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Materials Science and Engineering R 49 (2005) 89–112
Materials Science and Engineering R 49 (2005) 89–112
Materials Science and Engineering R 49 (2005) 89–112 Dispersion and alignment of carbon nanotubes in polymer

Dispersion and alignment of carbon nanotubes in polymer matrix: A review

Xiao-Lin Xie a,b , Yiu-Wing Mai a, * , Xing-Ping Zhou b

a Center for Advanced Materials Technology (CAMT), School of Aerospace, Mechanical and Mechatronic Engineering J07, University of Sydney, Sydney, NSW 2006, Australia b Department of Chemistry, Huazhong University of Science and Technology, Wuhan 430074, China

Received 28 November 2004; accepted 20 April 2005

Abstract

Polymer/carbon nanotube (CNT) composites are expected to have good processability characteristics of the polymer and excellent functional properties of the CNTs. The critical challenge, however, is how to enhance dispersion and alignment of CNTs in the matrix. Here, we review recent progress and advances that have been made on: (a) dispersion of CNTs in a polymer matrix, including optimum blending, in situ polymerization and chemical functionalization; and (b) alignment of CNTs in the matrix enhanced by ex situ techniques, force and magnetic fields, electrospinning and liquid crystalline phase-induced methods. In addition, discussions on mechanical, thermal, electrical, electrochemical, optical and super-hydrophobic properties; and applications of polymer/CNT composites are included. Enhanced dispersion and alignment of CNTs in the polymer matrix will promote and extend the applications and developments of polymer/CNT nanocomposites. # 2005 Elsevier B.V. All rights reserved.

Keywords: Polymer nanocomposites; Carbon nanotubes; Dispersion; Alignment; Applications

1. Introduction

The discovery of carbon nanotubes can be traced back to the origin of fullerene chemistry (buckyball, C 60 ) in 1985 [1]. Fullerenes have provided an exciting new insight into carbon nanostructures built from sp 2 carbon units based on geometric architectures. In 1991, Iijima [2] discovered carbon nanotubes (CNTs) that are elongated fullerenes where the walls of the tubes are hexagonal carbon and often capped at each end. There are two types of CNTs: multi-walled carbon nanotubes (MWCNTs) and single-walled carbon nanotubes (SWCNTs). The former consists of two or more concentric cylindrical shells of graphene sheets coaxially arranged around a central hollow core with interlayer separations as in graphite. In contrast, SWCNT comprises a single graphene cylinder. Both SWCNTs and MWCNTs have physical characteristics of solids and are micro-crystals with high aspect ratios of 1000 or more, although their diameter is close to molecular dimensions. Table 1 shows theoretical and experimental properties of carbon nanotubes [3,4]. From Table 1, it is clear that CNTs have unique mechanical, electrical, magnetic, optical and thermal properties. In some special applications, such as space explorations, high-performance lightweight structural materials are required, and they can be developed by adding CNTs to polymers or other matrix materials. Moreover, although graphite is a semi-metal, CNTs can be either metallic or

* Corresponding author. Tel.: +61 2 9351 2290; fax: +61 2 9351 3760. E-mail address: mai@aeromech.usyd.edu.au (Y.-W. Mai).

0927-796X/$ – see front matter # 2005 Elsevier B.V. All rights reserved.

doi:10.1016/j.mser.2005.04.002

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Table 1 Theoretical and experimental properties of carbon nanotubes

Property

CNTs

Graphite

Specic gravity

0.8 g/cm 3 for

SWCNT;

2.26

g/cm 3

1.8

g/cm 3 for MWCNT (theoretical)

 

Elastic modulus

1 TPa for SWCNT; 0.31 TPa for MWCNT

1 TPa (in-plane)

Strength

50500 GPa for SWCNT; 1060 GPa for MWCNT 550 mV cm

Resistivity

50 mV cm (in-plane) 3000 W m 1 K 1 (in-plane), 6Wm 1 K 1 (c-axis)

Thermal conductivity

3000

W m 1 K 1 (theoretical)

Magnetic susceptibility

Thermal expansion

Thermal stability Specic surface area

22 10 6 EMU/g (perpendicular with plane),

0.5 10 6 EMU/g (parallel with plane)

Negligible (theoretical)

>700 8 C (in air); 2800 8 C (in vacuum) 1020 m 2 /g

1 10 6 K 1 (in-plane),

29 10 6 K 1 (c-axis)

450650 8 C (in air)

semi-conducting due to the topological defects from the fullerene-like end caps in CNTs (pentagons in

a hexagonal lattice). Thus, the physico-mechanical properties of CNTs are dependent upon their

dimensions, helicity or chirality. The syntheses, structures, properties and applications of CNTs have been discussed in several books [5,6]. The superior properties of CNTs offer exciting opportunities for new composites. NASA has invested large sums of money to develop carbon nanotube-based composites for applications such as the Mars mission [6]. Recently, polymer/CNT composites have attracted considerable attention owing to

their unique mechanical, surface and multi-functional properties, and strong interactions with the matrix resulting from the nano-scale microstructure and extremely large interfacial area. Wagner et al. [7] experimentally studied the fragmentation of MWCNTs embedded within thin polymeric lms under both compressive and tensile strains. They found that the polymer/CNTinterfacial shear stress is of the order of 500 MPa, which is much larger than traditional ber composites. It suggests good bonding between CNTs and polymer matrix [8]. However, CNTs are easy to agglomerate, bundle together and entangle, leading to many defect sites in the composites, and limiting the efciency of CNTs on polymer matrices [9]. Salvetat et al. [10] studied the effect of dispersion of CNTs on the mechanical properties of polymer/CNT composites, and found that poor dispersion and rope-like entanglement of CNTs led to drastic weakening

of the composites. Thus, alignment of CNTs in the matrix has a predominant role on the mechanical and

functional properties of polymer/CNT composites [11,12]. To-date, the main challenges are to improve

the dispersion and alignment of CNTs in a polymer matrix when processing these nanocomposites. Recently, Thostenson et al. [13] reviewed CNTs and their composites. Our review given below is complementary to theirs and we focus on recent progress made towards the improvement of dispersion and alignment of CNTs in polymer matrices. Also, thermalphysicalmechanical properties and applications of polymer/CNT composites are discussed.

2. Enhancement of dispersion of CNTs in polymer matrices

To maximize the advantage of CNTs as effective reinforcements in high strength composites, they should not form aggregates and must be well dispersed to prevent slippage [14]. There are several techniques to improve the dispersion of CNTs in polymer matrices, such as by optimum physical blending, in situ polymerization and chemical functionalization.

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2.1. Optimum physical blending

The widely used compounding technique to prepare conventionally lled polymers is still the most convenient and practical way when nano-sized llers are considered to replace micron-sized llers for high-performance polymers. But the dispersion of nano-llers in polymer matrix is more difcult than that of micro-llers due to the strong tendency to agglomerate for the nano-llers. For polymer/CNT composites, the high power dispersion methods, such as ultrasound and high speed shearing, are the simplest and most convenient to improve the dispersion of CNTs in a polymer matrix. For example, Qian et al. [9] made use of a simple solution-evaporation method assisted by high energy sonication to prepare polystyrene (PS)/MWCNT composite lms, in which MWCNTs were dispersed homogeneously in the PS matrix. Similarly, Sandler et al. [15] dispersed CNTs in epoxy under high speed stirring (2000 rpm) for 1 h, and proved that intense stirring was an effective process to achieve dispersed CNTs uniformly in epoxy. Besides, adding a proper compatibilizer to polymer/ CNT composites is also another efcient method. Xie et al. [16] prepared polypropylene (PP)/CNT composites compatibilized with maleic anhydride grafted styrene(ethylene-co-butylene)styrene copolymer (MA-SEBS) by using a combination of ball milling and melt mixing. In Fig. 1, the viscosity of PP melts increases with CNTs loading but appears to atten beyond 5 wt.%. When MA-SEBS is added to PP/CNT composites, the melt viscosity of PP/CNT/MA-SEBS composites is further increased. Also, the surface electrical resistance of PP/CNT/MA-SEBS composites in Fig. 2 shows that CNTs increase the electrical conductivity of these nanocomposites, and the addition of MA-SEBS improves further their electrical conductivity. Thereby, the static electrical charges on the surface of the nanocomposites are easy to remove. Thus, the anti-static property of the nanocomposite is improved. These results conrm that MA-SEBS acts as a compatibilizer to enhance formation of a perfect percolation network and dispersion of CNTs in the matrix. Figs. 3 and 4 show that CNTs reinforce the PP matrix due to their large aspect ratio and high stiffness, but the ductility for PP/CNT composites is very low, Table 2. MA-SEBS improves the interaction and interfacial adhesion between CNTs and PP, and thus improves the tensile strength and ductility but reduces the stiffness of the PP/ CNT/MA-SEBS composites. In a further study on ultra-high molecular weight polyethylene (UHMWPE)/CNT composites, Xie et al. [17] have also conrmed that MA-SEBS is an effective compatibilizer, enhances the dispersion of CNTs in the UHMWPE matrix, and speeds up crystallization of the UHMWPE phase. Similarly, Jin et al. [18] coated MWCNTs by poly(vinylidene uoride) (PVDF) and then melt-blended

by poly(vinylidene fl uoride) (PVDF) and then melt-blended Fig. 1. Relationship between torque and CNT content

Fig. 1. Relationship between torque and CNT content for PP/CNT composite melt with and without MA-SEBS. After [16].

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/ Materials Science and Engineering R 49 (2005) 89 – 112 Fig. 2. Relationship between surface

Fig. 2. Relationship between surface resistance and CNT content for PP/CNT composite melt with and without MA-SEBS. After [16].

with poly(methyl methacrylate) (PMMA). PVDF was found to be a compatibilizer and assist dispersion of MWCNTs in PMMA and served as an adhesive to increase their interfacial bond strength, hence greatly improving the mechanical properties of PMMA/MWCNT composites. Additionally, surfactants can be used as a dispersing agent to improve the dispersion of CNTs in processing polymer/CNT composites. Gong et al. [19] used a non-ionic surfactant, polyoxyethylene- 8-lauryl, as a processing aid for epoxy/CNT composites due to the strong interactions between carbon of CNTs and the hydrophobic segment of the surfactant via van der Waals forces, as well as epoxy and the hydrophilic segment of the surfactant via hydrogen bonding. The homogeneous dispersion of CNTs in epoxy improved the thermomechanical properties of the composites. With only 1 wt.% CNTs in the epoxy/CNT composites, the glass transition temperature was increased by 25 8C (from 63 to 88 8 C) and the elastic modulus by over 30%. In sum, good dispersion of CNTs in polymer matrices can be achieved by means of high power dispersion, compatibilizer, polymer-assisted melt blending, and surfactants. We believe the addition of

melt blending, and surfactants. We believe the addition of Fig. 3. Relationship between modulus and CNT

Fig. 3. Relationship between modulus and CNT content for PP/CNT composite melt with and without MA-SEBS. After

[16].

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Science and Engineering R 49 (2005) 89 – 112 93 Fig. 4. Relationship between tensile strength

Fig. 4. Relationship between tensile strength and CNT content for PP/CNT composite melt with and without MA-SEBS. After [16].

compatibilizers, surfactants, etc., in conjunction with melt blending is most effective and will be widely used to enhance the dispersion and interfacial bonding of many polymer/CNT composites.

2.2. In situ polymerization

To improve the processability, electrical, magnetic and optical properties of CNTs, some conjugated or conducting polymers are attached to their surfaces by in situ polymerization. Tang and Xu [20] synthesized poly(phenylacetylene)-wrapped carbon nanotubes (PPA-CNTs), which were soluble in organic solvents, such as tetrahydrofuran, toluene, chloroform and 1,4-dioxane. Meanwhile, the fullerene tips and graphene sheets of CNTs may undergo nonlinear optical (NLO) absorption processes, and the cylindrical bodies of CNTs with a high aspect ratio may also function as light scattering centers. Both NLO absorption and light scattering of CNTs protect dramatically the PPA chains from being photo-degraded under severe laser irradiation. Therefore, PPA-CNTs show strong photo-stabilization effect. It is interesting that PPA-CNTs can be macroscopically processed, and shearing of their solutions readily aligns CNTs along the applied mechanical force direction. Fan et al. [21] synthesized conducting polypyrrole-coated carbon nanotubes (PPY-CNTs), and found that the magnetization of PPY-CNTs is the sum of the two components, PPY and CNTs. Star et al. [22] synthesized poly(metaphenylenevinylene)-wrapped single-walled carbon nanotubes (PmPV- SWCNTs), and UVvis absorption spectra conrmed pp interactions between SWCNT and fully conjugated PmPV backbone. The results indicate that the photo-excited PmPV has a dipole moment that alters the local electric eld at the surface of SWCNTs. Cochet et al. [23] synthesized polyaniline (PANI)/MWCNT composites by in situ polymerization in the presence of MWCNTs. Their results reveal the site-selective interaction between the quinoid ring of PANI and MWCNTs, thus opening the way for charge transfer processes, and improving the

Table 2 Elongation-at-break for PP/CNT and PP/CNT/MA-SEBS composites

CNT content (%) PP matrix % PP90/MA-SEBS10 matrix %

0

0.5

1.0

2.0

5.0

10

>146

5.69

7.59

9.99

11.73

10.04

>146

25.2

30.18

59.06

54.30

39.80

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electric properties of PANI/MWCNT composites. Xiao and Zhou [24] deposited polypyrrole (PPY) or poly(3-methylthiophene) (PMeT) on the surfaces of the MWCNTs by in situ polymerization. The Faraday effect of the conducting polymer enhances the performance of super-capacitors with MWCNTs deposited with the conducting polymer. High-performance structural composites based on CNTs and polymer have also been prepared by in situ polymerization. Jia et al. [25] rst synthesized PMMA/CNT composites by in situ polymer- ization of MMA with CNTs present. Later, Park et al. [26], Velasco-Santos et al. [27], and Jang et al. [28] polymerized in situ polyimide (PI)/SWCNT, PMMT/MWCNT, and liquid crystalline epoxide (LCE)/MWCNT composites. PI/SWCNT composite lms were anti-static and optically transparent with signicant conductivity enhancement (10 orders) at a very low loading (0.1 vol.%). For PMMA/ MWCNT composites containing 1 wt.% MWCNT, the storage modulus at 90 8C is increased by an outstanding 1135%, and the glass transition temperature is raised exceptionally by 40 8 C. For LCE/ MWCNT composites containing 1 wt.% MWCNT, the nematic phase temperature of liquid crystalline epoxide (LCE) is decreased. When the MWCNTs are modied by chemical surface oxidation (oxMWCNT), this LCE nematic phase temperature of LCE/oxMWCNT composites is shifted to a lower temperature. This is because the molecular alignment of the LCE for evolution of the LC phase is partially restricted by the interaction between the MWCNTs and LCE. In LCE/oxMWCNT composites, the LC domains form at a lower temperature.

2.3. Chemical functionalization

In addition, the surfaces of CNTs have to be chemically functionalized (including grafting copolymerization) to achieve good dispersion in polymer/CNT composites and strong interface adhesion between surrounding polymer chains, even though the interface area is very large. CNTs are assembled as ropes or bundles, and there are some catalyst residuals, bucky onions, spheroidal fullerenes, amorphous carbon, polyhedron graphite nano-particles, and other forms of impurities in as- grown CNTs. Thus, purication, ‘‘cutting’’ or disentangling, and activation treatments are needed before chemical functionalization.

2.3.1. Purification The rst method to purify MWCNTs is based on oxidation [4,29], which is observed to occur preferentially at the nanotube ends and on nano-particles that have a high concentration of topological defects. MWCNTs are puried by burning away of these tube ends, nano-particles and amorphous carbon at >700 8C in air or oxygen. However, the yield is extremely low (<5%). Hiura et al. [30] puried CNTs by a mixture of concentrated sulfuric acid and potassium permanganate, but this is still not proven to be a good method for large-scale separation. Tohji et al. [31] suggested a purication method that included hydrothermal treatment along with extraction of fullerenes, thermal oxidation and dissolution in 6 M hydrochloric acid. To prevent CNTs from being destroyed during purication, Bonard et al. [32], Bandow et al. [33] and Duesberg et al. [34] dispersed the CNTs in polar solvents assisted by surfactants, such as sodium dodecyl sulfate, followed by micro-ltration and size exclusion chromatography. These methods may be possible to separate CNTs in selected sizes without destruc- tion. Yamamoto et al. [35] used AC electrophoresis to treat the CNTs dispersed in iso-propyl alcohol. They found that the separation from impurity particles depended on the frequency of the applied eld. At the same time, it is worth noting that CNTs align along the electric eld direction. Coleman et al. [36] and McCarty et al. [37] used a functional organic polymer, poly(m-phenylene-co-2,5-dioctoxy-p- phenylenevinylene) (PmPV), as a ltration system to purify CNTs. They found that the solution of PmPV is capable of suspending nanotubes indenitely whilst the accompanying amorphous graphite

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separates out. Although these novel techniques are only suited to treat small amounts of the nanocomposite, they are denite advances to manipulate CNTs. Liu et al. [38] developed a purication method that consisted of reuxing in 2.6 M nitric acid and re-suspending CNTs in pH 10 water with surfactant followed by ltration with a cross-ow ltration system. This may be an efcient method to purify CNTs owing to the combined advantages of the chemical and physical methods.

2.3.2. ‘‘ Cutting ’’ or disentangling CNTs are long and entangled as ropes or in bundles. The ‘‘cutting’’ process is necessary for CNTs to disentangle, open up the tubes and provide active sites for chemical functionalization. Liu et al. [38] chose a 3:1 mixture of concentrated sulfuric acid and nitric acid to ‘‘cut’’ CNTs into 150 nm in length, Fig. 5. The short and open-ended CNTs are then treated by a 4:1 mixture of concentrated sulfuric acid and 30% aqueous hydrogen peroxide. Thus, more functional groups such as carboxylic acid and hydroxyl groups are formed on the CNT surface. Later, Shaffer et al. [39,40] used a 3:1 mixture of concentrated sulfuric acid and nitric acid to ‘‘cut’’ CNTs and produced an electrostatic stabilized dispersion of CNTs in water with an average length of 1.1 mm, Fig. 6. Chen et al. [41] also obtained disentangled SWCNTS with an average length >1 mm. Obviously, it is necessary to control and adjust the processing conditions to obtain short CNTs with different length.

2.3.3. Activation treatments In general, carboxylic acid and hydroxyl groups could be formed on the surface or open ends of CNTs during the oxidation process by oxygen, air, concentrated sulfuric acid, nitric acid and 30% aqueous hydrogen peroxide, and concentrated sulfuric acid and its mixture [38]. To further activate the carboxylic acid groups on the surface of CNTs, they are converted into acyl chloride groups by reaction with thionyl chloride at room temperature [38]. Wu et al. [42] converted the hydroxyl groups on the surface of CNTs into hydroxymethyl groups (CH 2 OH) by the formalization reaction with formaldehyde as below:

by the formalization reaction with formaldehyde as below: Fig. 5. Tapping mode AFM images of ‘‘
by the formalization reaction with formaldehyde as below: Fig. 5. Tapping mode AFM images of ‘‘

Fig. 5. Tapping mode AFM images of ‘‘cut’’ CNTs by Liu et al. After [38].

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/ Materials Science and Engineering R 49 (2005) 89 – 112 Fig. 6. Tapping mode AFM

Fig. 6. Tapping mode AFM images of ‘‘cut’’ CNTs by Chen et al. [41].

By using a redox initiating system, which consists of cerium ions and hydroxymethyl groups (CH 2 OH) on the surface of CNTs, free radical graft polymerization of vinyl monomers could occur. Zhou [43] also converted carboxylic acid and hydroxyl groups on the surface of CNTs into vinyl groups (CH CH 2 ) by reaction with 3-isopropenyl-a,a-dimethylbenzyl isocyanate:

with 3-isopropenyl- a , a -dimethylbenzyl isocyanate: Because of the presence of these vinyl groups (

Because of the presence of these vinyl groups (CH CH 2 ) on CNTs, some vinyl monomers could be grafted on the surface of CNTs. Besides the above activation methods, Chen et al. [44] activated CNTs surface by plasma modication. Acetaldehyde and ethylenediamine vapors were plasma polymerized on the surface of CNTs, thereby introducing active aldehyde (CHO) and amino (NH 2 ) groups. Moreover, Mickelson et al. [45] added functional groups to the side walls of SWCNTs by uorine at elevated temperatures. These uorinated SWCNTs could be solvated in alcohols and reacted with other species, particularly strong nucleophiles, such as alkylithium reagents. Mawhinney et al. [46] reported that carboxylic acids, anhydrides, quinines, and esters can also be introduced to CNTs by ozone oxidation. Bahr et al. [47] successfully functionalized SWCNTs with electrochemical reduction of aryl diazonium compounds, resulting in a free radical that could attach to the SWCNT surface. Georgakilas et al. [48] discovered a method to functionalize SWCNTs with 1,3-dipolar cycloaddition of azomethine ylides. Chen et al. [49] and Holzinger et al. [50] functionalized SWCNTs by direct additions based on nucleophilic carbenes, cycloaddition of nitrenes and radicals. These functionaliz- ing methods have been reviewed by Bahr and Tour [51].

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2.3.4. Chemical functionalization Riggs et al. [52] and Lin et al. [53] synthesized polymer grafted CNTs based on acylated CNTs with poly(propionylethylenimine-co-ethylenimine) (PPEI-EI), poly(vinyl acetate-co-vinyl alcohol) (PVA-VA) and poly(vinyl alcohol) (PVA), respectively. They found that PVA grafted CNTs were soluble in PVA solution, PVA-CNT nanocomposite lms so-formed are of high optical quality without any observable phase separation. The result indicates that chemical graft functionalization of CNTs by matrix polymer was an effective way to achieve homogeneous dispersion for high-performance polymer/CNT nanocomposites. Cao et al. [54] synthesized dodecylamine grafted CNTs with dodecylamine and acylated CNTs, and found that these grafted CNTs were miscible with poly- vinylbutyral (PVB) caused by the interaction between functional groups in polymer and long dodecylamine chains attached to the ends of CNTs. Also, Hill et al. [55] functionalized CNTs by the grafting reaction between carboxylic acid-bound CNTs and poly(styrene-co-p-(4-(4 0 -vinylphe- nyl)-3-oxabutanol)) (PSV). These PSV-grafted CNTs are soluble in common organic solvents and are homogeneously dispersed in the PS matrix. This offers an example for the widely held expectation that the solubility of CNTs will enable the preparation of desirable polymer/CNT nanocomposites. Meanwhile, Mitchell et al. [56] synthesized 4-(10-hydroxydecyl) benzoate-SWCNTs by in situ reaction of organic diazonium compounds, and prepared the composites based on the functionalized SWCNTs and PS. These nanocomposites show a percolated SWCNT network structure at 1 vol.% nanotubes, whilst for the unfunctionalized SWCNT/PS nanocomposites this occurs at twice SWCNTs loading. The reason is because the chemical functionalization of CNTs enhances their interaction with the polymer matrix and improves their dispersion in the composites. Recently, Viswanathan et al. [57] reported that introduction of carbanions on the SWCNTs surface by treatment with an anionic initiator served to exfoliate bundles of SWCNTs, and provided initiating sites for polymerization of styrene. Qin et al. [58] grafted poly(n-butyl methacrylate) (PBMA) brushes on the ends and sidewalls of SWCNTs by using atom transfer radical polymerization (ATRP). Kong et al. [59] successfully functionalized MWCNTs with various contents of poly(methyl methacrylate) layers by in situ ATRP grafting polymerization (Fig. 7). In summary, chemical functionalization can promote good dispersion in the polymer/CNT composites and will play a dominant role in future development and applications of these nano- composites.

3. Alignment of CNTs in polymer matrix

In common with conventional ber composites, both mechanical properties, such as stiffness and strength, and functional properties, such as electrical, magnetic and optical properties, of polymer/ CNT nanocomposites are linked directly to the alignment of carbon nanotubes in the matrix. This is a topic that has received much recent attention. Andrews et al. [60] prepared drawn isotropic petroleum

Andrews et al. [60] prepared drawn isotropic petroleum Fig. 7. Schematic of functionalized MWCNTs with PMMA

Fig. 7. Schematic of functionalized MWCNTs with PMMA layers by in situ ATRP. After [59].

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pitch/SWCNT composite bers with 5 wt.% SWCNTs. The tensile strength, modulus and electrical conductivity of these pitch composite bers are enhanced by 90, 150 and 340%, respectively, due to the orientation of the SWCNTs. These results conrm a new efcient method to develop high- performance carbon ber composites and the interest now is to develop effective techniques to align the CNTs in the polymer matrix.

3.1. Ex situ alignment of CNTs

‘‘Ex situ’’ is used to mean that the CNTs are aligned in advance, then compounded with the polymer matrix by in situ polymerization of some monomers. Feng et al. [61] prepared well-aligned polyaniline (PANI)/MWCNT composite lms by in situ polymerization of aniline in the presence of aligned MWCNTs, as shown in Fig. 8. It offers a general route for controlled assembly of organized nanocomposites and devices. Obviously, the challenge for the method is how to align CNTs in the rst place. These methods are described below.

3.1.1. Filtration

de Heer et al. [62] dispersed CNTs in ethanol, and prepared aligned CNT lms by drawing the suspension through a 0.2 mm-pore ceramic lter and transferring the uniformly aligned CNTs on the lter to a polymer surface. Later, Watters et al. [63], Casavant et al. [64] and Fischer et al. [65] prepared thick macroscopic membranes (10 mm thick, 125 cm 2 surface area) of aligned SWCNTs via high-pressure ltration of aqueous surfactant-suspended SWCNTs in a magnetic eld of 7 T.

3.1.2. Plasma-enhanced chemical vapor deposition (PECVD)

Ren et al. [6668] synthesized large arrays of well-aligned CNTs on glass by direct-current power generated plasma-enhanced chemical vapor deposition (PECVD), where the glass substrate is rst coated with a layer of nickel catalyst. Later, microwave plasma is also used to align CNTs on Si, Ni, and FeNiCr alloy substrates during growth by microwave plasma-enhanced chemical vapor deposition (MPECVD) [6972].

3.1.3. Template

Lie et al. [73] used meso-porous silica containing iron nano-particles embedded in the pores as a template, and synthesized large-scale aligned CNTs by chemical vapor deposition (CVD). The aligned CNTs are easily cleaved along the growth direction of the nanotubes. Later, Li et al. [74] reported that

highly ordered arrays of parallel CNTs were grown by pyrolysis of acetylene on cobalt within a hexagonal close-pack nano-channel alumina template at 650 8 C. Similarly, Sohn et al. [75] synthe- sized well-aligned CNTs and patterned selective grown CNTs with a porous Si substrate and a patterned Fe lm on Si substrate by thermal chemical vapor deposition. Also, Yuan et al. [76] prepared

chemical vapor deposition. Also, Yuan et al. [76] prepared Fig. 8. Schematic of preparing well-aligned PANI/MWCNT

Fig. 8. Schematic of preparing well-aligned PANI/MWCNT composites. After [58].

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highly ordered mono-dispersed CNTs based on self-ordered hexagonal nano-pore alumina templates by thermal decomposition of ethylene, Wang et al. [77] and Wei et al. [78] fabricated 3D controllable aligned CNTs as shown in Fig. 9. Additionally, Schlittler et al. [79] reported the self-assembly of single crystals of SWCNTs using thermolysis of nano-patterned precursors. It is noted that CNTs are useful for downsizing circuit dimensions, especially when the CNTs are aligned, thus paving a way for the development of novel nano-electronic applications. For example, CNT eld effect transistors are fabricated by lithographically applying electrodes to CNTs that are either randomly distributed on a silicon substrate or positioned on the substrate with an atomic force microscope [8082]. Integrated nano-electronic devices involve two or more CNT eld effect transistors and provide the basis for large-scale integration [81,82]. As discussed above, the methods to align CNTs all require porous substrates. However, Ago et al. [83] reported that Co nano-particles chemically synthesized by a reverse micelle method catalyzed the growth of MWCNTs aligned perpendicular to a substrate. Yanagi et al. [84] used highly oriented pyrolytic graphite (HOPG) as a template to prepare self-oriented short SWCNTs deposited on HOPG. Obviously, these methods offer processable approaches to align CNTs arrays over a large area. Summing up, highly ordered CNTs are useful for many applications, such as eld emission displays and sensors, data storage, and light-emitters. This also provides basic techniques to develop well-aligned polymer/CNT composites.

3.2. Force eld-induced alignment of CNTs

Ajayan et al. [85] developed a simple method to produce aligned arrays of CNTs by ‘‘cutting’’ an epoxy/CNT nanocomposite. Their research results demonstrated the nature of rheology in composite media on nanometer scales and ow-induced anisotropy produced by the ‘‘cutting’’ process. The fact that CNTs do not break and are straightened after the cutting process also suggests that they have excellent mechanical properties. However, the orientation of CNTs in epoxy/CNT composite is affected by the thickness of the slices, and the alignment effect becomes less pronounced with increasing slice thickness. Vigolo et al. [86] dispersed SWCNTs in a surfactant solution (sodium dodecyl sulfate, SDS), which was slowly injected through a syringe needle into a PVA solution. Because the latter is more

needle into a PVA solution. Because the latter is more Fig. 9. Schematic of fabricated 3D

Fig. 9. Schematic of fabricated 3D controllable aligned CNTs. After [77].

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viscous than the SWCNT dispersion, and there is a shear contribution in the ow at the tip of the syringe needle, the ow-induced alignment is maintained by the PVA solution, and SWCNTs are rapidly stuck together as they are injected out from the syringe. By pumping the polymer solution from the bottom, meter-long ribbons are easily drawn, and well-oriented PVA/CNT composite bers and ribbons are formed by a simple process. It offers a method to align CNTs by a ow eld. Lin et al. [11] aligned CNTs in composites by uniaxially stretching polymer/CNT composite lms at 100 8C. Haggenmuller et al. [87] prepared PMMA/SWCNT composite lms and bers by melt processing. They found the composite lms showed higher conductivity along the ow direction than perpendicular to it; the elastic modulus and yield strength of PMMA/SWCNT composite bers increased with draw ratio, and SWCNTs in the composite bers are well aligned. Thostenson and Chou [88] prepared PS/MWCNT composite lms by extruding the composite melt through a rectangular die and drawing the lm prior to cooling. Compared with the drawn PS lm, the tensile strength and modulus of the PS/MWCNT composite lms were increased by 137 and 49%, respectively. However, Safadi et al. [89] prepared PS/MWCNT composite lms by spin casting at high speed (2200 rpm) and found that MWCNTs were aligned in specic angles relative to the radial direction: 458 and 135 8 on average. The presence of 2.5 vol.% MWCNTs doubles the tensile modulus, and transforms the lm from insulating to conducting. It is noted that the CNTs have higher orientation than the polymer matrix during melt-drawing of the polymer/CNT composites [90]. Finally, Cooper et al. [91] claimed that they aligned CNTs in PMMA/CNT composites by melt extrusion. It provides an easy and effective method to develop high-performance composites for the materials industry.

3.3. Magnetic eld-induced alignment of CNTs

Kimura et al. [92] were rst to use a high magnetic eld to align MWCNTs in a polyester matrix and obtained electrically conductive and mechanically anisotropic composites. They dispersed MWCNTs in the monomer solution of unsaturated polyester, then applied a constant magnetic eld of 10 T to align the nanotubes. Polymerizing this MWCNT-monomer dispersion under the magnetic eld freezes the alignment of MWCNTs in the polyester matrix. It offers a new method to prepare special composites with anisotropic electric and mechanical properties based on the anisotropic nature of MWCNTs. Choi et al. [12] prepared aligned MWepoxy/CNT nanocomposites under a 25 T magnetic eld. Their thermal and electrical properties along the magnetic eld alignment direction are increased by 10 and 35%, compared with those epoxy/MWCNT nanocomposites without the application of a magnetic eld. As shown in Fig. 10, Takahashi et al. [93] applied a magnetic eld to the processing apparatus, such as a hot-press machine, and prepared polycarbonate (PC)/carbon ber nanocomposites. Based on wide angle X-ray diffraction (WAXD) by a step-scanning method, the orientation coefcients (S) of carbon ber (150 nm) and PC crystallite in the magneto-oriented sample were estimated from the following equations:

S ¼ 2 ð3 cos 2 u 1Þ

1

cos 2 u ¼ R

0

p=2

IðfÞ cos 2 f sin f df

p=2

R

0

IðfÞ sin f df

(1a)

(1b)

where u is the angle between carbon ber or PC crystallite and magnetic direction, and I(F) is the azimuthal intensity distribution. They found the orientation coefcients (S) of the carbon bers and the

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Science and Engineering R 49 (2005) 89 – 112 101 Fig. 10. Optical micrograph (a) and

Fig. 10. Optical micrograph (a) and wide angle X-ray diffraction (WAXD) pattern (b) of PC/carbon ber nanocomposites treated in molten state under a magnetic eld. After [93].

crystallites were 0.64 and 0.65, respectively. Since PC is usually categorized as an amorphous polymer due to its extremely slow crystallization without any additives, these results indicate that CNTs are aligned by the applied magnetic eld which also accelerates the crystallization of PC and the orientation of its crystallites in the magnetic eld direction.

3.4. Electrospinning-induced alignment of CNTs

Electrospinning is an electrostatic method for the fabrication of long organic bers. Recently, the electrospinning process [9499] was used to align CNTs in polymer nanobers, in which a high direct- current (dc) voltage (e.g. 25 kV) is generated between a negatively charged polymer uid and a metallic ber collector for random orientation or nano-scale bril alignment so that a continuous yarn is manufactured along with the ber mats [95]. The process of electrospinning-induced alignment of CNTs is shown in Fig. 11. It is seen that the polyacrylonitrile (PAN)/SWCNT nanobers are smooth and uniform, and SWCNTs are aligned along the direction of the nanobers as shown in Fig. 12. Sen et al. [96] fabricated SWCNT-reinforced polystyrene (PS) nanobers and poly-urethane (PU) membranes using the electrospinning process. They found that the SWCNT bundles are oriented

process. They found that the SWCNT bundles are oriented Fig. 11. Schematic of the electrospinning process.

Fig. 11. Schematic of the electrospinning process. After [95].

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/ Materials Science and Engineering R 49 (2005) 89 – 112 Fig. 12. TEM images of

Fig. 12. TEM images of PAN/SWCNT nanocomposite brils. After [92]. (The average diameter of SWCNTs is 1.3 nm).

parallel to the PS/SWCNT nanober axis. The tensile strength and the modulus of PU/ester functionalized SWCNT composite membranes are enhanced by 104 and 250% as compared to electrospun pure PU membranes. They have also developed a exible approach to the alignment of SWNT that allows their hierarchical assembly using electrospinning, and orientation of SWNT is directionally controllable. Thus, cross-aligned nanobers are shown in Fig. 13 [97]. A theoretical model is presented for the behavior of rod-like particles representing CNTs in electrospinning. Initially, the rods are randomly oriented, but due to the ‘‘sink-like’’ flow in a wedge- like jet they are gradually oriented mainly along the streamlines, so that straight CNTs are sucked into the electrospun jet and become oriented [94].

3.5. Liquid crystalline phase-induced alignment of CNTs

Due to the unique molecular structure of liquid crystals (LC), the liquid crystalline phase is easy to orient along the applied eld, such as force, electric and magnetic elds. Following this principle, Kawasumi et al. [100,101] prepared a nematic low molar mass liquid crystal/clay composite, and used the low molar mass LC to induce the orientation of clay layers along the direction of low-frequent electric eld. As shown in Fig. 14, when a low frequency electric eld was applied to the LC/clay system, the clay layers aligned parallel to the electric eld. Even after the electric eld was switched off, the oriented clay layers maintained their orientation due to their bulkiness. Recently, we prepared liquid crystalline copolyester/clay nanocomposites [102]. Under shear, the LCP domains are stretched into ultra-ne oriented LCP/clay bands, whose width is about 140 nm.

fi ne oriented LCP/clay bands, whose width is about 140 nm. Fig. 13. AFM images of:

Fig. 13. AFM images of: (a) cross-aligned SWNTs/PVP composite bers; (b) cross-aligned SWNT array. After [97].

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Science and Engineering R 49 (2005) 89 – 112 103 Fig. 14. Schematic of LC/clay composite

Fig. 14. Schematic of LC/clay composite system at different states. After [101].

Simultaneously, the exfoliated and randomly distributed clay layers are well aligned along the shearing direction induced by the LCP. Fig. 15 is AFM image of the sheared LCP/clay nanocomposite. It can be seen that exfoliated clay layers are oriented along the force eld induced by LCP, and there are no exfoliated clay layers in the transverse direction of the ultra-ne oriented LCP/clay band. This technique thus provides an efcient route to prepare high-performance structural polymer nanocom- posites. Similarly, Lynch and Patrick [103] oriented the nematic low molar mass LCs in an electric eld and used these matrices to align the suspended MWCNTs. As shown in Fig. 16, the MWCNTs were oriented along the direction of applied electric eld, and a 1.8 V/mm electric eld was strong enough to overcome the orientational effect of the grooves, which were perpendicular to the electric eld. Song et al. [104] rst demonstrated the nematic liquid crystallinity of MWCNTs in water. Examination of a series of aqueous dispersions with different MWCNTs concentrations showed a phase transition from isotropic to a Schlieren texture typical of lytropic nematic liquid crystals above a critical concentration of 4.3% by volume. Later, Mrozek et al. [105] reported that the ordered SWCNTs could be used to organize the liquid crystalline polymers (LCPs) via kinetic seeding of homogeneous liquid crystal domains from an LCP melt. Based on these reported results, we believe that CNTs in the liquid crystalline state can improve both liquid crystallinity and orientation of LCPs. It is obvious that the alignment of CNTs will induce anisotropy in structural, mechanical, electrical and thermal properties of polymer/CNT nanocomposites. For example, the ratios of electrical conductivity and thermal conductivity between the aligned and transverse directions of aligned MWCNT/epoxy nanocomposites are 1.4 and 1.9 corresponding, respectively, to the applica-

are 1.4 and 1.9 corresponding, respectively, to the applica- Fig. 15. AFM image of LCP/clay nanocomposite

Fig. 15. AFM image of LCP/clay nanocomposite containing 5 wt.% clay.

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/ Materials Science and Engineering R 49 (2005) 89 – 112 Fig. 16. AFM image of

Fig. 16. AFM image of LC/MWCNTs under 1.8 V/mm electric eld (5 mm 5 mm). After [103].

tion of a 15 and 25 T magnetic eld [12]. The temperature-dependent anisotropy is, however, very weak. Research on anisotropy of aligned polymer/CNT nanocomposites has just begun and there is little published work to-date. We believe the anisotropic mechanical, thermal and electric properties of polymer/CNT nanocomposites will be extremely useful in many structural and functional materials and devices.

4. Properties and applications of polymer/CNT nanocomposites

CNTs have been proposed for many potential applications including conductive and high- strength composites; energy storage and energy conversion devices; sensors; eld emission displays and radiation sources; hydrogen media; and nanometer-sized semi-conductor devices, probes, and interconnects, etc. [81]. Polymer/CNT nanocomposites are expected to have good processability of the polymers and high mechanical and functional properties of the CNTs. Continuing advances on dispersion and alignment of CNTs in polymer matrices will further promote developments in and expand the range of applications of these nanocomposites.

4.1. Mechanical properties

Incorporation of CNTs into a polymer matrix can potentially provide structural materials with dramatically increased modulus and strength. For example, adding 1 wt.% MWCNTs in the PS/ MWCNT composite lms by the solution-evaporation method, results in 3642 and 25% improve- ments in tensile modulus and break stress, respectively [9]. Biercuk et al. [106] have observed a monotonic increase of resistance to indentation (Vickers hardness) by up to 3.5 times on adding 2 wt.% SWCNTs in epoxy resin. Cadek et al. [107] also found that adding 1 wt.% MWSNTs to polyvinyl alcohol (PVA) increased the modulus and hardness by 1.8 times and 1.6 times, respectively. As discussed in Sections 2 and 3, the homogeneous dispersion and alignment of CNTs in polymer matrices are signicant to enhance the effectiveness of reinforcement. For example, for PMMA/ MWCNT composites containing 1 wt.% MWCNT, the storage modulus at 90 8C is increased by an

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outstanding 1135% due to the homogeneous dispersion enhanced by in situ polymerization [27]. The tensile strength and modulus of melt drawn PS/MWCNT composite lms are, respectively, increased by 137 and 49% compared to the drawn PS lm [88]. In general, inclusion of CNTs in polymer matrices leads to reductions in impact toughness of composites [108,109] and there is an additional effect due to the orientation of the CNTs [110]. However, opposite effects are also reported, which claim an improvement in toughness [111]. For example, Ruan et al. [112] have shown that, with 1 wt.% MWCNTs in UHMWPE, the toughness (that is, area under tensile stressstrain curve) was increased 150% and ductility by 104% due to the enhanced chain mobility in UHMWPE induced by MWCNTs. Similarly, Weisenberger et al. [113] found that addition of 1.8 vol.% MWCNTs enhanced the energies to yield and to break by about 80% for an aligned polyacylonitrile/MWCNT ber. Dalton et al. [114] prepared super-tough polyvinyl alcohol/SWCNT composite ber containing 60 wt.% SWCNTs caused by slippages between SWCNT bundles. Gorga and Cohen [110] proposed a failure mechanism, in which the orientation of MWCNTs (normal to the direction of craze/crack growth) enabled them to toughen PMMA by crake-wake bridging. Assouline et al. [115] found that addition of 1 wt.% MWCNTs in polypropylene (PP) matrix increased the composite toughness due to the brillar crystal structure of PP induced by MWCNTs. Recently, Blake et al. [116] modied butyl-lithium-functionalized MWCNTs with chlorinated polypropylene (CPP) to produce nanotubes covalently bonded to chlorinated polypropylene (MWCNT/CPP), and compounded the CPP/MWCNT with the CPP/tetrahydrofuran (THF) solution to obtain CPP/MWCNT composites. They claimed that as the MWCNT content was increased to 0.6 vol.%, the modulus increased by three times compared to pure CPP from 0.22 to 0.68 GPa, and both tensile strength and toughness (measured by the area under the stressstrain curve) increased by 3.8 times (from 13 to 49 MPa) and 4 times (from 27 to 108 J/g), respectively. These results show that the covalent functionalization of CNTs enables both efcient dispersion and excellent interfacial stress transfer [116]. A few words of caution should be made here on the denition and measurement of toughness of CNTs-polymer nanocomposites. From the above, it is seen, for convenience, that toughness is variably dened by the Izod impact strength (J/m) or the area under the tensile stressstrain curve (J/m 3 ) depending on the background and experience of the researchers. However, these two parameters do not give the correct toughness values. For proper toughness measurement techniques, the readers should refer to [117].

4.2. Thermal properties

The addition of CNTs could increase the glass transition, melting and thermal decomposition temperatures of the polymer matrix due to their constraint effect on the polymer segments and chains. It is important to improve the thermal endurance of polymer composites. Thus, with a surfactant, adding 1 wt.% CNTs to epoxy increases the glass transition temperature from 63 to 88 8C [19]. Similarly, with 1 wt.% well-dispersed SWCNTs, the glass transition temperature of PMMA is increased by 40 8 C [27]. Because CNTs act as nucleation sites in the matrix, their inclusion enhances polymer crystallization and increases the melting temperature [107]. Kashiwagi et al. [118] found that the thermal decomposition temperature of polypropylene (PP) at peak weight loss in nitrogen was increased by 12 8C with 2 vol.% MWCNTs, and that MWCNTs signicantly reduced the PP heat release rate making it as effective a re-retardant as PP/PP-g-MA/clay. Also, the incorporation of CNTs could improve the thermal transport properties of polymer composites due to the excellent thermal conductivity of CNTs. This offers an opportunity for polymer/ CNT composites for usages as printed circuit boards, connectors, thermal interface materials, heat

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sinks, lids and housings, and high-performance thermal management from satellite structures down to electronic device packaging. Biercuk et al. [106] found that 1 wt.% un-puried SWCNTs in epoxy showed a 70% increase in thermal conductivity at 40 K, rising to 125% at room temperature. Choi et al. [12] observed that the thermal conductivity of epoxy increased by up to 300% with 3 wt.% SWCNTs. It is noted that aligned MWCNTs will further improve the thermal conductivity. Compared to the epoxy/MWCNT nanocomposites without an applied magnetic eld, the alignment of MWCNTs under a 25 T magnetic eld has lead to a 10% increase in thermal conductivity [12].

4.3. Electrical and electrochemical properties

The rst realized major commercial application of carbon nanotubes is their use as electrically conducting components in polymer composites [81]. It is reported that GE Plastics has been using CNTs in a poly(phenylene oxide) (PPO)/polyamide (PA) blend for automotive mirror housings for Ford [119] to replace conventional micron-size conducting llers, which would require loadings as high as 15 wt.% to have a satisfactory anti-static property but which would impart poor mechanical properties and a high density to the composite. Coleman et al. [120] showed that the electric conductivity of poly(p-phenlyenevinylene-co-2,5- dioctoxy-m-phenylenevinylene) (PMPV) polymer could be dramatically increased by up to ten orders of magnitude when 8 wt.% CNTs were added, indicative of percolating behavior [121]. The in situ polymerized polyimide (PI)/SWCNT composite lms exhibited signicant conductivity enhancement (10 orders) at a very low loading (0.1 vol.%) without signicantly sacricing optical transmission [26]. Since their mechanical properties and thermal stability were also improved by addition of SWCNTs, they are potentially useful in a variety of aerospace and terrestrial applications. Again, alignment of CNTs affects the electrical properties of polymer/CNT nanocomposites. Thus, in epoxy/MWCNT nanocomposites with MWCNTs aligned under a 25 T magnetic eld leads to a 35% increase in electric conductivity compared to those similar composites without magnetic aligned CNTs [12]. Improve- ments on the dispersion and alignment of CNTs in a polymer matrix could decrease the percolation threshold value [12,15,122]. Recently, super-capacitors are attracting great attention because of their high capacitance and potential applications in electronic devices. It has been reported that the performance of super- capacitors with MWCNTs deposited with conducting polymers as active materials is greatly enhanced compared to electric double-layer super-capacitors with CNTs due to the Faraday effect of the conducting polymer [24]. Besides these, polymer/CNT nanocomposites could have many potential applications in electrochemical actuation, electromagnetic interference shielding (EMI), wave absorption, electronic packaging, self-regulating heater, and PTC resistors, etc. [123,124].

4.4. Optical and photovoltaic properties

Nonlinear optical organic materials, such as porphyrins, dyes and phthalocyanines, provide optical limiting properties for photonic devices to control light frequency and intensity in a predictable manner. However, these are narrow band optical materials. Carbon nanotubes, both SWCNTs and MWCNTs, have been studied [2]. OFlaherty et al. [125] noted that the optical limit saturated at carbon nanotubes exceeding 3.8 wt.%, relative to the polymer mass. Goh et al. [126] found that the aqueous MWCNT suspension showed only week optical limit towards laser at 532 nm operating at 20 Hz, but its mixture with double-C 60 -end-capped poly(ethylene oxide) (FPEOF) solution displayed enhanced optical limiting responses at 532 and 1064 nm. Polymer/CNT composites could also be used to protect human eyes, optical elements, optical sensors and optical switching. Chen et al. [127]

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demonstrated the ultra-fast optical switching property of polyimide (PI)/SWCNT composites at 1.55 mm. Another potentially important application of CNTs is in polymer-based light-emitting devices. The advantages for organic light-emitting diodes (OLEDs) based on conjugated polymers are low cost, low operating voltage, excellent processability and exibility. However, their low quantum efciency and stability have limited their applications and developments. Riggs et al. [52] observed strong luminescence of soluble polymer grafted CNTs. Ago et al. [128] revealed the electronic interaction between CNTs and photo-exited polymers, such as poly(p-phenylene vinylene) (PPV), and proposed ‘‘hole collecting’’ properties of MWCNTs from PPV at the composite interface via the non-radiative energy transfer of singlet excitons from PPV to MWCNTs. Woo et al. [129] found that SWCNTs in poly(m-phenylene vinylene-co-2,5-dioctoxy-p-phenylene vinylene) (PmPV) were responsible for blocking hole transport in the composite by forming hole traps in the polymer matrix induced by image charge effects between SWCNTs and the charge carriers. When the PmPV/MWCNT composite is used as an electron-transport layer in OLEDs based on poly(2,5-dimethoxy-1,4-phenylene- vinylene-2-methoxy-5(2 0 -ethylhexyloxy)-1,4-phenylene-vinylene) (M3EH-PPV), the brightness of OLEDs is greatly enhanced due to the low potential barrier reduced by the incorporation of CNTs in the PmPV/MWCNT composite [130]. Kim et al. [131] observed that the device qualities, such as external quantum efciency, were improved by 23 times for up to 0.2 wt.% SWCNTs in OLEDs. They ascribed this to the facile hole injection and the polymerSWCNT interactions which stiffened the polymer chains. Subsequently, the better hole transport in the metallic SWCNTpolymer medium induced more efcient single exciton formation at or near the interface region. Besides, CNTs are also widely used in organic photovoltaic devices. Doping with 6 wt.% chemical functionalized MWCNTs by grafting dodecylamine chains, the photosensitivity of oxoti- tanium phthalocyanine (TiOPc) is ve-fold higher than that of un-doped TiOPc when exposed to 570 nm wavelength [54]. It is benecial to design photo-conductive devices with high efciency of charge carrier generation. Clearly, polymer/CNT nanocomposites represent an alternative class of organic semi-conducting materials that are promising for organic photo-voltaic cells and devices with improved performance [132,133].

4.5. Super-hydrophobic properties

Li et al. [134] rst observed the contact angle for water on an aligned CNT lm by the pyrolysis of metal phthalocyanines is about 1288 . After the CNT lm is modied through immersion in a methanol solution of hydrolyzed uoroalkylsilane, the modied aligned CNT lms show super-‘‘amphiphobic’’ properties, the contact angles for water and rapeseed oil on the lm are 171 8 and 1618 , respectively. In

oil on the fi lm are 171 8 and 161 8 , respectively. In Fig. 17.

Fig. 17. SEM images of aligned CNT lms by pyrolysis of metal phthalocyanines: (a) top view; and (b) cross-sectional view. After [134].

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/ Materials Science and Engineering R 49 (2005) 89 – 112 Fig. 18. SEM images of

Fig. 18. SEM images of lotus-like and honeycomb-like aligned CNT lms: (a) top view of lotus-like aligned CNT lms; (b) enlarged view of single micro-papilla of the lotus-like aligned CNT lms; and (c) top view of honeycomb-like aligned CNT lms. After [136].

general, the contact angle (u) of a at surface and that of a suitably rough surface (u r ) is given by

(2)

where r is the surface roughness factor, f 1 and f 2 are fractions of CNTs and air on the aligned CNT lms. From Fig. 17, the structure of aligned CNT lms leads to a sufciently rough surface that the liquid may trap air to give a composite surface effect. The very large fraction (f 1 ) of air and the very small fraction (f 2 ) of CNTs on the lms give rise to large contact angles for water and oil. Following the above study, Sun et al. [135] and Feng et al. [136] prepared lotus-like and honeycomb-like aligned CNT lms with a combination of micro- and nano-structures (see Fig. 18) and they all displayed super-hydrophobicity. Thus, it is expected that well-aligned CNT compounded polymer lms or coatings should have wide applications including super-hydrophobic surfaces to textiles, coatings, gene delivery, micro-uid channels, non-wetting liquid transfer and so forth.

cos u r ¼ r f 1 cos u f 2

5. Concluding remarks

Enhanced dispersion and alignment of CNTs in polymer matrices greatly improve mechanical, electric, thermal, electrochemical, optical and super-hydrophobic properties of polymer/CNT com- posites. Thus, the critical challenge is the development of means and ways to promote and increase the dispersion and alignment of CNTs in the matrix. Optimum physical blending, in situ polymerization and chemical functionalization could improve the dispersion of CNTs, but the last method is the most efcient. The alignment of CNTs in a polymer matrix could be increased by ex situ alignment due to force, electrical and magnetic eld-induced methods, and liquid crystalline phase could also induce the orientation of CNTs along the direction of the applied eld. Currently, we are investigating the liquid crystalline polymer grafted CNTs, and we anticipate that the modied CNTs will be compatible with the polymer matrix, and easy to be aligned along the eld direction in a polymer matrix due to the high compliance of the CNTs. This seems to be a promising alignment method of CNTs not yet explored.

Acknowledgements

We wish to thank the Australian Research Council (ARC) and the National Natural Science Foundation of China (20474021 and 20490220) for the continuing nancial supports of our individual projects on polymer nanocomposites. Sincere thanks are due to our colleagues at the CAMT and

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HUST for many useful suggestions and comments on the manuscript. YWM is Australian Federation Fellow funded by the ARC tenable at the University of Sydney. XLX is Visiting Scholar to the CAMT supported by the ARC when this review was completed.

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Xiao-Lin Xie is a professor in the Department of Chemistry at Huazhong University of Science and Technology (HUST), China. He is Vice-Director of the Rheology Sectional Committee and Member of the Applied Chemistry Sectional Committee of the Chinese Society of Chemistry. Prof. Xies research interests are on polymer composites and liquid crystalline polymers. In 1995, he received a PhD degree from Sichuan University, which was followed by 2 years postdoctoral research at Zhejiang University. From April 2003 to March 2004, he was Visiting Scholar in the University of Sydney Centre for Advanced Materials Technology and undertook studies on polymermatrix nanocomposites.

Yiu-Wing Mai was a graduate of Hong Kong and Sydney universities. He now holds a University Chair in Sydney University and is an Australian Federation Fellow. He is also Director of the Centre for Advanced Materials Technology at Sydney University since 1988. Professor Mai has a general research interest on the processing-structureproperty relationships of a range of engineering materials including nanocomposites. He is listed in the ISI HighlyCited.com database as a highly cited researcher in Materials Science.

Xing-Ping Zhou is a lecturer in the Department of Chemistry, Huazhong University of Science and Technology (HUST), China. His research interest is on polymeric materials. He received a masters degree from HUST in 2001 and was a research assistant in the Department of Physics and Materials Science, City University of Hong Kong during the period November 2000 to February 2001. He is now a PhD student in HUST.