotube precursors

An improved, high strength, carbon fiber derived from islands-in-a-sea bi-component gel spun polyacrylonitrile (PAN)–carbon nanotube (CNT) precursor fibers containing 1 wt% mixture of single, double, and few walled CNTs was developed. Microscale experiments with properly designed MEMS tools provided the mechanical properties of individual, 1-μm diameter carbon filaments, which were isolated from bundles of 407 fibers. The statistics of the mechanical strength were described well by the cumulative Weibull probability density function that resulted in characteristic strength of 6.2 GPa and a Weibull modulus of 4.5, while the highest tensile strength and Young’s modulus values were 7.3 GPa and 318 GPa, respectively. At the lower end of the spectrum, the strength values correlated well with predictions based on an effective flaw size obtained from fracture cross-sections. On the other hand, the failure cross-sections of the high strength carbon fibers contained a large number of long and oriented CNTs but no discernible flaws. The high interfacial strength between the CNTs and the surrounding carbon resulted in fracture and telescopic pull-out of the CNTs, which was corroborated by individual CNT pull-out experiments with MEMS tools inside an SEM, and in situ fiber failure observations of telescopic pull-out of CNTs inside a TEM.     

Functional polymer–polymer/carbon nanotube bi-component fibers

Bi-component fibers typically combine multiple functions that arise from at least two distinct components. As a result, these fibers can incorporate carbon nanotubes, which impart specific and controllable mechanical, electrical, and thermal transport properties to the fibers. Using gel spinning, sheath-core polyacrylonitrile–polyacrylonitrile/carbon nanotube bi-component fibers with a diameter of less than 20 μm and carbon nanotube concentrations of up to 10 wt% were produced. In these fibers, the carbon nanotubes were well dispersed and aligned along the fiber axis. The fibers exhibited a tensile strength as high as 700 MPa, and a tensile modulus as high as 20 GPa, as well as enhanced electrical and thermal conductivities when compared to the fibers without carbon nanotubes.