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chemical vapor deposition (CVD)carbon nanoberlinear lamentvapor-grown carbon ber (VGCF)

Carbon Nano7. Carbon NanobersYoong Ahm Kim, Takuya Hayashi, Morinobu Endo, Mildred S. Dresselhaus

Carbon nanobers are sp2-based linear, non-continuous laments that are different fromcontinuous, several micrometer diameter carbonbers. This chapter gives a review on the growth,structural properties and practical applicationsof carbon nanobers as compared with those ofconventional carbon bers. Carbon nanoberscould be produced via the catalytic chemical va-por deposition (CVD) as well as the combinationof electrospinning of organic polymer and ther-mal treatment. The commercially available carbonnanober around the world is ca. 500 t/y. Carbonnanobers exhibit high specic area, exibility,and super strength due to their nanosized diameterthat allow them to be used in the electrode ma-terials of energy storage devices, hybrid-type llerin carbon ber reinforced plastics and bone tis-sue scaffold. It is envisaged that carbon nanoberswill be key materials of green science and tech-nology through close collaborations with carbonbers and carbon nanotubes.

7.1 Similarity and Difference Between CarbonFibers and Carbon Nanobers ................ 27.1.1 Basic Concepts ............................. 2

7.1.2 Synthesis and Propertiesof Carbon Fibers ........................... 3

7.1.3 Vapor-Grown Carbon Fibers........... 4

7.2 Growth and Structural Modicationsof Carbon Nanobers ............................ 67.2.1 Catalytically Grown

Cup-Stacked-Type ........................ 67.2.2 Catalytically Grown

Platelet-Type ............................... 97.2.3 Electrospun-Based Carbon

Nanobers .................................. 127.2.4 Electrospun-Based Porous Carbon

Nanobers .................................. 17

7.3 Applications of Carbon Nanobers.......... 197.3.1 Electrode Material in Lithium Ion

Secondary Battery ........................ 197.3.2 Electrode Material

for Supercapacitors....................... 217.3.3 Supporting Material

for Metal Nanoparticles ................. 247.3.4 Bone Tissue Scaffold ..................... 25

7.4 Concluding Remarks ............................. 25

References .................................................. 27

Carbon nanobers could be dened as sp2-based linearlaments with diameter of ca. 100 nm that are char-acterized by exibility and their aspect ratio (above100). Materials in a form of ber are of great prac-tical and scientic importance. The combination ofhigh specic area, exibility, and high mechanicalstrength allow nanobers to be used in our dailylife as well as in fabricating tough composites forvehicles and aerospace. However, they should be dis-tinguished from conventional carbon bers [7.13]and vapor-grown carbon bers (VGCFs) [7.410] intheir small diameter (Fig. 7.1). Conventional carbon

bers and VGCFs have several micrometer-sized diam-eters (Fig. 7.1c, d). In addition, they are differentfrom well-known carbon nanotubes [7.5, 1114]. Car-bon nanobers could be grown by passing carbonfeedstock over nanosized metal particles at high tem-perature [7.410], which is very similar to the growthcondition of carbon nanotubes. However, their ge-ometry is different from concentric carbon nanotubescontaining an entire hollow core, because they canbe visualized as regularly stacked truncated conicalor planar layers along the lament length [7.1518].Such a unique structure renders them to show semi-

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polymeric compositecarbon ber reinforced plasticcarbon bergraphite

1 101 102 103 104Diameter (nm)

Carbon nanotube Carbon nanofiber Carbon fiber

a) b) c) d) e)

Fig. 7.1 Schematic comparison of the diameter dimensions on a logscale for various types of brous carbons

conducting behavior [7.19] and to have chemicallyactive end planes on both the inner and outer sur-faces of the nanobers, thereby making them usefulas supporting materials for catalysts [7.20], reinforc-ing llers in polymeric composites [7.21], hybrid-type ller in carbon ber reinforced plastics [7.22

24], and photocurrent generators in photochemicalcells [7.25, 26].

Alternatively, carbon nanobers could be fab-ricated by the right combination of electrospin-ning of organic polymers and thermal treatmentin an inert atmosphere. The electro-spinning tech-nique has been considered to be one of theadvanced ber formation techniques from poly-mer solution by using electrostatic forces [7.2730]. Electrospun-based nanobers exhibited notice-able properties, such as nanosized diameter, highsurface area and thin web morphology, which makethem applicable to the fabrication of high-performancenanocomposites, tissue scaffolds and energy storage de-vices [7.3137].

Within these contexts, intensive studies on the syn-thesis, characterization, possible application of carbonnanobers have been carried out for the last decade. Inthis chapter, we have reviewed the synthesis techniques,their interesting textural properties, and, furthermore,the promising usages of carbon nanobers that havebeen developed over the past 10 years.

7.1 Similarity and Difference Between Carbon Fibersand Carbon Nanobers

Since carbon nanobers could be considered as the 1-Dform of carbon, their structure and properties are closelyrelated to those of other forms of carbon, especially tocrystalline three-dimensional graphite, turbostratic car-bons, and to their constituent 2-D layers. Therefore,several forms of conventional carbon materials shouldbe mentioned in terms of their similarities and differ-ences relative to a carbon nanober. Especially, a directcomparison should be made between brous carbonma-terials, because the carbon ber acts as a bridge betweencarbon nanobers and conventional bulky carbon ma-terials. In this section, the structures of carbon bers aswell as VGCFs are described with a strong emphasison the similarities and differences of these 1-D carbonmaterials.

7.1.1 Basic Concepts

Carbon bers represent an important class of graphite-related materials that are closely related to carbonnanobers, with regard to structure and properties.Carbon bers have been studied scientically sincethe late 1950s and fabricated industrially since 1963.

They are now becoming a technologically and commer-cially important material in the aerospace, construction,sports, electronic device and automobile industries.The global carbon ber market has now grown toabout 12 500 t/y of product, after 40 years of contin-uous R&D work [7.13]. Carbon bers are denedas a lamentary form of carbon with an aspect ra-tio (length/diameter) greater than 100. Probably, theearliest documented carbon bers are the bamboo-char laments made by Edison for use in the rstincandescent light bulb in 1880. With time, carbonbers were replaced by the more robust tungsten l-aments in light bulb applications, and consequentlycarbon ber R&D vanished at that early time. Butin the late 1950s, carbon bers once again becameimportant because of the aggressive demand fromaerospace technology for the fabrication of lightweight,strong composite materials, in which carbon bers areused as a reinforcement agent in conjunction withplastics, metals, ceramics, and bulk carbons. The spe-cic strength (strength/weight) and specic modulus(stiffness/weight) of carbon ber-reinforced compositesdemonstrate their importance as engineering mater-

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graphite bergraphite whiskergraphite whiskerdirect current (DC)carpet-rolling structuregraphite sheetgraphene sheetcarbon ber!propertypolyacrylonitrile (PAN)mesophase pitch-based carbon ber (MPCF)

ials, due to the high performance of their carbon berconstituents.

Since the temperature and pressure necessary toprepare a carbon ber from the liquid phase is at thetriple point (T = 4100K, p = 123 kbar), it would be al-most impossible to prepare carbon bers from the meltunder industrial processing conditions. Carbon bersare therefore prepared from organic precursors. Thispreparation is generally done in three steps, includingstabilization of a precursor ber in air (at 300 C),carbonization at 1100 C, and subsequent graphitiza-tion (> 2500 C). Fibers undergoing only the rst twosteps are commonly called carbon bers, while bersundergoing all three steps are called graphite bers.Carbon bers are generally used for their high strength,while graphite bers are used for their high modu-lus. Historically, Bacons graphite whisker (Fig. 7.2)has demonstrated the highest mechanical properties ofa carbon ber (with regard to both strength and mod-ulus), comparable to the ideal value for a graphitenetwork [7.38]. Graphitic whiskers were grown underconditions near the triple point of graphite. Then, thestructural model was proposed, in which the layers con-sisting of graphene sheets are wound around the axislike as in rolling up a carpet. These whiskers were usedas the performance target in the early stages of car-bon ber technology, even though they have never beenproduced on a large-scale.

Fig. 7.2 Model for graphitewhiskers grown by the directcurrent (DC) arc-dischargeof graphite electrodes.Whiskers were reported tohave the carpet-rolling struc-ture of graphite sheets andto have high mechanicalstrength and modulus alongthe ber axis, similar to theideal values of a graphenesheet

7.1.2 Synthesis and Propertiesof Carbon Fibers

SEM photographs together with schematic structuralmodels are shown in Fig. 7.3 for typical carbon bers:a high-strength polyacrylonitrile (PAN)-based ber(Fig. 7.3a), a high-modulus PAN-based ber (Fig. 7.3b)and a mesophase pitch-based carbon ber (MPCF)(Fig. 7.3c) [7.38, 39]. The PAN-based bers consist ofsmall sp2-carbon structural units preferentially alignedwith the carbon hexagonal segments parallel to the beraxis. This orientation is responsible for the high ten-sile strength of PAN-based carbon bers [7.40]. Byvarying the processing conditions (e.g., oxidation con-ditions, choice of precursor material, and especiallyby increasing the heat treatment temperature) of PANbers, a better alignment of the graphene layers can beachieved (structural model of Fig. 7.3b), thus leadingto stiffer, higher-modulus PAN bers, but with lowerstrength [7.39]. PAN-based bers are one of the typicalhard carbons. MPCFs consist of well-aligned graphiticlayers arranged nearly parallel to the ber axis, andthis high degree of preferred orientation is responsiblefor their high modulus or stiffness as well as their rel-atively high graphitizability. The structures describedabove give rise to different physical properties, althougheach type of ber features carbon hexagonal networks,possessing the strongest covalent bonds in nature (CCbonds). These strong interatomic bonds lie in sheets es-sentially parallel to the ber axis, and are responsiblefor the high mechanical performance of these carbonbers.

Referring to Fig. 7.4a we see that PAN-based bershave high strength and MPCFs have high modulus,while VGCFs provide mainly ultra-high modulus ma-terials [7.4, 41]. In this gure we also observe isotropicpitch-based (general grade) bers, exhibiting muchlower modulus and strength, but widely used in com-posites with cement matrix for construction due totheir low cost and chemical stability. Figure 7.4bdemonstrates a direct indication of the differences inthe mechanical properties of various carbon bers,from low modulus high strength to high modu-lus low strength bers from the lower left to theupper right in the photograph, where a yarn containing500 bers was initially placed in a horizontal posi-tion. These bers are combined with other materialsin order to design suitable mechanical properties andthe bers are used as a ller for various advancedcomposite materials. In order to get high performancein carbon and graphite bers, it is very important

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mesophase pitch-based berber structure!schematic diagramcarbon ber!vapor-growntubular lamentsp2-carbon

2 m

b) c)

Folded graphite sheet

3 m

a)

5 m

Transversesection

1 nm

Externalsection

Longitudinalsection

Transversesection

PoresPores

LongitudinalsectionExternalsection

Fig. 7.3ac SEMmicrographs of three types of carbon bers and their corresponding structural models. (a) High-strengthPAN-based ber, (b) High-modulus PAN-based ber, and (c) a mesophase pitch-based ber. In the second row of eachber type, a schematic diagram of the ber structure is shown

to control the microstructure by selecting the appro-priate organic precursor as well as the processingconditions.

7.1.3 Vapor-Grown Carbon Fibers

VGCFs have a very special structure like annular-rings(Fig. 7.5a) and are synthesized by a somewhat differentformation process than that used to produce PAN-basedand MPCFs. In particular, VGCFs are not preparedfrom a brous precursor, but rather from hydrocar-bon gas, using a catalytic growth process outlined inFig. 7.5b [7.510]. Ultrane transition metal particles,

such as iron particles with diameter less than 10 nm,are dispersed on a ceramic substrate, and a hydro-carbon, such as benzene diluted with hydrogen gas,is introduced at temperatures of about 1100 C. Hy-drocarbon decomposition takes place on the catalyticparticle, leading to a continuous carbon uptake by thecatalytic particle and a continuous output by the par-ticle of well-organized tubular laments of hexagonalsp2-carbon. The rapid growth rate of several tens ofm/min, which is 106 times faster than that observedfor the growth of common metal whiskers [7.37], al-lows the production of commercially viable quantitiesof VGCFs. Evidence in support of this growth model

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carbon!mechanical propertygraphite ber!mechanical propertyvapor-grown carbon bercarbon ber!vapor-growngrowth mechanismcatalytic metal particleelongation growthpyrolytic deposition

High modulus

Low modulus

High strength

0.5 %High modulus

Modulus (GPa)

Highstrength

General grade

Thin VGCFs

Ultra-highmodulus

High performance

Strain2 % 1.5 % 1 %7000

6000

5000

4000

3000

2000

1000

00 100 200 300 400 500 600 700

Tensile strength (MPa)

Ultra-highstrength

b)a)

Fig. 7.4 (a) The mechanical properties of various kinds of carbon and graphite bers and (b) a direct comparison of themechanical properties for high strength and high modulus bers. Low modulus ber droops under its own weight, butthe high modulus bers does not

Substrate

Catalyticparticle

C

C

Carbon supply C

Pyrolytic carbon layers

Primarily formed fiber

c) d)

2m

100 nm 100 nm

b)a)

Fig. 7.5 (a) SEM image of vapor-grown carbon bers, (b) suggested growth mechanism of VGCFs using ultra-ne cat-alytic metal particles, (c) very early stage of tubule growth in which the catalytic-particle is still active for promotingelongation growth. The primary tubule thus formed acts as a core for vapor grown bers. (d) The ber is obtainedthrough a thickening process, such as the pyrolytic deposition of carbon layers on the primary tubule. The encapsulatedcatalytic particle can be seen at the tip of the hollow core

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7.24 T. Yokozeki, Y. Iwahori, M. Ishibashi, T. Yanagisawa,K. Imai, M. Arai, T. Takayashi, K. Enomoto: Fracturetoughness improvement of CFRP laminates by dis-persion of cup-stacked carbon nanotubes, Compos.Sci. Technol. 69, 22682273 (2009)

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