Amorphous carbon nanocomposites

Amorphous carbon nanocomposites

12

M.P. Ho, A.K.-T. Lau The Hong Kong Polytechnic University, Kowloon, Hong Kong SAR, China

12.1

Introduction

By 2025, it is expected that nanocomposites will be a US$9 billion market, with volume nearing 5 million tons (Yang et al., 2005). Nanocomposites exhibit superior property enhancements even with lower reinforcement contents than their conventional micro-, macro-, or neat counterparts (Zhang et al., 2011). The properties of the nanocomposites are improved by adding various nanomaterials such as (1) onedimensional nanofilm/nanocoating, (2) two-dimensional nanofibers, and (3) threedimensional nanoparticles. Moreover, the control of experimental conditions permits morphology controls (shape, length, diameter, etc.) and the degree of crystallinity (degree of graphitization) of nanomaterial at the nanoscale level (Benedek et al., 2001; Chung, 2002). Among all of these nanocomposites, carbon-based nanomaterials are one of the most attractive materials from an application perspective. Carbon materials are conveniently classified as diamond, graphite, and carbyne. Each of the said carbons has its analogous amorphous form called amorphous carbon (a-C). Diamond is composed of a fully tetrahedral sp3-hybridized CeC bonding configuration. Graphite is a fully trigonal sp2 network that forms planar six-fold rings of single and double bonds with weak van der Waals interaction (p bonding) between planes; the in-plane s orbitals, directed along the x-axis, and a further two p orbitals in the y and z directions. Carbyne is a linear-chain carbon with sp1-hybrid configuration. a-C has existed since time immemorial, which has large diversity in the microstructure and properties of a-C. Figure 12.1 summarizes the main known allotropic forms of carbon, including many other novel carbon allotropes such as fullerenes, nanotubes, carbon onions, and graphene. a-C has a continuous random network with many types of short- and medium-range orders. High-energy sites are generated on the surface of aC when the regular arrays of carbon bonds are disrupted and the “free” valences, discontinuities, and other energetic abnormalities are formed. The surface concentration of high-energy sites increases with the decrease in carbon crystallite size, and, vice versa, it decreases as carbon becomes more well ordered (e.g., graphitization; Muradov and Smith, 2005). The structure of a-C can be divided into two structures: (1) the turbostratic lamellar, graphite-like structure (disordered forms of the graphite) and (2) the disordered, three dimensionally cross-linked structure (microcrystalline carbon) (Duley and Williams, 1981; John, 1986; Rilev, 1947; Silva and Ravi, 2003). Because a-C describes a group of carbon materials that can be a mix of sp3, sp2, and even sp1, the common method for characterizing a-C is through the ratio of the hybridized bonds Fillers and Reinforcements for Advanced Nanocomposites. http://dx.doi.org/10.1016/B978-0-08-100079-3.00012-0 Copyright © 2015 Elsevier Ltd. All rights reserved.

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Figure 12.1 A summary of carbon allotropes.

Carbon

Amorphous carbon Particle

Diamond

Fullerence

Graphite

Nanotube

Carbynes

Foam Film Fiber x

x

Mixture of sp hybridized Pure sp carbon atoms carbon atoms

x

Qusai sp carbon atoms

existing in the material (Ferrari and Robertson, 2000). Diaz (1996) has found that a higher sp3 concentration ratio deduced a harder a-C. This chapter extensively summaries the nano-a-C-reinforced nanocomposites and their manufacturing processes. Some of the major properties and applications of nano-a-C-reinforced nanocomposites are further discussed.

12.2

a-C nanoparticles

The use of a-C particles from fuel-rich partial combustion for ink, pigment, and tattoos dates back more than 3000 years, but it remains a topic of current research interest (Lee et al., 2006; Yang et al., 2006). a-C particles are highly condensed from incomplete combustion processes to carbonaceous residue formation, which is commonly described as charcoal, black carbon or carbon black, lampblack, coal, and coke (Gustafsson et al., 1996). a-C is applied in a wide range of applications, including tires, cars, printing, pencils, computers, printers, photocopiers, laboratory tables, etc. a-C nanoparticles have been obtained in a bottom-up approach, for example, by pyrolysis, laser ablation, microwave plasma-enhanced chemical vapor deposition (PECVD), electrolysis in molten salt, graphitization of particles obtained by microemulsion polymerization, or treatment in supercritical water (Galvez et al., 2002; Lou et al., 2013). Milling is the most common top-down method to general nanomaterial from bulk structures. Garrigue et al. (2004) have developed a top-down approach for the chemisorption of polyoxometalates on carbon surfaces. The driving force was generated for the gradual division of the large carbon aggregates into smaller particles, leading to highly dispersed carbon with a narrow particle size distribution. a-C nanoparticles have received great attention because of their ultimate properties such as low density, high specific surface area, uniform pore size, and thermal and

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mechanical stability. These materials have been studied for use in adsorbent, composite, catalyst support, and electronic material applications as well as use in drug delivery, medical imaging, cell delivery, and cancer vaccination (Jiang et al., 2009).

12.2.1 a-C nanoparticles/polymer composites a-C/polymer nanocomposites have been developed by the dispersion of a-C nanoparticles in thermoplastics, thermosetting plastics, and elastomers for improvement in mechanical, electrical, and thermal properties. The effectiveness is such that the amount of nanoparticles added is normally only 0.5e5.0 wt% (Pukanszky et al., 2005; Rahman et al., 2011). Because a-C nanoparticles exhibit high stiffness, strength, toughness, thermal stability, energy barrier, flame retardancy, chemical resistance, and moisture control in addition to their superior electrical properties, they can be used in various applications for aviation/aerospace, ballistic protection, thermal interfaces, hydrogen storage, and sensors (Rahman et al., 2011). Figure 12.2 shows that carbon black nanoparticles are randomly distributed in epoxy resin. Because the nanoparticles contact each other at high filler contents, the electrical conductivity and dielectric loss of the system increases (Xu and Wong, 2005). Moreover, carbon nanoparticles offer many opportunities in biomedicine and diagnostics, electrochemical devices including batteries, supercapacitors, and fuel cells. Nanocomposites are expected to embark on several key packaging applications, including packaging for soft drinks, beer, food, pharmaceuticals, and electronics as well as glass coating of

Figure 12.2 SEM micrograph of epoxy/carbon black nanocomposite (Ali Raza et al., 2012).

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windows, doors, and skylights for ultraviolet and heat protection (Achour et al., 2008; Chen and Chung, 1995: Jiang et al., 2009; Rahman et al., 2011; Raza et al., 2012). Figure 12.3 shows scanning electron microscopy (SEM) micrographs of asreceived bamboo nanocharcoals. It can be seen that bamboo nanocharcoals are in the form of large and small clusters. This large amount of agglomerated bamboo nanocharcoals was added into the polymer, as shown in Figure 12.4, which may affect the curing process of resin. Therefore, sufficient particle dispersion is essential for effective improvement of the composite properties. There are distinct approaches for dispersing nanoparticles into polymers based on several facilities, including

Figure 12.3 SEM micrograph of as-received bamboo nanocharcoals.

Figure 12.4 Agglomerated nanoparticles added into the polymer.

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ultrasonicators, high-pressure homogenizers, agitator bead mills, impinging jet mills, and rotor-stator-mixers (Hielscher, 2012). Ultrasonication is the most popular way for nanoparticle dispersion for research purposes. Nanoparticles were first dispersed in a polar solvent, such as acetone, by ultrasonication. After removing the polar solvent, the dispersed nanoparticles were mixed with polymer via ultrasonication. Cavitation ultrasonication describes the process of formation, growth, and collapse of bubbles. Ultrasonic waves generated by the sonicator create small vacuum bubbles or voids in the liquid. When the bubbles or void attains a volume at which they can no longer absorb energy, they violently collapse. Because cavitational collapse produces intense local heating (w5000 K), this extra energy imposed into the mixture under ultrasonication may also cause early curing of the resin and results in the brittleness of the resulting composites (Chan et al., 2011; Suslick, 1998). Thus, the viscosity of the mixture, interparticle distance, and ultrasonication time in the composite play a vital role in obtaining the best mechanical properties of the composite (Chan et al., 2011; Hatanaka et al., 1999). The tensile properties of bamboo nanocharcoal-reinforced epoxy using glassrod stirring and processing ultrasonication were investigated and are shown in Figure 12.5. The bamboo nanocharcoal-reinforced epoxy with ultrasonication exhibits higher tensile properties as compared with the samples without ultrasonication. There is strong technological interest in nanocharcoal-filled polymers because of the wide spectrum of engineering applications in the electronics, aerospace, and automotive industries. Given that nanoparticles kills bacterial cells by the disintegration of the cell wall or membrane, nanocharcoals are able to damage the plasma membrane of two foodborne bacteria. Cha et al. (2012) also found the bacteria killing effect when plastic chips mixed with charcoal powders were supplemented into bacterial cell culture media. Results in the antibacterial activity demonstrate that polymers incorporated with charcoal powder were very useful materials for food packaging. Carbon black nanoparticle-reinforced polyisoprene applied in electric heating elements and resistors as thermodynamically inactive materials for a high dielectric constant (>1000) has been studied. The dissipation factor (tand) of this carbon black nanocomposite was high (Xu and Wong, 2005). However, improving the dispersion of the nanoparticles in polymer lowers the percolation threshold of composites (Raza et al., 2012; Sumfleth et al., 2011). The electrical conductivity of rubbery epoxy/carbon black nanocomposites at 8 wt% filler loading was 2
103 S/m, which matched the criterion of electrical conductivity for electrostatic applications (106 S/m) (Ali Raza et al., 2012; Knite et al., 2004; Sasha Stankovich et al., 2006).

12.2.2 Activated charcoal nanocomposite The process to increase the surface area of a carbonized organic precursor is referred to as “activation”, and its resulting material is referred to as “activated carbons” or “activated charcoal.” Varying the carbon precursor and activation conditions (temperature, time, and gaseous environment) allows for some control over the resulting porosity and pore-size distribution. The processes of carbon activation can be placed into two general categories: thermal activation and chemical activation. Thermal activation (physical activation) is the modification of a carbon by controlled gasification in the

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Tensile strain (mm/mm)

(a)

0.05

Without sonication

0.04

With sonication

0.03 0.02 0.01 0

0

0.5

1

1.5

2

2.5

3

wt. % of nano BC

(b) 100 90 Tensile strength (MPa)

80 70 60 50 40 30 20 Without sonication

10

With sonication

0 0

Young's modulus (MPa)

(c)

0.5

1

1.5

2

2.5

3

wt. % of nano BC

4000

3000

2000 Without sonication With sonication

1000 0

0.5

1

1.5

2

2.5

3

wt. % of nano BC

Figure 12.5 (a) Tensile strain, (b) tensile strength, and (c) Young’s modulus of epoxy/bamboo charcoal (BC) nanocomposites with and without sonication.

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presence of suitable oxidizing gases such as steam, carbon dioxide, air, or mixtures of these gases with the controlled temperatures. For chemical activation, the precursor is impregnated with a certain chemical agent and is carbonated afterward. Burning off some carbon and the elimination of volatile pyrolysis in an oxidizing atmosphere greatly increases the pore volume and surface area of the material during gasification. As a result, a material with higher carbon content, ordered structure, and porosity is produced. A high degree of activation can be achieved by increments in burning off, but further activation is accompanied by pore widening, which results in a decrease in carbon strength, density, and yield. Chemical activation combines the carbonization and activation process in one step, usually at lower temperatures but with higher yield and better porous structure than the physical activation. Postactivation (washing) of the carbon is usually required to remove the residual reactants and inorganic residue (sometimes referred to as ash) that originates from the carbon precursor or is introduced during activation (Lozano-castello et al., 2003; Pierson, 1994). Activated carbon nanoparticles that were derived from the pyrolysis of biomass oil palm empty fruit bunch, bamboo stem, and coconut shells were used as fillers in the preparation of epoxy nanocomposites. In general, the thermal stability of epoxy/activated carbon nanocomposites improved as compared with that of pure epoxy. The degree of crystallinity of epoxy matrices was improved by adding the activated carbon because of interfacial interactions between activated carbon nanoparticles and epoxy matrices rather than filler loading. The nanocomposite using biomass as a resource reduces the material cost for its demanding applications such as insulating and packaging material (Abdul Khalil et al., 2012). On the other hand, activated carbon black nanoparticles have been studied to be used as a reheating agent and a co-catalyst in the esterification reaction during solid-state polycondensation (Bikiaris et al., 2006). Medical and health-care textiles, including bedding, surgical gowns, and hospital clothes, fulfill the comfort and hygienic properties, such as moisture management, thermal conductivity, breathability, antimicrobial activity, and odor resistance, and are rapidly growing in part of the textile industry (Guo et al., 2011; Rajendran and Anand, 2002). This growth is attributed to the continuous improvements in technology and the increasing consciousness of preventing health-care-associated infections. The unique characteristics of activated bamboo charcoal nanoparticles include high porosity, high breathability, and good wash durability as well as antielectrostatic, antibacterial, antimicrobial, and antifungal properties. Activated bamboo charcoal nanoparticles can be applied to thermal regulation, odor absorption, and infrared energy absorption and the emission, absorption, and decomposition of benzene, phenol, and methyl alcohol as well as other volatile substances. Medical textiles from polyester-based bamboo nanocharcoal yarn with the mentioned unique properties have been developed (Chio and Cho, 1997; Czajka, 2005; Kandhavadivu et al., 2011; Parthiban and Viju, 2009; Park et al., 1998).

12.2.3 Amorphous carbide-derived carbon nanocomposites Carbide-derived carbons (CDCs) can be amorphous or crystalline. The various structures of CDC can be obtained by varying its crystallinity. When chlorine gas extracts

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the metal from carbides such as Ti3SiC2, SiC, B4C, or ZrC, nearly pure carbon (CDC) is left (Adelhelm et al., 2011; Dusza et al., 2004; Falcao and Wudl, 2007; Zhong et al., 2011). CDC/xerogel nanocomposites were prepared by chlorine etching titanium carbide xerogel via the sol-gel technique, followed by a carbothermal reduction process. The nanocomposite takes advantage of the merit of both CDC and xerogel with improved electron conductivity. They have attracted much attention as prospective energy storage devices, hybrid vehicles, electrochemical capacitors, memory back-up systems, and other devices requiring high-power output occasions (Sun et al., 2011).

12.2.4

a-C/carbon nanocomposites

Superhydrophobic surfaces with a water contact angle larger than 150 and low water contact angle hysteresis bring great convenience in daily life as well as in various industrial processes. Superhydrophobic a-C nanoparticle-reinforced carbon nanotubes were fabricated by plasma immersion ion implantation. The microstructure of the fabricated nanocomposite is the arrays of carbon nanotubes capped with a-C nanoparticles. Both advancing and receding angles close to 180 can be achieved on the nanocomposites (Han et al., 2009). Superhydrophobic a-C nanocomposites are arousing much interest in self-cleaning, antisticking, anticontamination, antifouling, and low-friction coating applications (Cottin-Bizonne et al., 2003; Ostuni et al., 2001; Zimmermann et al., 2008).

12.2.5

Doping of a-C nanoparticles

Doping of heteroatoms into carbon materials has offered new opportunities for tailoring their chemical/physical properties (Yoon et al., 2007). Nitrogen and phosphorus have been found to act as n-type dopants for a-C for electrocatalyst applications (Mckenzie, 1996). Doping of a-C nanoparticles affects such properties as pH, catalytic activity, electrical conductivity, and nanostructure. Nitrogen-doped carbon nanoparticles were prepared through flame synthesis by directly burning acetonitrile in air atmosphere for the increment of lithium adsorption energies and the application in an anode material of lithium-ion batteries (Bhattacharjya et al., 2013). Furthermore, organic salt (ZnO or ZnS)-doped carbon nanoparticles have been studied to achieve much higher photoluminescence quantum yields for application in transistors, solar cells, LEDs, and diode lasers (Sun et al., 2008).

12.3

a-C foam nanocomposites

Carbon foam, a novel class of synthetic porous a-C, was developed by Pekala (1989) (Girgis et al., 2011; Pekala et al., 1992). Carbon foam classified as xerogel, aerogel, and cryogel is more electrically conductive than most activated carbons (Pandolfo and Hollenkamp, 2006). Rode et al. (2000) discovered a new form of carbon called “carbon nanofoam” with a rich fraction of sp3 bonding. However, the properties

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of the carbon nanofoam are distinct from conventional carbon foam because of its different formation conditions and techniques (Rode et al., 2002). Carbon aerogel is usually synthesized by polycondensation via the sol-gel process and subsequent pyrolysis at a high temperature (normally 800e1200  C), ambient pressure, and inert atmosphere. Figure 12.6 shows the scheme of the preparation of aerogel, carbonized aerogel, and activated carbon aerogel. They are attractive materials because their microstructure and physical properties can be tuned at the nanoscale level by varying the processing parameters in the sol-gel polymerization and pyrolysis steps (Du et al., 2013; Frackowiak and Beguin, 2001; Girgis et al., 2011; Moreno-Castilla and Maldonado-H
odar, 2005; Pierre and Gerard, 2002; Saquing et al., 2004). Furthermore, carbon aerogel with ultra-high specific surface area and more pores can be activated through thermal activation with carbon dioxide. It was also found that although a greater degree of activation increases the surface area of the carbon foam, the resulting volumetric capacitance passes through a maximum at surface areas of approximately 1000 m2g1 (Du et al., 2013; Li et al., 2006; Pandolfo and Hollenkamp, 2006). a-C nanofoam with a significantly high sp3 fraction (w35%) was produced by ultrafast ablation with a high pulse-rate laser. This nanofoam formed is a granular material with a specific surface area of approximately 300e400 m2 g1. A high concentration of unpaired spins results in a paramagnetic susceptibility compared with the diamagnetism characteristic of other carbon allotropes (Blinc et al., 2006; Falcao and Wudl, 2007; Munoz et al., 2006; Rode et al., 2002, 2000). Self-standing and highresilience a-C nanofoam was developed by Zhang and Sun (2007), and it could return to its original shape when subjected to 30% deformation by pressing without breaking down the bonding among the carbon particles. The density of the nanofoam was measured as 0.046 g cm3. Figure 12.7 shows the SEM images of a-C nanofoam. Carbon nanofoams are suggested for a wide variety of potential applications, including (1) broadband nonreflective materials, (2) deionization materials, (3) adsorbents for the removal of organosulfur compounds from diesel, (4) energy storage devices (e.g., as intercalation anodes for rechargeable lithium-ion cells as electrodes for electric double layer capacitors), (5) in thermal and phonic insulators, (6) chromatographic packing, (7) catalyst supports, and (8) electrochemistry applications (Du et al., 2013; Frackowiak and Beguin, 2001; Girgis et al., 2011; Moreno-Castilla and MaldonadoHodar, 2005; Pierre and Gerard, 2002; Saquing et al., 2004).

Pyrolysis (carbonization)

Activation

N2 >1000k

Aerogel

CO2 >1273k

Carbon aerogel

Activated carbon aerogel

Figure 12.6 The scheme of the preparation of aerogel, carbonized aerogel, and activated carbon aerogel.

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Figure 12.7 SEM images of carbon nanofoam produced at 700  C. Carbon particles with a relatively uniform particle size, produced at 700  C, are bonded together, forming an interconnected structure (Zhang and Sun, 2007).

Metal-doped a-C nanocomposites with adjustable pore volume and pore size have promoted the use of an electrocatalyst in fuel cells and nanoelectronics (Aksoylu et al., 2001; Auer et al., 1998; Glora et al., 2001). Platinum-doped a-C nanocomposite was synthesized and carbonated up to 1000  C to apply in an electrocatalyst for fuel cells (Saquing et al., 2004). In addition, an organometallic gold/a-C foam nanocomposite fabricated by laser ablation has been reported with improved transport, catalytic, and electrochemical properties (Munoz et al., 2006). A manganese oxide/carbon nanofoam composite has been developed that exhibited voltammetric characteristics in LiOH-containing alkaline electrolytes and could be applied for electrochemical capacitors or batteries (Long et al., 2009). Lytle et al. (2011) developed an a-C nanofoam/carbon fiber composite. This novel composite is a device-ready electrode that does not require conductive additives for the electrode fabrication with improved mechanical and electronic properties because the carbon fiber scaffolding imparts physical reinforcement, flexibility, and additional conductive pathways. a-C nanofoam/carbon fiber composites are device-ready electrode structures that are suitable for application in electrochemical capacitors, lithium-ion batteries, metal-air batteries, fuel cells, and ultrafiltration.

12.4

a-C nano-thin film

A random network of covalently bonded carbon in sp3, sp2, or sp1 local coordination with other carbon atoms or impurity dopants gives rise to a-C thin films that can be

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classified as diamond-like a-C, tetrahedral a-C, polymer-like a-C, or graphite-like a-C. a-C films can be hydrogenated or hydrogen-free. The hydrogenated a-C contains a random network with some of the bonds terminated by hydrogen and can achieve up to 60% hydrogen depending on the growth process (Robertson, 2002; Silva and Ravi, 2003). a-C thin film has been widely investigated and recognized as a tribocoating material, which is commonly synthesized by deposition techniques including filtered cathodic arc, PECVD, direct ion beam , electron cyclotron resonance plasma chemical vapor deposition, and radio frequency/direct current sputtering (Bhushan and Sundararajan, 1998; Gupta and Bhushan, 1995; Kim et al., 2003; Kumar et al., 2011; Meskinis et al., 2008). However, the thickness of the carbon-coating layer increased with decreasing processing temperature (Ng et al., 2007). Complementary electronic properties of a-C/diamond thin nanofilm can be obtained using conductive a-C nanofilm and perfectly nonconducting diamond substrate. Diamond/a-C nanofilms for conductive temperature and chemically sensing can be synthesized by annealing at temperature above 1000  C in vacuum or inert gas atmosphere, followed by plasma etching as the chemical sensitivity of the nanofilm to be further controlled by plasma treatment (Kumar et al., 2011). However, the nanofilm increases in amorphousity after plasma etching. Much attention has been paid to metal-containing a-C, especially the metalcontaining diamond-like carbon (DLC) because it exhibits excellent tribological performance (Corbella et al., 2004; Donnet, 1998; Pauleau and Thiery, 2004; Silva and Ravi, 2003; Uglov et al., 2000). The amorphous nature of DLC opens up the possibility of incorporating the elements of Si, F, P, Ag, and N (Ahmed et al., 2010; Jones et al., 2010; Roya et al., 2009; Yokota et al., 2007), which improves the functionality of the material. Titanium carbide/DLC nanocomposite films have been prepared by hybrid chemical vapor/physical vapor deposition (Meng et al., 2000; Meng and Gillispie, 1998; Shi et al., 2004; Zhang et al., 2013), unbalanced reactive magnetron sputtering deposition (Patschider et al., 2001; Pei et al., 2005), and filtered cathodic vacuum arc deposition (Wang et al., 2008). Because the difference between titanium and aluminum sputter yields is large, the composition is difficult to control. The PECVD process is thus adapted to control the coating composition via the flow rates of the respective source gases (Chou, 1992; Shieh and Hon, 2002). Depending on the sp3 (diamond-like) and sp2 (graphite-like) bond content and the hydrogen and other incorporated element concentrations, the physical properties of a-C thin nanofilm can be altered to obtain friction and wear reduction (Ikeyama et al., 2005; Liu et al., 1996), good biocompatibility and hemocompatibility, metal ion release prevention (Hauert, 2003; Mitura et al., 1994; Maguire et al., 2005), exceptional optical transmission, and antireflection (Lin et al., 2011; Litovchenko and Klyui, 2001). Thus, the potential applications of a-C nano-thin film composites include supercapacitors, electron field emission, electronic semiconductors (Silva and Ravi, 2003), diffusion barriers in electronics and food packaging (Robertson, 2002), glass windows of supermarket laser barcode scanners, sunglasses (Bhushan, 1999), scratch-resistant coatings (John, 1986; Silva and Ravi, 2003), sensors, and biological and medical devices (Kumar et al., 2011).

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12.5

Fillers and Reinforcements for Advanced Nanocomposites

a-C nanofibers

a-C nanofibers with their electromagnetic shielding, chemical inertness, and excellent mechanical and electrical properties are widely used in numerous high-technology applications. a-C nanofibers have the virtue of a high aspect ratio to allow for a low loading content to provide the desired properties. Carbon nanofibers can be synthesized at temperatures below 250  C. The nanofibers tend to be highly amorphous, containing at least 92 wt% carbon in composition. Figure 12.8 shows the SEM images of aligned and random carbon nanofibers (Chung, 2002; Coville et al., 2011). Commercially available carbon fibers are divided into general-purpose, high-performance, and activated carbon fibers with different degrees of crystallinity. They are produced from thermosetting organic materials such as cellulose (or rayon), phenolic resins, and polyacrylonitrile- and pitch-based materials (Falcao and Fred, 2007; Ma et al., 2003; Pandolfo and Hollenkamp, 2006). Generally, carbon nanofibers have been synthesized by (1) ion beam irradiation, (2) electrospinning, (3) catalytic chemical vapor deposition, and (4) a polymer blend technique (Coville et al., 2011; Falcao and Fred, 2007; Kimura et al., 2005; Sim et al., 2007; Suarez-Garcia et al., 2009). Catalytic decomposition of certain hydrocarbons can be used for growing carbon nanofibers on a metal particle substrate such as iron, cobalt, nickel, aluminum, and their alloys. Zamri et al. (2010) has studied carbon nanofibers that were directly grown on metal mesh substrates of copper and molybdenum by the ion irradiation method. The amorphousity of the a-C nanofiber composite is controllable by the current flow of induced resistive heating. Depending on the size of the catalyst particle, nanofibers with diameters ranging from 2 to 100 nm and lengths ranging from 5 to 100 mm can be obtained (Rodriguez, 1993; Tu et al., 2003). Qin et al. (2006) has found that helical a-C nanofibers are synthesized by thermal chemical vapor deposition using copper nanoparticles as a catalyst at 195  C. These helical carbon nanofibers shown in Figure 12.9

Figure 12.8 FESEM (field emission scanning electron microscopy) image of helical carbon nanofibers (Qin et al., 2006).

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(a)

(b)

Figure 12.9 SEM micrograph showing (a) aligned and (b) random carbon nanofibers (Coville et al., 2011).

contain high contents of hydrogen and exhibit good elasticity and processability. These fibers are highly graphitic and more economically attractive for the electronics, automotive, and aerospace industries (Ghose et al., 2006; Hammel et al., 2004; Zamri et al., 2010). Tin nanoparticle/a-C nanofiber composite was synthesized via electrospinning and subsequent calcination under a reducing atmosphere for lithium-ion batteries. It was reported that the defective structures in a-C fiber store more lithium through the electrospinning method than ordered lattice in graphite (Ji and Zhang, 2009; Kim et al., 2014). Polymer-blended a-C nanofibers using conventional mixing methods such as a twin-screw extruder, high shear mixer, and two-roll mill are common blending methods for reinforcing a-C nanofibers in polymer for lightweight structures. a-C nanofibers are further purified, ball-milled, functionalized, or surface treated with plasma to improve the dispersion of a-C nanofibers in polymer and the interfacial strength of polymer/nanofiber composites (Ma et al., 2003). a-C nanofibers have a high modulus and electrical and thermal conductivities, but a relatively lower coefficient of thermal expansion along the fiber axis than perpendicular to the fiber axis. a-C nanofibers as fillers also simultaneously provide enhanced electrical conductivity to the polymer (Chung, 2002; Yang et al., 2005).

12.6

Conclusions

a-C is one of the most important allotropes of carbon, which has been extensively studied because of its huge application potential. a-C can be synthesized at the nanoscale level with a remarkable range of physical, mechanical, electrical, and thermal properties. This chapter broadly reviews the nanosized a-C and its nanocomposite with emphasis on some experimental results and applications. On the basis of their superior and unique properties, these materials have been used in various applications for the

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Fillers and Reinforcements for Advanced Nanocomposites

textile, plastic, and health-care industries as well as in the fields of gas and water filtering, electrical applications, and food packaging.

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