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Recent Advances in Research on Carbon NanotubePolymer Composites


By Michele T. Byrne and Yurii K. Gunko*

Carbon nanotubes (CNTs) demonstrate remarkable electrical, thermal, and mechanical properties, which allow a number of exciting potential applications. In this article, we review the most recent progress in research on the development of CNTpolymer composites, with particular attention to their mechanical and electrical (conductive) properties. Various functionalization and fabrication approaches and their role in the preparation of CNTpolymer composites with improved mechanical and electrical properties are discussed. We tabulate the most recent values of Youngs modulus and electrical conductivities for various CNTpolymer composites and compare the effectiveness of different processing techniques. Finally, we give a future outlook for the development of CNTpolymer composites as potential alternative materials for various applications, including exible electrodes in displays, electronic paper, antistatic coatings, bullet-proof vests, protective clothing, and high-performance composites for aircraft and automotive industries.

1. Introduction
The area of carbon nanotube (CNT)polymer composites has been progressing extremely rapidly in recent years. Nanotubes themselves have remarkable electrical, thermal, and mechanical properties. For example, CNTs theoretically have exceptional mechanical properties such as elastic modulus and strengths 10100 times higher than the strongest steel at a fraction of the weight. In 2000, Yu et al. measured Youngs moduli values for individual multi-walled nanotubes (MWNT) of between 0.270.95 TPa, strengths in the 1163 GPa range, and a toughness of 1240 J g1.[1] For single-walled nanotubes (SWNT), Youngs moduli were found to be in the range of 0.321.47 TPa and strengths between 10 and 52 GPa with a toughness of 770 J g1.[2] CNTs also show unique electrical properties and electric-current-carrying capacity 1000 times higher than copper wire.[3] Frank et al. calculated the conductance of an average nanotube to be 1/12.9 kV1.[4] This combination of properties makes CNTs potentially ideal candidates for the formation of polymer composites with improved mechanical

properties and electrical conductivity. CNTpolymer composites have a multitude of potential applications ranging from ultrastrong materials for bullet-proof vests, to exible displays, and electronic paper.[5] Adding carbon-based llers to polymers to improve mechanical properties, decrease weight, and act as heat conductors is not a novel idea. Carbon black has been widely utilized to reinforce rubber and plastics, for example, it is extensively used in racing tires to reduce thermal damage. Carbon bers are also hugely popular industrial materials that are used in cars, airplanes, bicycles, etc. However, the carbon-based polymer additives with the greatest potential are CNTs. The ability to harness the mechanical strengths of CNTs has already given rise to new industrial products. For example, sports equipment, such as tennis racquets and golf clubs containing CNTs, has been produced and marketed. With CNTs becoming easier to produce and cheaper to buy, the CNT industry could potentially overtake that of the carbon ber industry and become one of the major additives for polymer-composite fabrication. There are a number of reviews on the conductive and mechanical properties of CNTpolymer composites.[618] However, a signicant progress has been made in the area of the preparation and utilization of nanotubepolymer composite materials lately. In this Progress Report, we will explore how CNTpolymer composites have been developed in recent years, with particular attention to their mechanical and electrical (conductive) properties.

2. Functionalization of Carbon Nanotubes for Polymer-Composite Preparation


The chemical functionalization of CNTs has been a subject of several reviews.[1923] Here, we are going to focus only on recent developments of functionalization of CNTs for polymer composite formation. It is known that nanotube solubility, dispersion, and stress transfer must all be maximized to reach optimum mechanical properties. Unless the interface between nanotube and polymer is carefully engineered, poor load transfer between nanotubes, when in bundles, and between nanotubes and surrounding polymer chains may result in interfacial slippage.[24]

[*] Prof. Y. K. Gunko, M. T. Byrne School of Chemistry and CRANN Istitute, Trinity College Dublin Dublin 2 (Ireland) E-mail: igounko@tcd.ie

DOI: 10.1002/adma.200901545

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Therefore, functionalization of nanotubes is extremely important for their processing and potential applications in polymer composites. In general, composites based on chemically modied nanotubes show the best mechanical results because functionalization enables a signicant improvement in both dispersion and stressstrain transfer. The treatment of CNTs by chemical functionalization and/or ultrasonication is widely used to increase the dispersion of nanotubes in solvents. In particular, a better dispersion of nanotubes in solvents overcomes the problems of nanotube aggregation in polymer composites processed by the solution casting technique.[2531] There are two major approaches to nanotube functionalization: covalent functionalization and non-covalent supramolecular modications.[23,32,33]

Michele Byrne graduated from The University of Dublin, Trinity College, with a degree in the Physics and Chemistry of Advanced Materials in 2005. She is currently nishing her Ph.D. degree in Chemistry. Her research focuses on the chemical functionalization of carbon and titania nanotubes for use in polymer composites; other research has been undertaken on the creation of highly conductive buckypapermetal composites using electroless deposition. Yurii Gunko received his degree (1987) and Ph.D degree in Inorganic Chemistry (1990) from Moscow State University. Then, he worked as a lecturer in Chemistry in the Belorussian Institute of Technology (Belarus). Between 1994 and 1999 he worked as a postdoctoral researcher in the groups of Professor M. F. Lappert at the University of Sussex (UK) and Professor F. T. Edelman at the University of Magdeburg (Germany). In 1999 Dr. Gunko became lecturer of Inorganic Chemistry in the Chemistry Department of Trinity College Dublin (Ireland), where he currently works as associate Professor. His main research interest and activities are: the chemical functionalization of carbon nanotubes (CNTs), preparation of CNTpolymer composites, magnetic nanoparticles and magnetic uids, and quantum-dot-based materials.

2.1. Covalent Functionalization Covalent functionalization of CNTs can be achieved by either direct addition reactions of reagents to the sidewalls of nanotubes or modication of appropriate surface-bound functional (e.g., carboxylic acid) groups on the nanotubes.[13,14,23] An example of direct functionalization of nanotubes with phenol groups via 1,3-dipolar cycloaddition is shown in Figure 1. This functionalization provided stable dispersions of CNTs in a range of polar solvents, including water. An advantage of the phenolic functionalities is that they allow post-functionalization of the MWNTs with other molecules that can be employed in preparing customized products. In fact, the functionalized CNTs were found to be compatible with polymers or layered aluminosilicate clay minerals, giving homogeneous, coherent, transparent CNT thin lms and/or gels.[34] However, the most common and facile method for the surface functionalization of CNTs is nanotube oxidation, which results in the formation of a number of carboxylic acid groups (COOH) on the surface of the nanotubes. These functionalized nanotubes are much more stable in polar solvents. For example, Feng et al.

showed that by treating MWNTs with HNO3/H2O2 and HNO3/ H2SO4 functionalized nanotubes formed, which were stable in water at room temperature for more than 100 days.[35] As a result, the water-stable nanotubes can be easily embedded into watersoluble polymers such as a poly(vinyl alcohol) (PVA), giving polymerCNT composites with homogeneous nanotube dispersion.[36] Oxidized nanotubes also show excellent stability in other solvents such as caprolactam, which is used in the production of polyamide (PA6).[37] It has been shown that acid functionalization signicantly improves the interfacial bonding properties between the CNTs and a polymer matrix. The carboxylic functional groups have been shown to give a stronger nanotubepolymer interaction, leading to enhanced values in Youngs modulus and mechanical strength.[3847] Acid-treated nanotubes can also be used to electrochemically deposit metal (e.g., gold) nanoparticles onto CNT surfaces.[48,49] When acid-treated nanotubes were heated under reux with HAuCl4 and HNO3 or with HAuCl4 and tetrakis(hydroxymethyl)phosphonium Figure 1. Schematic presentation of covalent functionalization of a CNTs via 1,3-dipolar cycloaddition for enhancing the ability to process CNTs and facilitating the preparation of hybrid chloride (THPC), this resulted in the formacomposites, which is achieved solely by mixing. Reproduced with permission from [34]. Copyright tion of individual gold nanoparticles with a range of 17 nm on the CNT surface.[50] 2008, American Chemical Society.

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A completely different strategy for the surface functionalization of CNTs with nitrogen-containing groups is the treatment of CNTs under an atomic-nitrogen ow obtained by molecularnitrogen dissociation in an Ar N2 microwave plasma. X-ray photoelectron spectroscopy of the nanotube surface demonstrated the presence of amides, oximes, and, mainly, amine and nitrile groups.[51,52] The presence of active functional groups such as carboxylic acids or amines allows for further covalent functionalization with polymer molecules (polymer grafting). Two main approaches for the covalent functionalization of CNTs with polymers have been reported: grafting from and grafting to.[13,14,33] The grafting-from approach is based on the initial immobilization of initiators onto the nanotube surface, followed by in situ polymerization with the formation of the polymer molecules bound to the nanotube. The benet of this technique is that polymer-functionalized nanotubes with high grafting density can be prepared. However, this method requires a strict control of the amounts of initiator and substrate. A recent example of the grafting-from technique is the preparation of oligohydroxyamide (oHA)-functionalized MWNTs for nanotube poly(p-phenylene benzobisoxazole) composites. In this case pristine MWNTs were rst oxidized to MWNTCOOH and then functionalized to MWNTCOCl with acyl chloride. Then MWNTCOCl was copolymerized with oHA to produce corresponding grafted MWNTs (MWNToHA).[53,54] The grafting-from technique was also used for the preparation of styryl-grafted nanotubes.[55] In this work, the carboxylic acid groups on the surface of oxidized MWNTs have been reacted with 4-vinylbenzyl chlorides via an esterication reaction followed by the polymerization to produce polystyrene (PS)-grafted CNTs. The grafting-to approach is based on the attachment of already preformed end-functionalized polymer molecules to functional groups on the nanotube surface via appropriate chemical reactions. An advantage of this method is that commercially available polymers containing reactive functional groups can be utilized. However, the main limitation of grafting-to technique is that initial binding of polymer chains sterically prevents diffusion of additional macromolecules to the surface leading to relatively low polymer loading. The grafting-to method was recently applied for the preparation of epoxy-polyamidoamineSWNT composites.[56] In this case, carboxylic acid groups of oxidized nanotubes have been further functionalized using polyamidoaminegeneration-0 (PAMAM-0) dendrimer and epoxy monomers. The functionalization resulted in composites with improved dispersion of SWNTs and enhanced mechanical properties.

There are several non-covalent approaches for nanotube functionalization such as surfactant-assisted dispersion, polymer wrapping, plasma polymerization-treatment, and polymerizationlling technique (PFT).[32] Surfactant-assisted dispersion is a very common technique that enables to transfer nanotubes to the aqueous phase in the presence of surface-active molecules such as sodium dodecylsulfate (SDS) or benzylalkonium chloride. The presence of an aromatic group in the surfactant molecule allows for pp stacking interactions with the graphitic sidewalls of the nanotubes, which results in their effective coating and dispersion.[58] Polymer wrapping involves the utilization of conjugated and aromatic group containing polymers [e.g., polyvinyl pyrrolidone (PVP), poly(phenylenevinylene), pyrenepoly(ethylene glycol) (PEG)], which can wrap around CNTs through pp stacking and van der Waals interactions.[33,59,60] Coleman and Ferreira showed that polymer wrapping can minimize energy for purely geometric reasons.[61] Poly(dimethylsiloxane) (PDMS) polymers have also been used for CNT coating via non-covalent CHp interactions.[57,62,63] Recently, Kevlar-functionalized nanotubes were prepared by heating Kevlar with MWNTs in the presence of sulfuric and nitric acids under reux. This resulted in the partial oxidation and functionalization of CNTs with carboxylic acid groups, which formed hydrogen bonds with amido-groups, as well as terminal carboxylic acid and amino groups in Kevlar. This process produced Kevlar-coated CNTs, which have been utilized for the fabrication of MWNTpolyvinylchloride (PVC) composites.[64] Plasma polymerization treatment enables the coating of CNTs with a very thin (3 nm) polymer layer. Polymer composites based on these coated nanotubes enhanced interfacial bonding in a PS polymer matrix.[65] PFT usually involves in situ copolymerization of olens catalyzed directly from nanotubes pretreated by a methylaluminoxane (MAO) or highly active metallocene-based complexes (e.g., Cp2ZrCl2).[32] This approach destroys nanotube bundles and results in homogeneously coated CNTs.

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3. Main Strategies for the Fabrication of Carbon NanotubePolymer Composites


3.1. Traditional Approaches Common traditional approaches for the fabrication of CNTpolymer composites include: solution processing of composites, melt spinning, melt processing, in situ polymerization, processing of composites based on thermosets, electrospinning, and coagulation spinning for composite bers and yarn production. These methods have been discussed in detail in recent reviews,[13,14] therefore, we are going to present only a brief overview of these strategies. Solution casting processing of composites is one of the most-usual methods for making polymernanotube composites on a laboratory scale. The nanotubes and polymer are mixed in a suitable solvent before evaporating the solvent to form a composite lm.[2531] One of the advantages of this method is

2.2. Non-covalent Functionalization The non-covalent functionalization of nanotubes normally involves van der Waals, pp, CHp or electrostatic interactions between polymer molecules and CNT surface.[33,57,58] The advantage of non-covalent functionalization is that it does not alter the structure of the nanotubes and, therefore, both electrical and mechanical properties should also remain unchanged. However, the efciency of the load transfer might decrease since the forces between the wrapping molecules and the nanotube surface might be relatively weak.

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the possibility to achieve debundling and good-quality dispersion of the nanotubes in an appropriate solvent. However, solution processing techniques cannot be utilized for insoluble polymers. In this case, melt processing is a good alternative technique, which is particularly useful for dealing with thermoplastic polymers.[26,59,6674] Furthermore, melt processing is the most promising approach for the production of polymerMWNT nanocomposites on industrial scale. Normally, melt processing involves mixing of CNTs with the molten polymer by shear mixing. Bulk composites can then be prepared by compression molding, injection molding, or extrusion. Advantages of melt processing are its speed and simplicity and easy integration into standard industrial facilities (e.g., extruders, blow-molding machines). Although under high temperatures, this approach can sometimes result in unexpected polymer degradation and oxidation. Melt processing can also be used for the production of both bulk-polymer composites, composite bers, and yarns.[9,66] Surface-coated CNTs produced by in situ polymerization, whether by covalent or noncovalent methods, enable the production of polymer nanocomposites displaying much-better thermomechanical, ame-retardant, and electrical conductive properties even at very-low nanotube loadings. As mentioned above, the covalent approach allows for the formation of a strong interface between the nanotube and polymer matrix due to strong chemical bonding of polymer molecules to the CNT surface. The in situ polymerization technique also enables the preparation of composites with very-high nanotube loadings. A closely related method of processing of composites is based on epoxy resins thermosets. In this approach, CNTs can be dispersed in a liquid epoxy precursor and, then, the mixtures can be cured by the addition of a hardener, such as triethylene tetramine (TETA), and the application of temperature or pressure.[20,7577] A study of SWNTpolyethylene (PE) composites, prepared with several different methods, found that polymerization was generally preferred as the method to disperse the nanotubes.[78] Widely used industrial approaches for the production of polymer bers and yarns, such as coagulation spinning and electrospinning, have also been utilized for the fabrication of polymernanotube composites. In coagulation spinning, for example, composite bers can be produced by an injection of a surfactant-stabilized nanotube dispersion in water into a rotating bath of polymer (e.g., PVA) dissolved in water, such that nanotube and polymer dispersions owed in the same direction at the point of injection. In this case, polymer molecules replace surfactant molecules on the nanotube surface, thus, destabilizing the nanotubes dispersion, which collapses to form a ber. These bers can then be retrieved from the bath, rinsed, and dried.[7981] The electrospinning technique involves electrostatically driving a jet of polymer and nanotube dispersions in an appropriate solvent out of a nozzle onto a metallic counter electrode. When the power supply is turned on, the composite solution becomes charged. This forces the solution out of the nozzle and toward the counter electrode. Charging of the solvent causes rapid evaporation, resulting in the coalescence of the composite into bers with diameters between 10 nm and 1 mm. Yarns can also be produced by collecting the bers on a rotating drum and twisting them.[82,83]

3.2. New Approaches for Preparation of PolymerComposite Films and Fibers 3.2.1. Layer-by-Layer Technique The layer-by-layer (LBL) approach involves building up a layered composite lm by alternate dipping of a substrate into dispersions of CNTs and polyelectrolyte solutions.[84,85] Additionally, to improve the structural integrity of the lm, crosslinking can be induced. LBL assembly is a simple, versatile, and relatively inexpensive approach, which provides multifunctional molecular assemblies of tailored architectures and material properties for various versatile reaction/sensing materials of nanometer thickness and will enable large-scale, reproducible production of membrane-based, highly integrated microsensors.[86,87] This method has signicant advantages as thickness and polymernanotube ratio can easily be controlled and very-high nanotube loading levels can be obtained. Therefore, this has led to recent exceptional growth in the use of LBL-generated nanocomposites. This technique has been used extensively to incorporate inorganic nanoparticles, nanowires, and nanotubes into organic polymers (Fig. 2).[88] For example, in the process of LBL assembly of active-ester-modied MWNTs and poly(allylamine hydrochloride) (PAH) on an activated surface of a quartz slide, a reaction occurred between the active ester on the surface of the MWNTs and the amine groups of polyallylamine-yielding amide bonds. This resulted in a mechanically stable free-standing thin lm.[89] In other work, LBL assemblies enabled to produce PVA/(SWNT poly(sodium 4-styrene-sulfonate)-

Figure 2. Principal scheme of the LBL lm-deposition. A) Steps 1 and 3 represent the adsorption of polyanion and polycation, steps 2 and 4 are washing steps. B) Two adsorption routes, depicting LBL deposition for polymers and polymers with nanoparticles or nanotubes. Reproduced with permission from [88]. Copyright 2008, American Chemical Society.

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layered coatings and free-standing lms, which have displayed high electrical conductivities and excellent mechanical strength.[90] Recently, highly conductive, smart electronic yarns and textiles have been prepared by LBL coatings of cotton threads with SWNTs and appropriate polyelectrolytes. These new materials demonstrated high chemical/mechanical durability, electrical conductivity, weavablity, and wearability, as well as interesting chemo- and biosensing opportunities. The high strength and conductivities of these composites are attributed to the unique homogeneity of the LBL-assembled composites.[91] 3.2.2. Swelling Technique Recently, high-strength, high-toughness Kevlar-nanotubecomposite bers have been produced by the swelling of commercially available Kevlar bers in a suspension of MWNTs in N-methylpyrrolidone (NMP) under ultrasonication. This process allowed the nanotubes to diffuse into the interior of the ber. The resulting composites were stronger and tougher than the original Kevlar bers at only 12 wt% of nanotube loadings.[92] There is also another very recent report on new conductive CNTPE composites, which have been prepared similarly by swelling a thin PE lm in MWNT dispersions in tetrahydrofuran (THF) under ultrasonication.[93] This new approach is a very promising post-processing technique, which allows us to incorporate CNTs into already formed polymer products, including insoluble or temperature-sensitive polymers, such as Kevlar. In addition, this technology enables the inclusion of nanotubes into a very thin (several hundred nm) top polymer layer. Therefore, only a very small percentage (12%) of nanotubes is needed to produce polymer composites with potentially high electrical surface conductivity and improved mechanical parameters. 3.2.3. Buckypaper-Based Approach Buckypaper is a thin porous assembly of CNTs, usually formed by ltration from their dispersion in a solvent. Over the last few years, the electrical and mechanical properties of buckypaper have been studied extensively.[9496] In order to prepare buckypaper, CNTs must be dispersed in an appropriate solvent. One of the solvents used to prepare buckypaper is NMP, which enables to fabricate good quality buckypaper without the need for centrifugation.[97100] N,N-dimethylformamide (DMF),[101] 3-aminopropyltriethoxysilane[102] and g -butyrolactone, also known as liquid ecstasy and well known for its narcotic properties, have all been shown to be good solvents for CNTs.[103] However, using an appropriate surfactant in water can be cheaper than using DMF and NMP, which also exhibit the disadvantage of high boiling points. The most common surfactants are sodium dodecyl benzene sulfonate (SDBS) and sodium dodecyl sulphate (SDS). Aqueous dispersion of SWNTs in the presence of the water-soluble perylene derivatives has also been reported.[104] After the nanotubes are dispersed in a solvent, the buckypaper can usually be fabricated by chner ltration. a simple Bu Another way to produce buckypaper without the dispersion and ltration method is the domino pushing effect (Fig. 3). Ding et al. present a simple and effective macroscopic manipulation of aligned CNT arrays.[105] The domino pushing

Figure 3. Domino pushing of a CNT array to produce high-quality buckypaper. Reproduced with permission from [105]. Copyright 2008, IOP Publishing.

of the CNT arrays can efciently ensure that most of the CNTs are well aligned tightly in the buckypaper. Initial measurements indicate that these buckypapers have better performance in thermal and electrical conductance. Overall, there is an enormous interest in developing new buckypaper-based composite materials with improved mechanical properties and conductivity for a number of potential applications from hydrogen absorption to re retardation.[106108] Buckypaper, normally, has a laminar structure with a random orientation of the bundles of tubes in the plane of the sheet.[109] It is therefore a porous material and, thus, liquids and gases can permeate through it.[110] However, the exibility of the individual nanotubes and their afnity for each other conspire to obstruct the porosity in such lms limiting the perfusion rate of liquids and gases, restricting the accessible surface area, and, thereby, limiting their utility in important applications.[111] These pores are characterized by a diameter distribution that varies from one to well over a hundred nanometers.[112] This is underlined by the low density of the material, which was found to be rpaper 520 100 kg m3.[112] The interbundle fractional free volume (Vf/VT) can be calculated from the density by Vf/VT 1 rpaper/rNT, where rNT is the nanotube bundle density, which can be estimated as 1500 kg m3.[113] This results in an interbundle free volume of Vf/VT 66 7% showing that the material is dominated by the pores. The pore size is theoretically tuneable depending on the nanotube size and shape and the casting solvent.[114] Infusing the porous buckypaper with polymer is a facile way of improving the buckypaper mechanical properties and create polymer composites with high loadings of nanotubes (>60%). To increase the mechanical properties, sheets of buckypaper can also be inserted between laminates.[115,116] Polymers or epoxies have been layered on top of buckypaper to develop a ply material that has electrochemical actuation properties.[117] In addition, nanotubes may also be chemically cross-linked to create stronger buckypaper. For example, using the nitrene reaction, functionalized nanotubes

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Figure 4. SWNT lm on a exed PE sheet. Reproduced with permission from [120]. Copyright 2006, American Chemical Society.

can be linked within a bundle as well as between bundles. By ltering and drying, a buckypaper of linked nanotubes was obtained. This linked buckypaper has the potential to have better mechanical properties than pristine buckypaper.[118] An interesting dry-transfer approach, initially developed by Zhou et al.,[119] can be used to transfer the thin buckypaper onto a substrate of choice. This approach uses an adhesive, soft, and at PDMS stamp to peel the SWNT lm off of the ltration membrane and then release it onto a desired substrate such as PE in Figure 4.[120]

Youngs modulus (Y) to the volume fraction of nanotubes to polymer (Vf ) are important.[121] We can use these values to quantitatively estimate the reinforcement of both modulus and strength at low nanotube volume fractions. For a thin lm composite, where the nanotubes are aligned in the plane of the lm, the maximum theoretically expected value of dY/dVf is 400 GPa.[13,122] In our calculations, densities of nanotubes used were assumed to be r 1350 kg m3 for SWNTs and r 2150 kg m3 MWNTs.[123] There is a huge number of variables that effect the mechanical properties of CNTpolymer composites including the type of CNTs used, choice of solvent,[124] nanotube functionality, polymer used, composite preparation, etc. As this procedure, potentially, has some errors, these values are to be taken as a guideline only. In this section, we will discuss mechanical properties of most recently reported nanotubepolymer composites and compare those with values reported in some previous reviews.[13,14] We are going to focus on the two main factors strongly inuencing the properties of the composites: functionalization of nanotubes and polymer composite fabrication techniques. 4.1. The Role of Nanotube Functionalization Functionalization of nanotubes is extremely important for their processing and has a direct impact on the mechanical characteristics of CNTpolymer composites. The Y and dY/dVf values of some polymer composites that contain various functionalized and non-functionalized nanotubes are summarized in Table 1 and 2, respectively. As we can see, the highest dY/dVf values are observed for polymers loaded with alkyl-, amine-, or ferritine-protein functionalized nanotubes at very low nanotubes contents (<1 wt%). Normally, nanotube loadings of more than 2 wt% results in a decrease of the mechanical properties due to the

4. A Comparison of Youngs Moduli of Carbon NanotubePolymer Composites


In order to compare the mechanical parameters of new composites, whenever possible, the rate of increase (dY/dVf ) of

Table 1. Mechanical properties of polymer composites containing functionalized CNTs.


Nanotube/Polymer Composite Nanotube Functionality Preparation Techniques YPoly [GPa] 1.64 2.02 0.44 2.4 3.4 2.0 2.7 0.56 1.48 1.5 0.05 1.6 2.76 1.5 1.56 1.29 YMax [GPa] 2.62 3.4 1.2 4.3 7.2 3.8 2.9 0.9 2.63 2.1 0.42 1.9 3.49 2.5 2.4 1.63 NT content [wt%] 10 4 1.5 0.8 1.5 5 3 1 1 5 20 0.125 1 2 0.6 0.25 dY/dVf [GPa] 15 95 120 305 380 95.5 18.15 115 304 24.25 4.5 381 153 300 355 433 Reference and Year [131] 2004 [77] 2004 [132] 2005 [133] 2005 [134] 2005 [135] 2006 [136] 2006 [129] 2006 [129] 2006 [44] 2006 [46] 2006 [122] 2007 [56] 2008 [64] 2008 [126] 2008 [130] 2008

CVD-MWNT/methyl and ethyl methacrylate P(MMA-co-EMA) SWNT/epoxy SWNT/polyamide 6 (PA6) SWNT/PVA CVD-MWNT/PVA MWNT/PC MWNT/PMMA CVD-MWNT/PVC CVD-MWNT/PS SWNT/copolymers of styrene and vinyl phenol (PSVPh) CVD-MWNT/PU SWNT/biosteel (synthetic spider silk) SWNT/PAMAM CVD-MWNT/Kevlar CVD-MWNT/epoxy CVD-MWNT/PS

Octadecylamine Large organic groups PA6 Hydroxyl Ferritin protein Epoxide PMMA CPP CPP Carboxylic acid Carboxylic acid Octadecylamine Epoxy PVC TETA Butyl

Solution casting Solution casting and curing Solution casting and melt spinning Solution casting Solution casting Solution casting and injection molding Melt mixing and extrusion Solution casting Solution casting Solution casting Solution casting Solution casting Solution casting and curing Solution casting Cast molding Solution casting

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www.advmat.de www.MaterialsViews.com Table 2. Youngs moduli and dY/dVf values for CNTpolymer composites produced by various processing techniques.
Solution Casting Nanotube/Polymer Composite CVD-MWNT/PS Arc-MWNT/polyvinylcarbazole (PVK) CVD-MWNT/elastomer CVD-MWNT/PS CVD-MWNT/high density PE DWNT/PVA CVD-MWNT/Cl-PP CVD-MWNT/PVA CVD-MWNT/PC Annealed SWNT/PS MWNT/PE SWNT/epoxy CVD-MWNT/PVC SWNT/poly(3-hydroxybutyrate) (PHB) SWNT/poly(3-hydroxyoctanoate) (PHO) YPoly [GPa] 1.2 2 0.52 103 1.53 0.98 2 0.22 1.9 2.0 2.23 0.682 2.76 1.5 5.66 0.12 YMax [GPa] 1.69 5.6 3.54 103 3.4 1.35 3.6 0.68 7.04 3.3 2.275 1.24 3.27 1.76 11.74 0.53 Melt Processing[a] Nanotube/Polymer Composite Arc-MWNT/PMMA CVD-MWNT/PS CVD-MWNT/PC, DMA[b] CVD-MWNT/PMMA CVD-MWNT/PA6 CVD-MWNT/nylon SWNT/PC Arc-SWNT/PP YPoly [GPa] 0.73 2.3 0.8 2.7 2.6 0.4 0.6 0.85 YMax [GPa] 1.63 2.6 1.04 3.7 4.2 1.24 0.9 1.19 In situ Polymerization Composite SWNT/PBO Arc-MWNT/PMMA MWNT/PA6 MWNT/PMMA SWNT/polyimide SWNT/benzyl peroxide-PP CVD-MWNT/iPP CVD-MWNT/sPP YPoly [GPa] 138 1.5 0.44 0.71 3.8 0.452 1.2 0.38 YMax [GPa] 167 2.5 1.2 1.38 7.2 1.075 1.65 0.635 Buckypaper Composite SWNT/PVA SWNT/resin SWNT/PC Composite SWNT/PU SWNT/PC YBuckypaper [GPa] 2.3 2.55 2.29 Ypolymer [GPa] 0.004 1.8 YMax [GPa] 6.9 15.10 5.08 YMax [GPa] 3.4 6.2 Max NT content [%] 70 31.3 48 Max NT content [%] 100 20 Modulus Increase 300% 429% 220% Modulus Increase 700% 240% Reference and year [113] 2003 [155] 2004 [156] 2008 Reference and year [157] 2008 [158] 2007 Maximum NT content [wt%] 10 1 1.5 0.3 1 7.5 2.1 0.4 dY/dVf [GPa] 550 150 143 583 336 19.27 74 208 Reference and year [149] 2002 [150] 2003 [37] 2005 [151] 2006 [152] 2006 [153] 2007 [154] 2008 [154] 2008 Maximum NT content [wt%] 17 5 15 10 12.5 2 7.5 0.75 dY/dVf [GPa] 7 9 2.4 17 34 64 7.8 68 Reference and year [143] 2001 [144] 2002 [68] 2003 [145] 2004 [67] 2004 [146] 2004 [147] 2004 [148] 2005 NT content [wt%] 1 8 15 5 1 1 1 1 5 2 5 1 2 10 10 dY/dVf [GPa] 74 75 35 103 122 57 1244 72 754 69 5.04 30 107 204 125 8.43 Reference and Year [137] 2000 [25] 2002 [29] 2002 [138] 2002 [139] 2003 [121] 2004 [27] 2004 [27] 2004 [135] 2006 [140] 2006 [141] 2007 [56] 2008 [64] 2008 [142] 2008 [142] 2008

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[a] Melt mixing dY/dVf values appear lower due to higher quantities of nanotubes used. [b] Dynamic mechanical analysis for mechanical testing.

aggregation of nanotubes and reduction in nanotubepolymer interaction. In general, there are greater increases in mechanical parameters and dY/dVf values for covalently functionalized CNTs due to more efcient interfacial stressstrain transfer between the nanotubes and the polymer matrix. However, sometimes CNTs

can act as nucleation centers enhancing polymer crystallinity, as reported by Coleman et al.[27] It has been shown that in nanotubePVA composites the polymer crystallinity increases linearly with an increase in the volume fraction of nanotube, indicating a crystalline polymer coating at the nanotube

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surface.[121] In these cases very high values of Y (e.g., 7.04 GPa) and dY/dVf (e.g., 754 GPa) can be achieved even for nonfunctionalized nanotubes,[27,121] (see Table 2). Nanotubes with carboxylic acid functionalities have demonstrated signicant increases in Youngs moduli for various polymer composites, in particular for those that are produced by solution casting techniques.[44] For example, acid- or alkali-treated CNTs in PVA increased the tensile strength and toughness of the PVA/CNT coated thread by 117 and 560%, respectively.[36] Acid treated CNTs in poly(epsilon-caprolactone) (PCL) increased the strength and modulus of the composite by 12.1 and 164.3%, respectively, at 1.2 wt% of MWNT content.[125] Acid treated CNTs in PU composites gave a remarkable 740% increase in Y from 0.05 to 0.42 GPa at 20 vol% with dY/dVf 4.5 GPa.[46] Similar trends are also observed for other functional groups. For instance, TETA-functionalized MWNTepoxy composites showed an increase in Y of 38% and about 30% in the tensile strength at very low nanotube loadings, which corresponds to dY/dVf 355 GPa.[126] In another example MWNTs were coated with silica, functionalized with 3-methacryloxypropyltrimethoxysilane (3-MPTS) and added to polypropylene (PP). As expected, the 3-MPTS functionalized MWNTPP composite has a higher tensile strength than the pristine MWNTPP composite.[127] Very considerable increases in mechanical properties of polymer composites have also been demonstrated by CNTs functionalized via organometallic approaches, e.g., using butyl lithium.[128] This method allowed the preparation of MWNTs covalently functionalized with chlorinated PP and then utilized as additives in both PS and PVC composites. This gave a two-fold increase in both modulus and strength in polymer composite lms at nanotube loading levels of less than 1 wt%.[129] Also, PS composites based on butyllithium functionalized MWNTs demonstrated an increase in up to 25% in Y and up to 50% in their tensile strength over pure PS at low nanotube loadings of 0.25 wt%, which corresponds to dY/dVf 433 GPa. This value corresponds to the theoretical maximum (400 GPa),[130] thus, organometallic chemistry approaches enable the achievement of very strong binding between the nanotube and the polymer matrix and, as result, demonstrate an excellent interfacial stress transfer in corresponding polymer composites.

4.2. The Role of Fabrication and Processing Techniques Mechanical properties of polymer composites strongly depend on fabrication and processing approaches used. Solution casting is one of the most frequently used techniques for the fabrication of nanotubepolymer composites. This method allows the preparation of quite strong composites at the low nanotube loadings (Table 2). For example the solution casting of PVC composites with MWNTs gave dY/dVf values of 204 GPa. With Kevlarfunctionalized MWNT/PVC composites, however, a substantial increase in dY/dVf of 300 GPa is obtained.[64] These values are quite close to the expected maximum value of dY/dVf,[13,122] indicating very good stressstrain transfer between PVC and the Kevlar-coated nanotubes. Most importantly, the reinforcement was achieved at less than 2 wt% nanotube content, which is a great advantage if we take into account the nanotube costs.

In another example, SWNTs/epoxy composites gave a dY/dVf value of 107.3 GPa.[56] However PAMAM-0-functionalized SWNT/epoxy composites had a higher dY/dVf of 153.6 GPa. In this paper,[56] the authors used the HalpinTsai equation[159,160] to predict the modulus of ber reinforced composites. The experimental values were only half of those from the model prediction. The reason for this was that most of the SWNTs in epoxy showed signicant curvature. If the experimental values of their work were scaled up, their theoretical maximum values would be dY/dVf 300 GPa, which is in excellent agreement with previous theoretical predictions.[13,64,122] Melt processing techniques allow the preparation of composites with higher nanotube loadings (over 10 wt%). Increases in Youngs moduli of 100%,[67] 150%,[66] and even 200%[146] are obtained by this method. However, a higher content of nanotubes usually results in much lower dY/dVf values (Table 2). In this case, polymer composites with lower nanotube loadings should be considered. If we look at melt-mixing dY/dVf values more closely and calculate percentage increases for lower optimal nanotube contents, we can see that the melt mixing technique is quite efcient. For example, Potschke et al. reported SWNT polycarbonate (PC) composites, which showed increases in Youngs modulus up to 7.5 wt% nanotube loading.[147] If we calculate the dY/dVf values at 7.5 wt% (at which Youngs modulus reaches its maximum) we nd dY/dVf 7.8 GPa; if we calculate the dY/dVf value at 1 wt% (the most linear increase) we nd a signicantly higher number of 52.6 GPa. The same applies to MWNTPA6[67] and MWNTPC[68] composites if dY/dVf are calculated at lower nanotube contents (46 wt%). Therefore, for composites formed by melt mixing the dY/dVf values corresponding to maximal Youngs modulus increases in Table 2 should be used as a standard reference only. There is also a great difference in mechanical properties between samples produced by shear controlled orientation in injection molding (dynamic samples) and conventional injection molding (static samples). For example, the morphological observation of MWNT-lled polymer composites based on PC and PE indicated that in dynamic samples the MWNTs are predominantly localized in the PC microbrils without obvious migration to PE matrix. With such unique morphology, the tensile properties of the dynamic samples are considerably higher than for the static samples.[161] In addition, injection molding can give a high degree of CNT orientation, which can affect signicantly the stressstrain curves, as shown by Weidisch and co-workers.[162] The authors measured stressstrain curves for nanocomposites in the injection-molded direction and perpendicular to the injection-molded direction. Not only were the shapes of the stressstrain curves different, but the strain at break was considerably higher when the composites were measured in the direction of injection molding. In situ polymerization is a good way to fabricate very strong nanotubepolymer composites with extremely high dY/dVf values (Table 2).[43] Acid-treated nanotubes are normally very good precursors for the preparation of nanotubepolymer composites by in situ polymerization. For example, composite lms of CNTs with polyaniline (PANI),[163] polypyrrole (PPY) or poly(3,4ethylenedioxythiophene) (PEDOT) were prepared via electrochemical co-deposition from solutions containing acid-treated CNTs and the corresponding monomer.[164] All of the composites

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showed improved mechanical integrity and higher electronic and ionic conductivity. In another example, PA6MWNTs composites, produced in situ, have shown large dY/dVf values of 143 GPa.[37] Ma et al. have found that the polymerization process was 4500 times faster when a self-doped PANI nanocomposite was fabricated using in situ polymerization in the presence of single-stranded-DNA-dispersed and -functionalized SWNTs.[165] The mechanical properties of the MWNTPMMA nanocomposites were studied as a function of both nanotube concentration and surface treatment. Youngs modulus of non-functionalized MWNTPMMA composites was comparable to the pristine PMMA, both gave Y values of 2.7 GPa. Plasma-enhanced chemical vapor deposition (PECVD), was successfully used to produce a PMMA conformal coating (using methylmethacrylate monomer) on MWNTs, which increased Y to 2.85 GPa at 3 wt% corresponding to dY/dVf 28.4 GPa.[136] The overall set of mechanical properties indicates that the polymer coating had a signicant effect on the mechanical properties at 1 wt% concentration, suggesting improved interfacial adhesion between the nanotube and the matrix material.[136] Direct shear testing of poly(butyl methacrylate) (PBMA)-NT composites prepared by in situ polymerization showed strong mechanical behavior with up to a 200% increase in Youngs modulus over PBMA. The PBMACNT hybrid composite was sandwiched between two opposing steel plates, which also served as the grips for the shear testing. The steel plates and the composite were heated to 200 8C and, then, bonded together under pressure (1 MPa) for 10 min. The applied load and the induced strain are recorded at frequent intervals to determine a stressstrain curve for the conning stress. From TGA analysis these composites consist of 40% nanotubes.[166] For PMMA-functionalized MWNTPMMA composites, prepared in situ, all mechanical properties increase. These increases are 94% in Youngs modulus, 360% in the ultimate tensile strength, 373% in the breaking strength, 1282% in toughness, and 526% in the elongation at break. A maximum is reached at 0.5 wt%.[151] It should be mentioned that nucleation of crystallinity[27] in the presence of nanotubes may occur in solution casting, melt processing, and in situ polymerization processing of some polymernanotube composites. The reported mechanical properties of buckypaper composed of SWNTs show a wide variation. The reported moduli range from 0.5 MPa to 2 GPa[99,167] and the reported breaking strengths range from 6.3 to 33 MPa.[109,168170] The mechanical properties of buckypaper are dominated by the nature of the junctions between individual tubes,[171] although tube entanglement is also important.[172] Composites with high nanotube loadings based on buckypapers use mostly polymer intercalation to reinforce bulk-nanotube materials. Binding agents, such as organic polymers, can be intercalated into the porous internal structure of the buckypaper. The mechanical properties vary vastly with buckypaper type and preparation, thus, any increases will be presented as a percentage increase over the control sample given in the paper. In some cases the control sample given was buckypaper (without polymer), denoted as Ybuckypaper. In other cases the control samples given was the polymer without any nanotubes, denoted as Ypolymer. Wang et al. used a low-viscosity resin solution, which was allowed to inltrate the buckypapers to impregnate the SWNT

rope networks. A hot-press molding process was used for molding and curing to produce the nal composites. Nanocomposites with preformed tube networks and high SWNT loading (up to 39% by weight) were manufactured.[155] The permeability of the produced buckypapers was measured to predict the resin inltration time. The storage modulus of the resulting composites was found to be 15 GPa, which is 429% higher than the neat resin modulus. In this way it is possible to transform a brittle polymer into a conductive exible lm. CNTPANI composites can have important potential applications as the electrodes in energy storage devices for their attractive electrochemical properties. Meng et al. very recently reported a novel method to prepare the interesting paper-like CNTPANI composites by using the CNT network as the template. Compared with the conventional brittle CNTPANI composites, these paper-like composites were much thinner and more exible.[173] The research on oxidized-MWNTPVA composite sheets show that the best compromise of mechanical and electrical properties was obtained for a PVA weight fraction of about 30 wt%.[174] The same authors also demonstrate the critical importance of covalent or non-covalent surface functionalization for the conductive properties of nanocomposites.[175] Coleman et al. intercalated PVA into SWNT buckypaper, these composites displayed improvements in Youngs modulus and tensile strength by factors of 3 and 9, respectively.[113] Intercalating both high-molecular-weight and low-molecular- weight PVP into buckypaper from solution also resulted in increases in the mechanical properties. A 3.5 times increase in Youngs modulus and a 6 times increase in tensile strength was observed in these new composites at low polymer loadings (<50% of the total composite mass) compared to original buckypaper. A large increase in toughness (25 times) occurred for the lowmolecular-weight polymer.[112] SWNT buckypaper can also be impregnated with a PC solution to prodice thermoplastic nanocomposites.[156,158] Dynamic mechanical property tests indicated that the storage modulus of the resulting nanocomposites at 20 wt% nanotubes loading was improved by a factor of 3.4, compared with neat PC material.[158] Composites based on polyurethane (PU), with mass fractions of up to 80% PEG-functionalized nanotubes showed increases in Youngs modulus compared to PU lms by up to 800 times.[157] Finally, LBL technique enables to fabricate nanotubepolymer composite lms of signicant tensile strength. For example, PVA[SWNT poly(sodium 4-styrene-sulfonate)] free-standing lms, produced by LBL, were highly exible and possessed tensile strengths of 160 MPa at a volume fraction of SWNTs around 10%.[90] Unfortunately, Youngs moduli and corresponding dY/dVf values have not been reported, therefore it is difcult to compare this samples with those made by other methods. The same authors have also used LBL to reinforce cotton yarns, which resulted in a more than two-fold increase in the ultimate yield strength (from 41.6 to 87.8 MPa) and Youngs modulus (from 140 to 342 MPa). In summary, several researchers have produced nanotube polymer composites with mechanical increases close to the theoretical maximum using a variety of preparation and functional procedures. However, it could be argued that in some cases where nucleation of crystallinity occurs, nanotubes should

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only be considered as a pseudo-reinforcement agent in polymer composites.

5. Conductive Properties of Carbon NanotubePolymer Composites


Conductive nanotubepolymer composites are regarded as promising materials for use in lithium batteries, supercapacitors, polyactuators,[176] biosensors,[177] exible transparent electrodes, etc.[178181] In particular, new transparent and electrically conductive coatings and lms have a variety of fast-growing applications ranging from window glass to at-panel displays. This section will focus on the conductivity of new CNTpolymer composites. As in the case of the mechanical properties, the electrical properties of composites based on CNTs are dependent on their processing technique and nanotube content and also correlate with their structure and morphology.[182]

induced by van der Waals and dipoledipole interactions were not considered in this theory, so experimental values can be much lower. A new resistance formulation for CNTs is suggested using fractal approach. The theoretical prediction agrees well with experimental observation.[187] Most nanotubepolymer composite studies have been aimed at reducing the percolation threshold. In a recent paper in 2006, Gojny et al. compare the conductivity values of SWNTs, double-walled nanotubes (DWNTs), MWNTs, and amino functionalized DWNTs and MWNTs, all within an epoxy matrix.[188] The functionalized DWNTepoxy composites gave the highest percolation threshold, as the functional process added defects to the CNTs and reduced the aspect ratio. The unfunctionalized MWNTs and SWNTsepoxy composites demonstrated lower percolation thresholds. Polyphenylene sulde (PPS)MWNT conductive composites were produced by the simple mixing of PPS granules with MWNT powder and subsequent compression. The electrical properties as a function of MWNT loading clearly showed a low percolation threshold of about 0.22 vol%.[189]

5.1. Percolation Threshold 5.2. Conductive CNTPolymer Composites Electrical conductivity of CNTpolymer composites can be explained by the established percolation theory with an onset of the conductivity when a critical ller concentration, commonly named percolation threshold, is reached to form conductive pathways. As with the mechanical properties of CNTpolymer composites a large number of factors have to be taken into account. The choice of polymer, nanotube type, and solvent (if any) all affect the percolation threshold. In addition, the processing technique, mixing stresses applied during preparation, as well as the shaping procedure play very important roles. For instance, Villmow et al. show that holding pressure, injection velocity, mold temperature, and melt temperature have effects of up to ve orders of magnitude (for a nanotube content of 2 wt%) on the electrical surface and volume resistivities.[183] By adjusting compression molding parameters, similar large orders of magnitude (up to ten orders) in volume resistivity were obtained for MWNTPC composites.[184] The direct incorporation method of nanotubes into PC composites via melt mixing gave a uniform distribution of nanotubes in the composite.[71] It was found, that the type of nanotube affected the percolation threshold. Commercial MWNTs achieved a percolation at 1.0 and 3.0 wt% depending on the aspect ratio and purity of the MWNTs. For high-pressure CO conversion (HiPCO)SWNT (CNI, Texas) percolation occurred between 0.25 and 0.5 wt% SWNT. Thus, sample preparation and type of nanotubes are key factors in achieving high conductivity in nanotubepolymer composites at low nanotube content. Usually, a modied percolation theory is needed to take into account the high aspect ratio of nanowires, nanobers, and nanotubes.[185,186] This can determine the critical volume fraction required to achieve a conducting, percolated network. The percolation threshold for rod-like particles with aspect ratios of >100, was calculated to be 0.241.35 vol%.[185] However, many forces such as particleparticle or particlematrix interaction, 5.2.1. Composites of CNT and Conductive Polymers Composite materials based on conjugated conductive polymers and conductive llers have been intensively investigated. For example PANI is a typical conductive polymer, which has been shown to act as a charge transfer component between basal planes of graphite.[190] A good review on PANICNT composites by Gajendran and Saraswathi show that, apart from in situ chemical polymerization and electrochemical deposition, a number of interesting approaches including the use of aniline functionalized CNTs and ultrasound/microwave/g -radiation initiated polymerization have been used in the preparation of composites. Experimental results indicate favorable interaction between PANI and CNTs.[191,192] PEDOT-doped and -stabilized with poly(styrenesulfonate) (PEDOT/PSS) is another typical conductive polymer. SWNTPEDOT/PSS composites showed high conductivity with relatively low nanotube loadings <3 wt%. The best result obtained was a resistivity of 3 V cm1 for the 2% loaded lms. As the host bulk conductivity is increased, enhancements of the overall composite conductivity are observed to be proportional. These results suggest that the energy barrier to nanotubenanotube carrier hopping within the matrix can be modied in accordance with a heterogeneous conduction model.[193] Transparent and conductive patterns of carboxyl-functionalized SWNTPEDOT/PSS composites have also been deposited on various substrates by inkjet printing. For low print repetitions, the PEDOT/PSSSWNTCOOH composite patterns show enhanced conductance compared to the corresponding PEDOT/PSS conductors. The results suggest a decrease in percolation threshold for the printed composite, since the nanotubes establish electrical interconnections between the separate PEDOT/PSS (conductive phase) islands being dispersed in the

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Composite Material ITO Touch screen SWNT-PA SWNT-PA SWNT-polyamide SWNT-PEDOT/PSS SWNT-PEDOT/PSS glycerol SWNT buckypaper-PEDOT SWNT buckypaper SWNT buckypaper SWNT-cotton MWNT-poly(allylamine hydrochloride) SWNT-cellulose paper MWNT-PE Surface Resistivity 8V U 500 V U1 1 V cm1 200500 V 8.1 1063.7 107 V U1 3 V cm1 1.2 103 V U1 160 V U1 40 V U1 70 V U1 20 V cm1 1 104 V 0.53 V cm1 5 104 V U1
1

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Nanotube Content N/A N/A 8 vol% high >20 wt% 2 wt% 1 wt% N/A 100% 100% high high 8.32 wt % 0.8 vol %

Transparency 90% 85% investigated investigated 80% investigated investigated 87% 70% 80% investigated 70% investigated 80%

Reference and Year

Not Not Not Not

Not Not

[192] 2003 [217] 2004 [198] 2005 [193] 2005 [193] 2005 [120] 2006 [207] 2007 [207] 2007 [91] 2008 [89] 2008 [214] 2008 [219] 2009

insulating PSS-phase. However, when the amount of PEDOT/ PSS is sufcient to form a continuous conducting phase, the interaction between PEDOT/PSS and SWNTs becomes insignificant and the conductivity is not enhanced by the nanotubes. Although there is a trade-off between transparency and conductivity, the authors achieved highly transparent patterns (similar to 90%) with a reasonably low resistivity similar to 10 k V U1.[194] A comparison of surface resistivities of various conductive CNTpolymer composites is presented in Table 3.

polymers, such as polyoxymethylene and polyamide, demonstrating the generality of this observation.[197]

5.3. Novel Methods of Producing Conductive CNTPolymer Composites In order to increase the conductivity of polymerCNT composites a number of new processes have been developed in recent years. These include: spray-coating, latex technology, hot pressing, static casting, melt processing, LBL, and swelling. SWNTs that were spray-coated onto prepared polyamide lms gave surface resistivities ranging from 8.1 106 to 3.7 107 V U1. These composites demonstrated excellent transmission (over 80%) even though a high amount of NTs were used (over 20 wt%). Importantly, bending, folding, or crumpling did not affect the surface resistivity of the coated lms.[198] New latex technologies involve the ultrasonication dispersion of NTs in water with a surfactant, centrifugation to remove large bundles, and the mixture of the supernatant with latex particles obtained by emulsion polymerization. This allows the production of conductive composites, which consist of SWNTs in a polymer matrix of choice, with very low percolation threshold. Conductivities of 1 S m1 were achieved at 1.6 wt% of nanotube loading.[199] Grunlan et al. used latex to make CNTpolymer composites and the authors achieved an even lower percolation threshold <0.04 wt% SWNT.[200] MWNTsPS nanocomposites were also fabricated using latex technology. The maximum conductivity was 4.9 106 S m1 at 6.5 wt%, which is ten orders in magnitude higher than that of pure PS.[201] The advantages of this technique are many, including high conductivities at a low percolation threshold, due to good incorporation of nanotubes into the polymer matrix and this method does not require toxic solvents. In another approach PS pellets coated with SWNTs were hot-pressed to make a contiguous, cellular SWNT structure. A SWNTPS composite with 0.5 wt% NTs made by this hot-pressing process has an electrical conductivity of

5.2.2. Composites of CNT and Non-conductive Polymers Unfortunately, conductive polymers have limited thermal and electrical stability, low durability, and relatively poor mechanical properties. These characteristics are very important for transparent-electrode applications. Therefore, signicant efforts are carried out to produce new conductive polymer composites by addition of conductive llers to initially non-conductive polymer matrixes. For example, conductive SWNTultrahigh-molecularweight PE (UHMWPE) and MWNTUHMWPE composites with very-low percolation thresholds (0.095 wt% for SWNTs and 0.05 wt% for MWNTs) can be obtained through the sintering of UHMWPE granules covered with CNTs under optimized sintering conditions from the different types of CNTs and their dispersions.[195] PPS-grafted MWNTs gave surface conductivities of 0.117 and 0.036 S m1 for as-prepared linear PSS-grafted MWNTs and hyperbranched-PSS-grafted MWNTs, respectively.[196] Electrically conducting polybenzazoleMWNT-nanocomposite lms were prepared by ultrasonication and drop casting on glass slides. At 5 wt% of nanotubes, the composite lms exhibited a dramatic enhancement in electrical conductivity by eight orders of magnitude from 1014 to 1.6 106 S m1 without signicantly sacricing optical transparency.[54] Interestingly the addition of electrically inert particulate llers, such as calcium carbonate (CaCO3), can result in a signicant reduction in electrical resistivity of electrically conductive PPMWNT composites. Similar results were obtained for different inert llers, including talc and wollastonite, and host

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3 106 S m1, while a well-dispersed composite made by a coagulation method with the same SWNT amount has an electrical conductivity of only 1010 S m1.[202] Xu et al. in 2007 fabricated the lightest (density of 0.05 g cm3) conductive polymer composite currently available. The conductive MWNT-rigid PU-foam composite was prepared by static casting. This generated an ultralight foam. The highest conductivity level was 2.4 102 S m1 at 2 wt%.[203] The LBL approach has been used to prepare novel conductive and transparent nanotubepolymer composites.[87,88] MWNTs and poly(allylamine hydrochloride) thin multilayered composite lms displayed surface resistance around 10 kV and with a reasonable transparency (70% at 500 nm).[89] PVA[SWNT poly(sodium 4-styrene-sulfonate)]-layered coatings gave electrical conductivities of 102 to 103 S m1 without doping with nanotube loading as low 10%. Transmission of thin lms was 97%. Thicker layers, which were less transparent, showed higher conductivities of 4.15 104 S m1.[90] Finally, a recently reported new swelling under ultrasound approach resulted in novel PE composite lms, which demonstrated conductivities of up to 66 S m1, and sheet resistances of 50 kV U1 at optical transparencies of 80%.[93]

5.4. Buckypaper-Based Polymer Composites

In order to meet the requirements of touch screens for practical applications the buckypaper must have a sheet resistance of 500 V U1 and 85% transmittance (T). However, for transparent conducting electrodes, the conductivity must be much higher (50 V U1, 85% T). Typical buckypaper contains a mixture of semi-conducting and metallic, conducting nanotubes,[204,205] and has a reasonable conductivity, which has been reported in the order of 103 S cm1.[206,207] The conductivity of buckypaper increases with an increase in nanotube graphitization but decreases with an increase in lm porosity and mean bundle diameter. Computational studies show that the network conductivity is expected to scale linearly with the density of interbundle junctions.[208] The electrical properties depend on the quantity of defects on the CNTs,[99] the length of the nanotube is a factor too.[209] Buckypaper is physically strong yet highly exible, therefore, expectations are high that thin buckypaper lms may be used as exible electrodes. Acid treating of buckypaper has long been shown to dope the nanotubes. For example, Barros et al. used Raman spectroscopy to demonstrate that H2SO4 can dope both the outer walls of DWNTs in the buckypaper and the inner wall of any metallic nanotubes.[210] Several groups attribute increases in the Figure 5. a) Sheet resistance versus transmittance at 550 nm before (open circle) and after conductivity of buckypaper to acid dop- (solid-circle) nitric acid treatment with previously reported values for comparison and b) the [120,211,212] ing. Geng et al. showed with X-ray corresponding conductivity as a function of lm thickness before and after acid treatment. SEM photoelectron spectroscopy (XPS) analysis that images of before (c) and after (d) acid treatment, taken at a viewing angle of 608. Reproduced with it is the removal of the residual SDS surfactant permission from [207]. Copyright 2007, American Chemical Society.

that increases the buckypaper conductivity, not the functionalization of the nanotubes by acid treatment. The authors achieved sheet resistances of 40 and 70 V U1 at the corresponding transmittances of 70 and 80%, Figure 5.[207] We can suggest that the increase in conductivity is a combination of both doping and removal of trace surfactant. Li et al. found that, as an electrically conductive and optically transparent thin coating material, DWNT networks have better transparency-conductance performance, as compared with SWNT and MWNT.[213] It was also found that the electronic transportability and optical properties of the SWNT lms can be altered by chemical modication of thionyl chloride (SOCl2). Additionally, the conductancetemperature-dependence analysis revealed that a variable-range hopping mechanism dominates the conductance of few-wall nanotube mats, while uctuation-assisted tunneling plays a more important role in that of MWNT lms. Using PEDOT passivation for better surface smoothness and SOCl2 to lower sheet resistance enabled Zhang et al. to achieve the astonishing 160 V U1 resistance and 87% transparency. The surface roughness of these lms was comparable to that of indium tin oxide (ITO) substrates.[120] In another example, buckypaper was combined with cellulose paper, allowing to produce electrically conductive composites with only 8.32 wt% CNTs and a volume resistance of 5.3 101 V cm1.[214] Fukushima et al. performed free-radical polymerization of an imidazolium ion-based ionic liquid bearing a methacrylate group, gelling with SWNTs.[215] This allowed fabrication of a mechanically reinforced, electroconductive, soft material, which they called buckyplastic. A lm sample of this material displays an excellent conductivity of 0.01 S m1 at a 7 wt% content of SWNTs. The conductivity is temperature dependent in the range 5300 K, suggesting that the conductive process involves carrier hopping. Although a buckyplastic derived from a vinylimidazolium-ion-based ionic liquid monomer shows a comparable conductivity to that of the methacrylate version, the lm is brittle, irrespective of the presence or absence of

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SWNTs. It seems, that high quantities of nanotubes (>theoretical percolation threshold of 1.35 vol%) are needed to receive highly conductive, transparent, exible NTpolymer composites. We believe that buckypaper and buckypaperpolymer composites will be able to achieve this goal. Ferrer-Anglada et al. reported on the characterization and optimization of thin, transparent, and electrically conducting lms (from 120 to 180 nm thick) based on SWNTs and conducting polymers, PPY or PANI.[216] A buckypaper matrix was deposited onto a transparent substrate and used as electrodes in order to electrochemically grow a thin lm of the conducting polymer on the substrate.[217] However, these lms were still 10100 times less conductive compared to the well-known transparent conducting oxides (TCOs) like ITO. In any way, this electrochemical deposition method offers great potential to create an alternative to ITO conductive transparent substrates. The best values obtained were for CNTPA composites with resistances of 200500 V, thus, two to three times more conductive than the nanotube matrix alone. Also, recently, Byrne et al. have shown the utilization of substrate-enhanced electroless deposition to deposit copper from copper nitrate solution onto the surface of the buckypaper.[218] This method gave an increase in conductivity of 350% and resulted in a three-fold increase in mechanical properties. Potentially, the utilization of this approach could allow the preparation of CNTmetalpolymer composites with high conductivities and improved mechanical properties.

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Figure 6. Photographs of SWNT-cotton yarn. a) Comparison of the original and surface modied yarn. b) 1 m long piece as fabricated. c) Demonstration of LED emission with the current passing through the yarn. Reproduced with permission from [91]. Copyright 2008, American Chemical Society.

5.5. Conductive Fibers and Yarns The use of intelligent materials reacting to external stimuli is rapidly growing in the eld of technical textiles. In addition to chemical/mechanical durability and high electrical conductivity, important yarn-material qualications include weavablity, wearability, light weight, and smart functionalities. Different conductive yarns, where MWNTs are used as both a reinforcing and a conductive nanoller for spinnable polymers, such as PANI, have been fabricated.[220] The major inuence of the homogeneous dispersion of the nanotubes in the host matrix is particularly pointed out and the electrical behavior of the nanocomposite yarns has been investigated.[220] Melt-spun PC bers containing both MWNTs and SWNTs showed signicant increases in both Youngs modulus and yield strength, with MWNTPC bers displaying the highest increase of 71% in Youngs modulus at a concentration of 5 wt% nanotubes.[221] Melt-spinning also shows increases in the mechanical properties of polyamide-12MWNT composite bers.[26] Problems in determining ller dimensions, orientation, and arrangement are common to these nanocomposites. Recently, extremely low-density PVA and water-soluble functionalized SWNTs membranes were prepared by the electrospinning technique. As expected, the mechanical properties increased (dY/dVf 20 GPa at 0.43 vol%). Blond et al. were able to enhance the mechanical properties by using a rotating drum collector instead of a stationary plate collector.[222] This helped to align the membrane bers in a preferential direction, increasing the mechanical properties, and overcoming the problem of orientation.

Kotov and coworkers demonstrated a simple process of transforming general commodity cotton threads into intelligent e-textiles using a polyelectrolyte-based coating with CNTs.[91] Efcient charge transport through the network of nanotubes was 20 V cm1. The authors even demonstrated the powering of a light-emitting diode (LED) device using a battery and prepared conductive threads as wires (Fig. 6). Along with integrated humidity sensing, it was demonstrated that CNT-cotton threads can be used to detect albumin, the key protein of blood, with high sensitivity and selectivity. Wearable biomonitoring and telemedicine sensors seem very much a reality.[91] In another example, conductive PC composite bers, containing 2 wt% MWNT and pure PC have been produced by melt spinning. The nanotubes aligned somewhat with this method. Interestingly, with an increase in alignment, electrical conductivity of these bers is lost.[223]

6. Conclusions and Future Outlook


In conclusion, signicant progress was achieved in the area of nanotubepolymer composites over last few years. A range of new composites have demonstrated astonishing mechanical parameters and conductivity values. Overall, covalently functionalized nanotubes have been shown as particularly good additives for polymer reinforcement, allowing for an excellent stressstrain transfer between nanotubes and polymer matrix. However, nanotube functionalization does not have any positive impact on the conductivities of polymernanotube composites and normally results in higher percolation threshold values. Therefore, it is still quite challenging to achieve both good mechanical properties and high conductivities in one composite. LBL technique seems to be an excellent choice for the fabrication of mechanically strong and highly conductive nanocomposites, because the technique minimizes the damage to the nanotubes during processing. Also, new swelling under ultrasound, post-processing techniques have a great potential for the preparation of both mechanically strong and conductive polymer composites. There is large interest in the further development of polymernanotube composite materials, which are promising for a broad range of important applications. The production of

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conductive polymerCNTs composites for exible electrodes in displays and electronic paper as well as antistatic coatings will be of particular importance in the nearest future. The new exible displays will have a drastic impact on society directly, by radically expanding our ability to receive and process information. Widespread applications will also be in publishing, electronic paper, newsprint, and communications. Existing display technology is mostly based on ITO coated substrates. ITO is the standard for visible wavelengths, with commercially available 150200-nm-thick lms with more than 90% transparency and a sheet resistance of  8 V U1. However, displays using this system are only suitable for a limited range of applications, because ITO is an extremely brittle and inexible material. ITO can also degrade the organic light-emitting layers. Another drawback is that ITO technology requires high temperature processes to achieve good qualities of conductive lms. In addition, the worldwide resources of indium are limited (the at panel industry currently consumes more than 800 tons of indium per year) and therefore in the near future it will be difcult to satisfy the increasing demand for large-area transparent conductive electrodes using ITO technology. ITO coated substrates also serve as electrodes in multilayered copper indium gallium selenide (CIGS)- and TiO2-based photovoltaic cells. These solar-cell technologies face the same supply and rising-cost problems for indium. Alternative TCO materials, such as doped ZnO, are also very brittle to be used in exible electrodes. Another approach to the fabrication of exible transparent electrodes is based on the utilization of conductive polymers (e.g., PEDOT/PSS) as exible electrodes. This technology resulted in the fabrication of the rst exible organic LED (OLED) displays, which can be bent and rolled. However, conductive polymers have limited thermal and electrical stability, low durability, and relatively poor mechanical properties. Therefore, potentially, the most likely solution of this problem will be the development of polymerCNT composite-based transparent electrodes. Alternatively a combination of ITO, CNTs and a polymer material can be used. For example, Al/SWNT-polymer/ ITO thin-lm devices, which exhibit promising photoconductive and photovoltaic responses in a broad spectral range, typically from 300 to 1600 nm have been reported.[224] Finally, another very important area in the near future will be the development of new ultrastrong polymernanotube materials for application in bullet-proof vests, protective clothing, highperformance composites for aircraft, and automotive industries (e.g., seat belts, cables, reinforcement of tires, break linings, bumpers, etc.) These large sectors will require huge quantities of CNTs. For these reasons the development of new cost-effective CNTpolymer composites will be necessary to meet these needs.

Acknowledgements
We thank Science Foundation Ireland and CRANN for nancial support. Received: May 8, 2009 Revised: August 17, 2009 Published online: November 25, 2009

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