Electrical and mechanical properties of carbon nanotube‐epoxy nanocomposites

In this work, electrical conductivity and thermo‐mechanical properties have been measured for carbon nanotube reinforced epoxy matrix composites. These nanocomposites consisted of two types of nanofillers, single walled carbon nanotubes (SW‐CNT) and electrical grade carbon nanotubes (XD‐CNT). The influence of the type of nanotubes and their corresponding loading weight fraction on the microstructure and the resulting electrical and mechanical properties of the nanocomposites have been investigated. The electrical conductivity of the nanocomposites showed a significantly high, about seven orders of magnitude, improvement at very low loading weight fractions of nanotubes in both types of nanocomposites. The percolation threshold in nanocomposites with SW‐CNT fillers was found to be around 0.015 wt % and that with XD‐CNT fillers around 0.0225 wt %. Transmission optical microscopy of the nanocomposites revealed some differences in the microstructure of the two types of nanocomposites which can be related to the variation in the percolation thresholds of these nanocomposites. The mechanical properties (storage modulus and loss modulus) and the glass transition temperature have not been compromised with the addition of fillers compared with significant enhancement of electrical properties. The main significance of these results is that XD‐CNTs can be used as a cost effective nanofiller for electrical applications of epoxy based nanocomposites at a fraction of SW‐CNT cost. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Trends in Conducting Polymer and Hybrids of Conducting Polymer/Carbon Nanotube: A Review

Several conducting polymers, including polyaniline, polypyrrole, polythiophene, polyvinylpyrrolidone, poly(3,4-ethylenedioxythiophene), poly(m-phenylenediamine), polynaphthylamine, poly(p-phenylene sulfide), and their carbon nanotube reinforced nanocomposites are discussed in this review. The physical, electrical, structural and thermal properties of polymers along with synthesis methods are discussed. A concise note on carbon nanotubes regarding their purification, functionalization, properties and production are reported. Moreover, the article focuses upon synthesis methods, properties and applications of conducting polymer/carbon nanotube nanocomposites are focused. Nanotube dispersion, loading concentration and alignment within conducting polymer/carbon nanotube nanocomposite affect their performance and morphology. The conducting polymer/carbon nanotube nanocomposites are substantially used in sensors, energy storage devices, supercapacitors, solar cells, EMI materials, diodes, and coatings.     

In situ preparation of polyimide/amino‐functionalized carbon nanotube composites and their properties

In order to improve the dispersion of carbon nanotubes (CNTs) in polyimide (PI) matrix and the interfacial interaction between CNTs and PI, 4,4′‐diaminodiphenyl ether (ODA)‐functionalized carbon nanotubes (CNTs‐ODA) were synthesized by oxidation and amidation reactions. The structures and morphologies of CNTs‐ODA were characterized using Fourier transform infrared spectrometer, transmission electron microscopy, and thermal gravimetric analysis. Then a series of polyimide/amino‐functionalized carbon nanotube (PI/CNT‐ODA) nanocomposites were prepared by in situ polymerization. CNTs‐ODA were homogeneously dispersed in PI matrix. The influence of CNT‐ODA content on mechanical properties of PI/CNT‐ODA nanocomposites was investigated. It was found that the mechanical properties of nanocomposites were enhanced with the increase in CNT‐ODA loading. When the content of CNTs‐ODA was 3 wt%, the tensile strength of PI/CNT‐ODA nanocomposites was up to 169.07 MPa (87.11% higher than that of neat PI). The modulus of PI/CNTs‐ODA was increased by 62.64%, while elongation at break was increased by 66.05%. The improvement of the mechanical properties of PI/CNT‐ODA nanocomposites were due to the strong chemical bond and interfacial interaction between CNTs‐ODA and PI matrix. POLYM. COMPOS., 35:1952–1959, 2014. © 2014 Society of Plastics Engineers     

Thermal conductivity of carbon nanotubes and their polymer nanocomposites: A review

Thermally conductive polymer composites offer new possibilities for replacing metal parts in several applications, including power electronics, electric motors and generators, heat exchangers, etc., thanks to the polymer advantages such as light weight, corrosion resistance and ease of processing. Current interest to improve the thermal conductivity of polymers is focused on the selective addition of nanofillers with high thermal conductivity. Unusually high thermal conductivity makes carbon nanotube (CNT) the best promising candidate material for thermally conductive composites. However, the thermal conductivities of polymer/CNT nanocomposites are relatively low compared with expectations from the intrinsic thermal conductivity of CNTs. The challenge primarily comes from the large interfacial thermal resistance between the CNT and the surrounding polymer matrix, which hinders the transfer of phonon dominating heat conduction in polymer and CNT.This article reviews the status of worldwide research in the thermal conductivity of CNTs and their polymer nanocomposites. The dependence of thermal conductivity of nanotubes on the atomic structure, the tube size, the morphology, the defect and the purification is reviewed. The roles of particle/polymer and particle/particle interfaces on the thermal conductivity of polymer/CNT nanocomposites are discussed in detail, as well as the relationship between the thermal conductivity and the micro- and nano-structure of the composites.     

Electrophoretic deposition of carbon nanotubes

Electrophoretic deposition (EPD) has been gaining increasing interest as an economical and versatile processing technique for the production of novel coatings or films of carbon nanotubes (CNTs) on conductive substrates. The purpose of the paper is to present an up-to-date comprehensive overview of current research progress in the field of EPD of CNTs. The paper specifically reviews the preparation and characterisation of stable CNT suspensions, and the mechanism of the EPD process; it includes discussion of pure CNT coatings and CNT/nanoparticle composite films. A complete discussion of the EPD parameters is presented, including electrode materials, deposition time, electrode separation, deposition voltage and resultant electric field. The paper highlights potential applications of the resulting CNT and CNT/composite structures, in areas such as field emission devices, fuel cells, and supercapacitors.     

Synthesis,microstructure and electrical conductivity of carbon nanotube–alumina nanocomposites

Carbon nanotube–alumina (CNT–Al₂O₃) nanocomposites have been synthesized by direct growth of carbon nanotubes on alumina by chemical vapor deposition (CVD) and the as-grown nanocomposites were densified by spark plasma sintering (SPS). Surface morphology analysis shows that the CNTs and CNT bundles are very well distributed between the matrix grains creating a web of CNTs as a consequence of their in situ synthesis. Even after the SPS treatment, the CNTs in the composite material are still intact. Experimental result shows that the electrical conductivity of the composites increases with the CNT content and falls in the range of the conductivity of semiconductors. The nanocomposite with highest CNT content has electrical conductivity of 3336 S/m at near room temperature, which is about 13 orders of magnitude increase over that of pure alumina.     

Endohedral and exohedral hybrids involving fullerenes and carbon nanotubes

Since fullerenes and carbon nanotubes (CNTs) were discovered, these materials have attracted a great deal of attention in the scientific community due to their unique structures and properties. The properties of both carbon allotropes can be modulated by chemical functionalization, and merging fullerenes and CNTs combines the electronic and optical properties of CNTs with the excellent electron acceptor characteristic of fullerenes; moreover, a synergistic effect of these hybrids can be found, as the properties of both the nanotube and the fullerene are affected by the presence of the other. In these hybrids, the fullerene can be located inside (endohedral) or outside (exohedral) the CNT and both types of hybrid have specific features. CNT-fullerene hybrids have been studied for various applications, including photovoltaics, optical limiting and flame retardancy amongst others. This review outlines the progress in research on CNT-fullerene hybrids, including endohedral and exohedral combinations, their properties, functionalization, applications and outlook.     

The biocompatibility of carbon nanotubes

Carbon nanotubes (CNT) are well-ordered, high aspect ratio allotropes of carbon. The two main variants, single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT) both possess a high tensile strength, are ultra-light weight, and have excellent chemical and thermal stability. They also possess semi- and metallic-conductive properties. This startling array of features has led to many proposed applications in the biomedical field, including biosensors, drug and vaccine delivery and the preparation of unique biomaterials such as reinforced and/or conductive polymer nanocomposites. Despite an explosion of research into potential devices and applications, it is only recently that information on toxicity and biocompatibility has become available. This review presents a summary of the performance of existing carbon biomaterials and gives an outline of the emerging field of nanotoxicology, before reviewing the available and often conflicting investigations into the cytotoxicity and biocompatibility of CNT. Finally, future areas of investigation and possible solutions to current problems are proposed.     

Wear properties of 3‐aminopropyltriethoxysilane‐functionalized carbon nanotubes reinforced ultra high molecular weight polyethylene nanocomposites

Ultra high molecular weight polyethylene (UHMWPE) is extensively used as a material in various high‐end applications with superior mechanical properties. Carbon nanotubes (CNTs) reinforced UHMWPE (CNT/UHMWPE) nanocomposite is a promising material that can compensate for the weak durability of UHMWPE. In this study, multiwalled carbon nanotubes were oxidized and silanized using acid mixture and 3‐aminopropyltriethoxysilane, respectively, to improve the interfacial strength between CNTs and UHMWPE. The CNT/UHMWPE nanocomposite was fabricated using these oxidized and silanized CNTs. The treatment effect of CNTs on the wear behavior of the CNT/UHMWPE nanocomposites was investigated through wear tests. The oxidization and silanization of CNTs were confirmed by infrared spectroscopy. Scanning electron microscope analysis showed that the silane‐treated CNT/UHMWPE nanocomposites showed better dispersion and interfacial adhesion between UHMWPE and CNTs becaue of the newly formed functional groups on the CNTs. The friction coefficient and wear rate of silanized CNT/UHMWPE nanocomposite were also found to be lower than those of raw UHMWPE and oxidized CNT/UHMWPE nanocomposite. CNTs were functionalized using oxidation and silanization methods to improve the interfacial adhesion between CNTs and UHMWPE. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Carbon nanotube induced polymer crystallization: The formation of nanohybrid shish-kebabs

Carbon nanotubes (CNTs) have attracted tremendous attention in recent years because of their superb optical, electronic and mechanical properties. In this article, we aim to discuss CNT-induced polymer crystallization with the focus on the newly discovered nanohybrid shish-kebab (NHSK) structure, wherein the CNT serves as the shish and polymer crystals are the kebabs. Polyethylene (PE) and Nylon 6,6 were successfully decorated on single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs), and vapor grown carbon nanofibers (CNFs). The formation mechanism was attributed to “size-dependent soft epitaxy”. Polymer CNT nanocomposites (PCNs) containing PE, Nylon 6,6 were prepared using a solution blending technique. Both pristine CNTs and NHSKs were used as the precursors for the PCN preparation. The impact of CNTs on the polymer crystallization behavior will be discussed. Furthermore, four different polymers were decorated on CNTs using the physical vapor deposition method, forming a two-dimensional NHSK structure. These NHSKs represent a new type of nanoscale architecture. A variety of possible applications will be discussed.     

Optimized process for the inclusion of carbon nanotubes in elastomers with improved thermal and mechanical properties

The effects of addition of reinforcing carbon nanotubes (CNTs) into hydrogenated nitrile–butadiene rubber (HNBR) matrix on the mechanical, dynamic viscoelastic, and permeability properties were studied in this investigation. Different techniques of incorporating nanotubes in HNBR were investigated in this research. The techniques considered were more suitable for industrial preparation of rubber composites. The nanotubes were modified with different surfactants and dispersion agents to improve the compatibility and adhesion of nanotubes on the HNBR matrix. The effects of the surface modification of the nanotubes on various properties were examined in detail. The amount of CNTs was varied from 2.5 to 10 phr in different formulations prepared to identify the optimum CNT levels. A detailed analysis was made to investigate the morphological structure and mechanical behavior at room temperature. The viscoelastic behavior of the nanotube filler elastomer was studied by dynamic mechanical thermal analysis (DMTA). Morphological analysis indicated a very good dispersion of the CNTs for a low nanotube loading of 3.5 phr. A significant improvement in the mechanical properties was observed with the addition of nanotubes. DMTA studies revealed an increase in the storage modulus and a reduction in the glass‐transition temperature after the incorporation of the nanotubes. Further, the HNBR/CNT nanocomposites were subjected to permeability studies. The studies showed a significant reduction in the permeability of nitrogen gas. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

The characteristics of carbon nanotube‐reinforced poly(phenylene sulfide) nanocomposites

Multiwall carbon nanotube reinforced poly (phenylene sulfide) (PPS) nanocomposites were successfully fabricated through melt compounding. Structural, electrical, thermal, rheological, and mechanical properties of the nanocomposites were systematically studied as a function of carbon nanotube (CNT) fraction. Electrical conductivity of the polymer was dramatically enhanced at low loading level of the nanotubes; the electrical percolation threshold lay between 1 and 2 wt % of the CNTs. Rheological properties of the PPS nanocomposites also showed a sudden change with the CNT fraction; the percolation threshold was in the range of 0–0.5 wt % of CNTs. The difference in electrical and rheological percolation threshold was mainly due to the different requirements needed in the carbon nanotube network in different stages. The crystallization and melting behavior of CNT‐filled PPS nanocomposites were studied with differential scanning calorimetry; no new crystalline form of PPS was observed in the nanocomposites, but the crystallization rate was reduced. The thermal and mechanical properties of the nanocomposites were also investigated, and both of them showed significant increase with CNT fraction. For 5 wt % of CNT‐filled PPS composite, the onset of degradation temperature increased by about 13.5°C, the modulus increased by about 33%, and tensile strength increased by about 172%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Robust and wear resistant in-situ carbon nanotube/Si3N4 nanocomposites with a high loading of nanotubes

Highly homogenous carbon nanotube (CNT)/silicon nitride (Si₃N₄) nanocomposites with high CNTs loadings, up to 22 vol.%, are developed through the in-situ synthesis of CNTs on the ceramic powders, and further densification using the spark plasma sintering technique. The CNTs dispersion degree, the composite density, and their properties, especially the tribological ones, are evaluated and compared with those obtained for nanocomposites processed by the ex-situ method based on the mixing of nanotubes and ceramic powders in a solvent media. Fully dense in-situ 12 vol.% CNTs nanocomposites are 87% and 65% more wear resistant than monolithic Si₃N₄ materials and ex-situ nanocomposites, respectively, in the latter case due to the higher nanotubes dispersion and better mechanical properties attained by the in-situ process. These new in-situ CNTs nanocomposites present multifunctionality and are promising for emerging applications, especially for gasoline direct injection systems.     

Predicting mechanical properties of multiscale composites

Abstract

The effect of carbon nanotube (CNT) integration in polymer matrixes (two-phase) and fibre reinforced composites (three-phase) was studied. Simulations for CNT/polymer composites (nanocomposites) and CNT/fibre/polymer composites (multiscale) were carried out by combining micromechanical theories applied to nanoscale and woven fibre micromechanic theories. The mechanical properties (Young’s modulus, Poisson’s ratio and shear modulus) of a multiscale composite were predicted. The relationships between the mechanical properties of nano- and multiscale composite systems for various CNT aspect ratios were studied. A comparison was made between a multiscale system with CNTs infused throughout and one with nanotubes excluded from the fabric tows. The mechanical properties of the composites improved with increased CNT loading. The influence of CNT aspect ratio on the mechanical properties was more pronounced in the nanocomposites than in the multiscale composites. Composites with CNTs in the fibre strands generated more desirable mechanical properties than those with no CNTs in the fibre strands.     

Dispersion of solvent-wet carbon nanotubes for electrical CNT/polydimethylsiloxane composite

Highly entangled carbon nanotube (CNT) aggregates contain lots of empty spaces formed by entangled nanotubes wherein a viscous fluid has difficultly to diffuse through these spaces without strong driving force. It is necessary to fill the free volume with the matrix before the dispersion of CNTs. This study is focused on the investigation of the solvent wetting effect of CNTs on their dispersion. The heterogeneously distributed narrow and long tunnels, like porous media in entangled clumps, are wetted with a solvent before dispersion. It results in the improved electrical performance of CNT/PDMS composite since the solvent-wet CNTs have reduced surface energy and may improve the dispersion of CNTs under flow. The dispersion of the solvent-wet CNTs may reduce the entangled CNT aggregates since they have sufficient time to wet and the external energy transferred to the composite during dispersion is used only to disperse the CNT aggregate. Also, if the solvent with a low evaporation temperature is chosen, it does not remain in the composite product at all. The solvent-wetting method is suggested as a novel dispersion method having a high potential for industrial applications, from storage of CNTs to dispersion.     

Alignment and properties of carbon nanotube buckypaper/liquid crystalline polymer composites

Carbon nanotubes (CNTs) have been recognized as a potential superior reinforcement for high‐performance, multifunctional composites. However, non‐uniform CNT dispersion within the polymer matrix, the lack of adequate adhesion between the constituents of the composites, and lack of nanotube alignment have hindered significant improvements in composite performance. In this study, we present the development of a layer‐by‐layer assembly method to produce high mechanical performance and electrical conductivity CNT‐reinforced liquid crystalline polymer (LCP) composites using CNT sheets or buckypaper (BP) and self‐reinforcing polyphenylene resin, Parmax. The Parmax/BP composite morphology, X‐ray diffraction, mechanical, thermal, and electrical properties have been investigated. SEM observations and X‐ray diffraction demonstrate alignment of the CNTs due to flow‐induced orientational ordering of LCP chains. The tensile strength and Young's modulus of the Parmax/BP nanocomposites with 6.23 wt % multi‐walled carbon nanotube content were 390 MPa and 33 GPa, respectively, which were substantially improved when compared to the neat LCP. Noticeable improvements in the thermal stability and glass transition temperature with increasing CNT content due to the restriction in chain mobility imposed by the CNTs was demonstrated. Moreover, the electrical conductivity of the composites increased sharply to 100.23 S/cm (from approximately 10^?13 S/cm) with the addition of CNT BP. These results suggest that the developed approach would be an effective method to fabricate high‐performance, multifunctional CNT/LCP nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Supramolecular self-assembly of biopolymers with carbon nanotubes for biomimetic and bio-inspired sensing and actuation

Biopolymers are important natural multifunctional macromolecules for biomimetic and bio-inspired advanced functional material design. They are not only simple dispersants for carbon nanotube stabilization as they have been found to have specific interactions with carbon nanotubes. Their molecular activity, orientation and crystallization are influenced by the CNTs, which endow their composites with a variety of novel sensing and actuation performances. This review focuses on the progress in supramolecular self-assembly of biopolymers with carbon nanotubes, and their advances in sensing and actuation. To promote the development of advanced biopolymer/CNT functional materials, new electromechanical characteristics of biopolymer/CNT composites are discussed in detail based on the relationship between the microscopic biopolymer structures and the macroscopic composite properties.     

Enhanced electrical properties of polycarbonate/carbon nanotube nanocomposites prepared by a supercritical carbon dioxide aided melt blending method

Polycarbonate/carbon nanotube (CNT) nanocomposites were generated using a supercritical carbon dioxide (scCO₂) aided melt blending method, yielding nanocomposites with enhanced electrical properties and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Baytubes^® C 150 P CNTs were benignly deagglomerated with scCO₂ resulting in 5 fold (5X), 10X and 15X decreases in bulk density from the as-received CNTs. This was followed by melt compounding with polycarbonate to generate the CNT nanocomposites. Electrical percolation thresholds were realized at CNT loading levels as low as 0.83 wt% for composites prepared with 15X CNT using the scCO₂ aided melt blending method. By comparison, a concentration of 1.5 wt% was required without scCO₂ processing. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO₂ processing compared to direct melt blending, but was significantly worse than that of twin screw melt compounded nanocomposites reported in the literature. A rheologically percolated network was observed near the electrical percolation of the nanocomposites. The importance of maintaining longer carbon nanotubes during nanocomposite processing rather than focusing on dispersion alone is highlighted in the current efforts.     

Non-covalent interactions between carbon nanotubes and conjugated polymers

Carbon nanotubes (CNTs) are interest to many different disciplines including chemistry, physics, biology, material science and engineering because of their unique properties and potential applications in various areas spanning from optoelectronics to biotechnology. However, one of the drawbacks associated with these materials is their insolubility which limits their wide accessibility for many applications. Various approaches have been adopted to circumvent this problem including modification of carbon nanotube surfaces by non-covalent and covalent attachments of solubilizing groups. Covalent approach modification may alter the intrinsic properties of carbon nanotubes and, in turn make them undesirable for many applications. On the other hand, a non-covalent approach helps to improve the solubility of CNTs while preserving their intrinsic properties. Among many non-covalent modifiers of CNTs, conjugated polymers are receiving increasing attention and highly appealing because of a number of reasons. To this end, the aim of this feature article is to review the recent results on the conjugated polymer-based non-covalent functionalization of CNTs with an emphasis on the effect of conjugated polymers in the dispersibility/solubility, optical, thermal and mechanical properties of carbon nanotubes as well as their usage in the purification and isolation of a specific single-walled nanotube from the mixture of the various tubes.