Production and characterization of polymer nanocomposites with highly aligned single-walled carbon nanotubes

We report the production and characterization of polymer nanocomposites with single-walled carbon nanotubes having improved mechanical properties and exceptional nanotube alignment. High-pressure carbon monoxide nanotubes (HiPco) were efficiently distributed in polystyrene (PS) and polyethylene (PE) with a twin-screw compounder. Nanotube concentrations were 1, 5, 10, and 20 wt% in PE composites and 0.7 wt% in PS composites. PE composites were melt-spun into fibers to achieve highly aligned nanotubes. Polarized Raman spectroscopy shows that the degree of alignment increases with decreasing fiber diameter and decreases with increasing nanotube loading. The orientation distribution function of a 1 wt% HiPco/PE composite had a full width at half-maximum of approximately 5 degrees. The elastic modulus increases up to 450% relative to PE fibers for 20 wt% nanotube loading at an intermediate fiber diameter of 100 microns.     

A novel approach to fabricate high volume fraction nanocomposites with long aligned carbon nanotubes

Conventional micro-fiber-reinforced composites provide insight into critical structural features needed for obtaining maximum composite strength and stiffness: the reinforcements should be long, well aligned in a unidirectional orientation, and should have a high reinforcement volume fraction. It has long been a challenge for researchers to process CNT composites with such structural features. Here we report a method to quickly produce macroscopic CNT composites with a high volume fraction of millimeter long, well aligned CNTs. Specifically, we use the novel method, shear pressing, to process tall, vertically aligned CNT arrays into dense aligned CNT preforms, which are subsequently processed into composites. Alignment was confirmed through SEM analysis while a CNT volume fraction in the composites was calculated to be 27%, based on thermogravimetric analysis data. Tensile testing of the preforms and composites showed promising mechanical properties with tensile strengths reaching 400 MPa.     

Effect of aligned carbon nanotubes on electrical conductivity behaviour in polycarbonate matrix

This article reports effects of alignment of embedded carbon nanotubes in a polycarbonate polymer matrix under magnetic, direct and alternating current electric fields on the electrical properties of the resulting nanocomposites. Composites consisting of different quantities of carbon nanotubes in a polycarbonate matrix have been prepared using a solution casting technique. The effects of field strength and nanotube concentration on the resulted network structure and conductivity of the composites were studied by in situ optical microscopy, transmission electron microscopy and four-point probe technique. The results showed that the composites prepared in the presence of field had better conductivity than those of as-prepared composites. It was also concluded that the application of alternating current electric field and magnetic field in this system led to the formation of relatively continuing networks while direct current electric field only prevented agglomeration of the carbon nanotubes in the polycarbonate matrix and created relatively uniform distribution of nanotubes in the matrix.     

Reinforcing polyamide 1212 nanocomposites with aligned carbon nanofibers

In this study, the mechanical properties and structure orientation of pure polyamide 1212 (PA1212) were compared with those of PA1212–carbon nanofibers (CNFs) nanocomposites. The tensile strength of the composite containing 0.3 wt.% modified CNFs was improved from 328 MPa (pure PA1212) to 373 MPa after drawing. The reinforcing effect was investigated in terms of crystallization behavior, crystal morphology, alignment of CNFs, and crystal orientation degree. Spherulites developed into oriented crystals after drawing, and the CNFs aligned along the drawing direction. The heterogeneous nucleation effect of the aligned CNFs improved the crystal orientation degree, which produced the reinforcing effect. The oriented fibril structures with rigid nanofibers acting as nuclei reinforced the entire oriented crystals in the composites.     

Biocompatibility of immobilized aligned carbon nanotubes

In vivo host responses to an electrode-like array of aligned carbon nanotubes (ACNTs) embedded within a biopolymer sheet are reported. This biocompatibility study assesses the suitability of immobilized carbon nanotubes for bionic devices. Inflammatory responses and foreign-body histiocytic reactions are not substantially elevated when compared to negative controls following 12 weeks implantation. A fibrous capsule isolates the implanted ACNTs from the surrounding muscle tissue. Filamentous nanotube fragments are engulfed by macrophages, and globular debris is incorporated into the fibrous capsule with no further reaction. Scattered leukocytes are observed, adherent to the ACNT surface. These data indicate that there is a minimal local foreign-body response to immobilized ACNTs, that detached fragments are phagocytosed into an inert material, and that ACNTs do not attract high levels of surface fouling. Collectively, these results suggest that immobilized nanotube structures should be considered for further investigation as bionic components.     

Re-grown aligned carbon nanotubes with improved field emission

In this work, a simple technique to improve the field emission property of multi-walled carbon nanotubes is presented. Re-grown multi-walled carbon nanotubes are grown on the same substrates after the as-grown multi-walled carbon nanotubes are transferred to other substrates using polydimethylsiloxane as intermediation. For the duration of the synthesis of the re-grown multi-walled carbon nanotubes, similar synthesis parameters used in growing the as-grown multi-walled carbon nanotubes are utilized. As a form of possible application, field emission studies show -2.6 times improvement in field enhancement factor and more uniform emission for the re-grown multi-walled carbon nanotubes. In addition, the turn-on field is reduced from 2.85 V/microm to 1.40 V/microm. Such significant improvements are attributed to new emission sites comprising of sharp carbonaceous impurities encompassing both tip and upper portion of the multi-walled carbon nanotubes. As such, this technique presents a viable route for the production of multi-walled carbon nanotubes with better field emission quality.     

Creep behavior of polyurethane nanocomposites with carbon nanotubes

The polyurethane (PU) nanocomposites containing carbon nanotubes (CNTs) were prepared through in situ polymerization for the creep study. The results show that the presence of CNTs leads to a significant improvement of creep resistance of PU. However, this creep resistance does not increase monotonously with increase of CNT contents because it is highly dependent on the dispersion of CNTs. Several theoretical models were then used to establish the relations between CNT dispersion and final creep and creep–recovery behaviors of nanocomposites. The as-obtained viscoelastic and viscoplastic parameters of PU matrix and structural parameters of CNTs further confirmed the retardation effect by CNTs during creep of the nanocomposite systems. Besides, the time–temperature superposition (TTS) principle was also employed in this work to make a further evaluation on the creep of PU/CNT nanocomposites with long-term time scale.     

Controlled two-dimensional pattern of spontaneously aligned carbon nanotubes

We report a simple solution process to form controlled patterns of aligned single-walled carbon nanotubes on solid substrates. The essential step of the process is to deposit a dilute solution of DNA-wrapped carbon nanotubes (DNA-CNTs) on a SiO(2) surface covered with a thin hydrophobic layer. This leads to deposition of fully aligned CNTs. The alignment pattern can be controlled by metal electrodes in the deposition region and can be quantitatively modeled by the behavior of a quasi-two-dimensional DNA-CNT nematic phase near the solution/SiO(2) interface. These results point to the possibility of rational design and economical fabrication of CNT alignment patterns on solid substrates.     

Highly oriented carbon nanotube papers made of aligned carbon nanotubes

Paper-like carbon nanotube (CNT) materials have many important applications such as in catalysts, in filtration, actuators, capacitor or battery electrodes, and so on. Up to now, the most popular way of preparing buckypapers has involved the procedures of dispersion and filtration of a suspension of CNTs. In this work, we present a simple and effective macroscopic manipulation of aligned CNT arrays called 'domino pushing' in the preparation of the aligned thick buckypapers with large areas. This simple method can efficiently ensure that most of the CNTs are well aligned tightly in the buckypaper. The initial measurements indicate that these buckypapers have better performance on thermal and electrical conductance. These buckypapers with controllable structure also have many potential applications, including supercapacitor electrodes.     

High-rate low-temperature growth of vertically aligned carbon nanotubes

We report the low-temperature growth of vertically aligned carbon nanotubes (CNTs) at high growth rates by a photo-thermal chemical vapour deposition (PTCVD) technique using a Ti/Fe bilayer film as the catalyst. The bulk growth temperature of the substrate is as low as 370?°C and the growth rate is up to 1.3 μm min(-1), at least eight times faster than the values reported by traditional thermal CVD methods. Transmission electron microscopy observations reveal that as-grown CNTs are uniformly made of highly crystalline 5-6 graphene shells with an approximately 10 nm outer diameter and a 5-6 nm inner diameter. The low-temperature rapid growth of CNTs is strongly related to the unique top-down heating mode of PTCVD and the use of a Ti/Fe bimetallic solid solution catalyst. The present study will advance the development of CNTs as interconnects in nanoelectronics, through a CMOS-compatible low-temperature deposition method suitable for back-end-of-line processes.     

Study on dispersion and electrical property of multi-walled carbon nanotubes/low-density polyethylene nanocomposites

Sonication is one of the promising approaches to disperse nanoparticles into the base material thoroughly. Furthermore, coupling treatments for MWNTs and polymer matrix also contribute to homogenous dispersion of MWNTs among polymer matrix. In this paper, MWNTs and KH-550 were dispersed with acetone via sonication method, then, the MWNTs/low density polyethylene (LDPE) composites was prepared by using melt blending process. Effects of MWNTs and LDPE coupling treatment on dispersion and electrical property of the MWNTs/LDPE nanocomposites were investigated. SEM observation on fracture surfaces of the nanocomposites explained the functions of sonication and coupling treatment on the dispersion, and electrical conductivity of the nanocomposites was measured by four-contact scheme. The results displayed that the optimum sonication temperature was 70 °C and the optimum sonication amount of MWNTs particles in 200 ml KH-550 acetone solution was 20 g. Moreover, dispersion of the nanocomposites was improved with increasing sonication power amplitude. Furthermore, dispersion and electrical conductivity of the nanocomposites with coupling treatment LDPE were better than those of the nanocomposites with uncoupling treatment LDPE. The good dispersion and electrical conductivity enhancement are based on the strong bonding and coupling reaction of MWNTs and LDPE matrix, which associated greatly with sonication and coupling treatment.     

Interlaminar and intralaminar reinforcement of composite laminates with aligned carbon nanotubes

Three-dimensional reinforcement of woven advanced polymer–matrix composites using aligned carbon nanotubes (CNTs) is explored experimentally and theoretically. Radially-aligned CNTs grown in situ on the surface of fibers in a woven cloth provide significant three-dimensional reinforcement, as measured by Mode I interlaminar fracture testing and tension-bearing experiments. Aligned CNTs bridge the ply interfaces giving enhancement in both initiation and steady-state toughness, improving the already tough system by 76% in steady state (more than 1.5 kJ/m² increase). CNT pull-out on the crack faces is the observed toughening mechanism, and an analytical model is correlated to the experimental fracture data. In the plane of the laminate, aligned CNTs enhance the tension-bearing response with increases of: 19% in bearing stiffness, 9% in critical strength, and 5% in ultimate strength accompanied by a clear change in failure mode from shear-out failure (matrix dominated) without CNTs to tensile fracture (fiber dominated) with CNTs.     

Controllable fabrication of aligned carbon nanotubes by pulsed plasma: selective positioning and electrical transport phenomena

Selective growth of aligned carbon nanotubes (CNTs) at low temperature by pulsed plasma on Si₃N₄/Si substrates patterned by metallic platinum has been demonstrated. Field emission and atomic force microscopy (AFM) have shown that platinum does not support CNT growth, so that nanotubes can selectively grow on substrates patterned by platinum. This feasible fabrication method has been used to measure the electrical resistivity of as-aligned CNT film perpendicular to the tube axis without a complex postsynthesis manipulation. The prepared samples show a monotonic decrease in the resistivity with increasing temperature. We propose that the transport is governed by the formation of crossed junctions of nanotubes in the mat.     

Coherent phonon anisotropy in aligned single-walled carbon nanotubes

By time-resolved reflectivity measurements with sub-10 fs laser pulses at 395 nm, the coherent phonons of aligned bundles of single-walled carbon nanotubes are observed for various polarization directions of the pump and probe pulses. In the isotropic reflectivity measurement, we observe the radial breathing modes, G, and even D modes, while in the anisotropic reflectivity mode, only the G mode appears. A complex polarization dependence of the G band phonon amplitude in the isotropic reflectivity is explained by the superposition of G band phonons with different symmetries.     

Versatile transfer of aligned carbon nanotubes with polydimethylsiloxane as the intermediate

A simple technique to transfer aligned multi-walled carbon nanotubes (MWCNTs) is demonstrated in this work. With polydimethylsiloxane (PDMS) as the transfer medium, as-grown or patterned MWCNT arrays are directly transferred onto a wide variety of Pt-coated substrates such as glossy paper, cloth, polymers, glass slides, and metal foils at low temperatures. The surface of the transferred CNTs is cleaner with better alignment, compared with the as-grown one. Furthermore, the transferred CNTs show strong adhesion and good electric contact with the target substrates. A maximal current density of ～10(4)?A?cm(-2) has been achieved from the CNT interconnects prepared with this technique. Because of the lower density and open-ended structures, improved field emission performance has been obtained from CNTs transferred on polymers, based on which flexible emitter devices can be fabricated. In addition, the surface of transferred CNTs becomes more hydrophilic, with an averaged contact angle of 93.4 ± 5.8°, in contrast to the super-hydrophobic as-grown CNT surface (contact angle 151.6 ± 5.5°). With versatile properties and flexible applications, the technique provides a simple and cost-effective way towards future nanodevices based on CNTs.     

Mesoscale evolution of non-graphitizing pyrolytic carbon in aligned carbon nanotube carbon matrix nanocomposites

Polymer-derived pyrolytic carbons (PyCs) are highly desirable building blocks for high-strength low-density ceramic meta-materials, and reinforcement with nanofibers is of interest to address brittleness and tailor multi-functional properties. The properties of carbon nanotubes (CNTs) make them leading candidates for nanocomposite reinforcement, but how CNT confinement influences the structural evolution of the PyC matrix is unknown. Here, the influence of aligned CNT proximity interactions on nano- and mesoscale structural evolution of phenol-formaldehyde-derived PyCs is established as a function of pyrolysis temperature (\(T_{\mathrm {p}}\)) using X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy. Aligned CNT PyC matrix nanocomposites are found to evolve faster at the mesoscale by plateauing in crystallite size at \(T_{\mathrm {p}}\) \(\sim\)800 \(^{\circ }\hbox {C}\), which is more than \(200\,\,^{\circ }\hbox {C}\) below that of unconfined PyCs. Since the aligned CNTs used here exhibit \(\sim\)80 nm average separations and \(\sim\)8 nm diameters, confinement effects are surprisingly not found to influence PyC structure on the atomic-scale at \(T_{\mathrm {p}}\) \(\le \)1400 \(^{\circ }\hbox {C}\). Since CNT confinement could lead to anisotropic crystallite growth in PyCs synthesized below \(\sim\)1000 \(^{\circ }\hbox {C}\), and recent modeling indicates that more slender crystallites increase PyC hardness, these results inform fabrication of PyC-based meta-materials with unrivaled specific mechanical properties.     

Thermal stability and electrical properties of dodecyl-benzene-sulfonic-acid doped nanocomposites of polyaniline and multi-walled carbon nanotubes

Electrically conductive dodecyl-benzene-sulfonic-acid (DBSA) doped polyaniline (Pani) nanocomposites were prepared with multi-walled carbon nanotubes (MWCNTs) by in situ oxidative polymerization of aniline in the presence of different amounts of MWCNTs. The stability of the nanocomposites in terms of DC electrical conductivity retention was studied in ambient atmosphere by isothermal accelerated aging and cyclic accelerated aging techniques. The MWCNT/Pani nanocomposites were observed to be thermally more stable under ambient environmental conditions than Pani. Such nanocomposites with high thermal stability may find a place as future materials for the replacement for Pani.     

Thermal stability and electrical properties of dodecyl-benzene-sulfonic-acid doped nanocomposites of polyaniline and multi-walled carbon nanotubes

Electrically conductive dodecyl-benzene-sulfonic-acid (DBSA) doped polyaniline (Pani) nanocomposites were prepared with multi-walled carbon nanotubes (MWCNTs) by in situ oxidative polymerization of aniline in the presence of different amounts of MWCNTs. The stability of the nanocomposites in terms of DC electrical conductivity retention was studied in ambient atmosphere by isothermal accelerated aging and cyclic accelerated aging techniques. The MWCNT/Pani nanocomposites were observed to be thermally more stable under ambient environmental conditions than Pani. Such nanocomposites with high thermal stability may find a place as future materials for the replacement for Pani.     

Dramatic effect of multiwalled carbon nanotubes on the electrical properties of alumina based ceramic nanocomposites

We report recent work on electrical properties of multiwalled carbon nanotubes (MWNTs)/alumina composites. The composites with different contents of MWNTs were consolidated by spark plasma sintering and their temperature dependence dc conductivity was scrutinized in the temperature range from 5 to 300 K. The analysis of the temperature dependence of the conductivity suggests that for temperatures higher than 50 K, conduction can be ascribed to thermal fluctuation induced tunneling of the charge carriers through insulating barriers between MWNTs, while at temperatures below 50 K, the conduction can be attributed to three dimensional variable range hopping through MWNTs network in the alumina matrix. The frequency dependence of the conductivity was studied from 5 to 1.3 × 10⁷ Hz. The universality of the ac conduction in MWNT/alumina composites was examined by construction of master curve.     

Adsorption of fluoride from water by aligned carbon nanotubes

Aligned carbon nanotubes (ACNTs), a new type of carbon material, were prepared by catalytic decomposition of xylene using ferrocene as catalyst. The kinetics experiment of ACNTs shows that fluoride adsorption rate is fast in the first 60 min and the adsorption capacity reaches 3.0 mg/g rapidly, then it decreases and adsorption achieves equilibrium gradually in about 180 min. The fluoride adsorption of ACNTs depends slightly on the solution pH value. The highest adsorption capacity of ACNTs occurs at pH 7 and reaches 4.5 mg/g at equilibrium fluoride concentration of 15 mg/l. The experimental results indicate that ACNTs are promising candidate materials for fluoride removal.