8. Carbon Nanotubes Is Expectedexothermic to and Become Also Increasingly Coverages

193 Carbon8. Carbon Nano Nanotubes 8 | B Part Marc Monthioux, Philippe Serp, Brigitte Caussat, Emmanuel Flahaut, Manitra Razafinimanana, Flavien Valensi, Christophe Laurent, Alain Peigney, David Mesguich, Alicia Weibel, Wolfgang Bacsa, Jean-Marc Broto

Carbon nanotubes (CNTs) are remarkable objects robustness, the ability of their electronic struc- that once looked set to revolutionize the tech- ture to be given a gap, and their wide typology nological landscape in the near future. Since the etc. Therefore, carbon nanotubes may provide the 1990s and for twenty years thereafter, it was re- building blocks for further technological progress, peatedly claimed that tomorrow’s society would be enhancing our standard of living. shaped by nanotube applications, just as silicon- In this chapter, we first describe the structures, based technologies dominate society today. Space syntheses, growth mechanisms, and properties of elevators tethered by the strongest of cables, carbon nanotubes. Then we introduce nanotube- hydrogen-powered vehicles, artificial muscles: based materials, which comprise on the one hand these were just a few of the technological mar- those formed by reactions and associations of all- vels that we were told would be made possible by carbon nanotubes with foreign atoms, molecules the science of carbon nanotubes. and compounds, and on the other hand, compos- Of course, this prediction is still some way from ites, obtained by incorporating carbon nanotubes becoming reality; most often the possibilities and in various matrices. Finally, we will provide a list of potential have been evaluated, but actual tech- applications currently on the market, while skip- nological development is facing the unforgiving ping the potentially endless and speculative list of rule that drives the transfer of a new material or possible applications. a new device to market: profitability. New materials, even more so for nanomaterials, no matter 8.1 Structure how wonderful they are, have to be cheap to pro- of Carbon Nanotubes...... 194 duce, constant in quality, easy to handle, and 8.1.1 Single-Wall Nanotubes ...... 194 nontoxic. Those are the conditions for an indus- 8.1.2 Multiwall Nanotubes ...... 197 try to accept a change in its production lines to make them nanocompatible. Consider the ex- 8.2 Synthesis ample of fullerenes – molecules closely related of Carbon Nanotubes...... 199 to nanotubes. The anticipation that surrounded 8.2.1 Solid Carbon Source-Based Synthesis these molecules, first reported in 1985, resulted in Techniques: The DC Electric Arc...... 199 the bestowment of a Nobel Prize for their discov- 8.2.2 Gaseous Carbon Source-Based ery in 1996. However, two decades later, very few Synthesis Techniques ...... 202 fullerene applications have reached the market, 8.2.3 Miscellaneous Techniques ...... 207 suggesting that similarly enthusiastic predictions 8.2.4 Synthesis with Controlled Orientation.. 208 about nanotubes should be approached with cau- 8.3 Growth Mechanisms tion, and so should it be with graphene, another of Carbon Nanotubes...... 210 member of the carbon nanoform family which 8.3.1 Catalyst-Free Growth ...... 210 joined the game in 2004, again acknowledged by 8.3.2 Catalytically Activated Growth...... 210 aNobelPrizein2010. There is no denying, however, that the ex- 8.4 Properties pectations surrounding carbon nanotubes are still of Carbon Nanotubes...... 213 high, because of specificities that make them spe- 8.4.1 Overall Properties of SWNTs...... 213 cial compared to fullerenes and graphene: their 8.4.2 Adsorption Properties ...... 213 easiness of production, their dual molecule/nano- 8.4.3 Electronic and Optical Properties...... 215 8.4.4 Mechanical Properties...... 216 Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright object nature, their unique aspect ratio, their 8.4.5 Reactivity...... 216

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ). ), ]. 6 231 230 231 230 230 233 233 230 229 229 227 229 229 )led 8.4 8.6 )yet ]. Con- 8.5 8.7 8 ..... et al. [8...... ) simultaneously 5nm[8. : 2 ...... 8.1 Bethune ...... ]and 5 4 nm have been synthesized : 35 nm, the most frequent di- ...... : ...... [8. 1 ). Consequently, it still remains an ]. A suitable energetic compromise is ...... Ichihashi 8.8 ...... and Concluding Remarks Toxicity and Environmental Impact of Carbon Nanotubes Industry Memory Iijima 8.9 8.7.11 Catalyst Support 8.8 8.7.9 Anodes8.7.10 for Li-Ion Batteries Chemical Sensors References 8.7.8 High-Tech Goods and Clothes 8.7.7 Automotive and Aeronautic 8.7.38.7.4 Electron Emitter Flexible and Touch-Screen Displays 8.7.2 Near-Field Microscopy Probes 8.7.5 Nonvolatile Random Access 8.7.6 Light Absorbants successfully9 [8. therefore reached for 8.1.1 Single-Wall Nanotubes Calculations have shown that collapsing the single-wall tube into a flattenedmore two-layer favorable than ribbon maintaining isogy the energetically tubular beyond morphol- a diameter value of versely, the shorter thethe radius of stress curvature, the andwith higher diameters the as low energetic as 0 cost, although SWNTs the nanotubes in situ with various metals (Sect. to the discoverycarbon – nanotubes again (SWNTs) (Sect. unexpected – of single-wall SWNTs were really newand nano-objects behaviors with that properties are often quite specific (Sect. by They are also beautiful objects foras fundamental physics well asistry. unique Potential molecules for applicationsCNTs experimental seem or chem- countless CNTs for combined such with a matrix (Sect. and some have reached the market (Sect. toxicity and environmentalnored issues (Sect. should notextraordinarily active be – ig- andof highly competitive research, – field graphene as now that is,bon of which, nano-objects by fullerenes structurally the closelytubes. was related way, to and are nano- again that car- of ]

4 and 227 225 224 223 223 223 221 220 217 217 217 ]. The first 1 ...... )[8. Radushkevich ...... -hybridized carbon ...... 2 8.2 ...... ) was reported [8. ). But the real break- ...... ter the catalyst-free for- 8.1 ]. Worldwide enthusiasm 8.3 3 ]. Since then, the interest in ...... 2 ...... a–c). in 1952 [8. 8.2 ), making sure that the hexagonal rings placed Current Applications of Carbon Nanotubes (on the Market) Materials Carbon-Nanotube-Containing Materials (Composites) Carbon Nanotube-Based Nano-Objects (Carbon Meta-Nanotubes) 8.1 Then the tips of the tube are sealed by two caps, Lukyanovich evidence that the nanofilamentswere actually produced nanotubes in – this thatcavity – they way exhibited can an be inner croscope found micrographs in published the by transmission electron mi- 8.7.1 Carbon Nanotubes and Master Batches 227 8.7 8.6.4 Composites as Multifunctional 8.6.3 Polymer-Matrix Composites 8.6.2 Ceramic Matrix Composites 8.6.1 Metal Matrix Composites 8.6 8.5.4 Coated/Decorated Nanotubes 8.5.3 Functionalized Nanotubes 8.5.2 Filled Carbon Nanotubes It is relativelynanotube easy (SWNT). to Ideally, imaginea it perfect a is graphene single-wall enough sheetmonoatomic carbon layer (graphene to consisting is consider of a sp polyaromatic 8.1 Structure of Carbon Nanotubes Carbon nanotubes (CNTs)sized as have products longgaseous of species been the originating synthe- actionposition from of of the a thermal hydrocarbons catalyst decom- (Sect. on the 8.5 carbon nanofilaments/nanotubes was recurrent, though within a scientific area almost limitedterial to scientist the community [8. carbon ma- 8.5.1 Heteronanotubes began unexpectedly in 1991, af mation of nearlynanotubes perfect (c-MWNTs, concentric Sect. multiwall carbon atoms arranged in hexagons; genuineof graphite layers consists of this graphene)(Fig. and to roll it into a cylinder in contact join coherently. each cap being a hemifullereneameter with (Fig. the appropriate di- through occurred two years later, when attempts to fill as by-products of theelectric-arc formation technique of (Sect. fullerenes via the Nanomaterial and Nanostructures Part B

194 Part B | 8.1

Created from viennaut on 2018-11-17 04:18:29. Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Carbon Nanotubes 8.1 Structure of Carbon Nanotubes 195 atB|8.1 | B Part y a)

x b)

θ T

A c)

a1 O Ch

Fig. 8.1 Making an SWNT, starting from a graphene sheet (after [8.7]) Fig. 8.2a–c Sketches of three different SWNT structures that are examples of (a) a zigzag-type nanotube, ameter encountered when the growth is free from the (b) an armchair-type nanotube, (c) a helical nanotube (af- influence of the catalytic particle size (as for the syn- ter [8.10]) thesis technique based on solid carbon sources) and when conditions ensuring high SWNT yields are used. As illustrated by Fig. 8.2, there are many ways Nanotube length only depends on the specific synthe- to roll a graphene into a single-walled nanotube, with sis conditions (thermal gradients, residence time, and some of the resulting nanotubes possessing planes of so on). Experimental data are consistent with these symmetry both parallel and perpendicular to the na- statements, since SWNTs wider than 2:5 nm are only notube axis (such as the SWNTs from Fig. 8.2a,b), rarely reported in the literature, whatever the prepara- while others do not (such as the SWNT from Fig. 8.2c). tion method, while the length of the SWNTs can be in Similar to the terms used for molecules, the latter are the micrometer or the millimeter range. These features commonly called chiral nanotubes, since one cannot su- make SWNTs a unique example of single molecules perimpose them on their own image in a mirror. Helical with huge aspect ratios. should however be preferred (see below). The various Two important consequences derive from the ways to roll graphene into tubes are therefore mathe- SWNT structure as described above: matically defined by the vector of helicity Ch,andthe angle of helicity , as follows (referring to Fig. 8.1) 1. All carbon atoms are involved in hexagonal aromatic rings only and are therefore in equivalent OA D Ch D na1 C ma2 positions, except at each nanotube tip, where 6 5 D 30 atoms are involved in pentagonal rings (con- with sidering that adjacent pentagons are unlikely) as p p a 3 a a 3 a a consequence of Euler’s rule that also governs the a1 D x C y and a2 D x C y ; fullerene structure. For ideal SWNTs, chemical re- 2 2 2 2 activity will therefore be highly favored at the tube where a D 2:46 Å, and tips, at the locations of the pentagonal rings. 2. Although carbon atoms are involved in aromatic 2n C m cos D p ; rings, the CDC bond angles are not planar. This 2 n2 C m2 C mn means that the hybridization of carbon atoms is not pure sp2; it has some degree of sp3 character, in where n and m are the integers of the vector OA consid- a proportion that increases as the tube radius of cur- ering the unit vectors a1 and a2. vature decreases. The effect is the same as for the The vector of helicity Ch .D OA/ is perpendicular C60 fullerene molecules, whose radius of curvature to the tube axis, while the angle of helicity is taken is 0:35 nm, and whose bonds therefore have 10% sp3 with respect to the so-called zigzag axis: the vector of

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright character [8.11]. This has consequences for SWNT helicity that results in nanotubes of the zigzag type (see reactivity and electronic behavior (Sect. 8.4). below). The diameter D of the corresponding nanotube

Longitudinal 30 electrons which ) b). This feature a ( 8.4 < < positions, as in graphite High-resolution trans- , while having the vector / 0 ; n ABAB . Cross-sectional view (after [8. ) b view. An isolated single SWNTappears also at the top( of the image. Fig. 8.4a,b mission microscopy (TEM) images of an SWNT rope. C bond directions will provide zigzag- D 4 nm Image of two neighboring chiral SWNTs within ) nanotubes is such that 0 m ; ). Conversely, because of the sixfold symmetry of n The graphenes in graphite have n ; n provides two examples of what chiral SWNTsas look like, seen via atomic force microscopy. are accommodated bylowing the van stacking der of Waalssons forces graphenes, make to al- fullerenes develop.crystals gather Similar and rea- and SWNTs order into into fullerite SWNT ropes (Fig. three overall C type SWNTs, denoted rections will provide armchair-type( SWNTs, denoted Fig. 8.3 an SWNT bundle astunneling seen microscopy using (courtesy high-resolution ofsity scanning Prof. of Yazdani, Illinois Univer- at Urbana, USA) turbostratic polyaromatic carbon crystals.structure corresponds Turbostratic to graphenes that are stackedrandom with rotations or translations insteadup of following sequential being piled structure. This implies that noother than lattice the atom graphene planes plane themselves exists (corresponding to the (001)odicities atom give speciﬁc plane diffraction family). patterns These that are new quite peri- Provided the SWNTthe diameter SWNTs distribution in isinto ropes narrow, hexagonal arrays, tend whichest to correspond compactness spontaneously to achievable arrange thebrings (Fig. high- new periodicities with respect to graphite or of helicity parallel to one of the three C the graphene sheet, the angleral ( of helicity

D for na- and and / m n n ), and ; ı b) n ,and ﬁrst and .

1 and Zigzag athathav- a , . ), armchair- h ,theSWNT n 4 nm ı 8.2 ; C a,b). Generally 8.1 / 8.2 and nm . Armchair C 8.1 2 chiral angle separate the extremities m : C helical

/ 2 . The values of 60 n / . C 44 Å : . 3 m 1 ; p n Ä . fullerene molecule is a reasonable CC C a 60 D is sometimes inappropriate and should by the relation C D h a j ]. In the example of Fig. C h 7 Ä vector following the unit vector qualiﬁcations for achiral nanotubes refer to

C chiral j C bond length is actually elongated by the h [8. a–c are (9,0), (5,5), and (10,5) nanotubes re- C 2 D 41 Å a : 8.2 1 (graphite) D a) , they are sufficient to define any particular SWNT type SWNT (with an angle of helicity of 30 is related to are all expressedm as a functionby of denoting the them integers then The C curvature imposed by thelength structure; in the the averageupper bond C limit, while thegenuine bond graphite length is in thean flat lower graphene infinite limit in radius (corresponding to of curvature). Since a chiral SWNT, respectively.the This term also illustrates why preferably be replaced with where that is obtainedtwo by shaded aromatic rolling cyclesactly the is can a graphene be (4,2) chiral superimposed so nanotube.Fig. Similarly, ex- SWNTs that from the spectively, thereby providing examplesSWNT of zigzag-type (with an angle of helicity = 0 a given SWNTthe can number be of simply hexagonsof obtained the that by counting of the nanotube crossspeaking, section it (Fig. is clearing from the Figs. vector of helicity perpendicular to any of the notubes, although definitely achiral from theof standpoint symmetry, exhibit a nonzero armchair the way that the carbon atoms are displayed at the edge Nanomaterial and Nanostructures Part B

196 Part B | 8.1

2 different to those of other sp -carbon-based crystals, al- 8.1 | B Part though hk reflections, which account for the hexagonal symmetry of the graphene plane, are still present. Con- versely, 00l reflections, which account for the stacking sequence of graphenes in regular, multilayered polyaromatic crystals (which do not exist in SWNT ropes) are absent. This hexagonal packing of SWNTs within the ropes requires that SWNTs exhibit similar diameters, which is the usual case for SWNTs prepared by electric arc or laser vaporization processes. SWNTs prepared using these methods are actually about 1:35 nm wide (diameter of a (10,10) tube, among others), for reasons related to the energetic compromise mentioned earlier that the latter synthesis techniques allow to occur during the specific growth mechanisms taking place (Sect. 8.3).

8.1.2 Multiwall Nanotubes

Building MWNTs (multiwall carbon nanotubes) is a lit- 5 nm tle bit more complex, since it involves the various ways graphenes can be displayed and mutually arranged Fig. 8.5 High-resolution TEM image (longitudinal view) within filamentary morphology. A similar versatility of a concentric MWNT (c-MWNT prepared using an can be expected to the usual textural versatility of pol- electric arc). The insert shows a model of the related yaromatic solids. Likewise, their diffraction patterns Russian doll-like arrangement of graphenes (image by M. are barely differentiable from those of anisotropic pol- Monthioux, CNRS. Model by I. Suarez-Martinez, Curtin yaromatic solids. The easiest MWNT to imagine is University) the concentric type (c-MWNT), in which SWNTs with regularly increasing diameters are coaxially arranged and graphitic outer parts [8.13]. The other case oc- (according to a Russian-doll model) into a multiwall na- curs for c-MWNTs exhibiting faceted morphologies, notube (Fig. 8.5). Such nanotubes are generally formed usually originating from subsequent heat treatment at either by the electric-arc technique (without the need high temperature (e.g., 2000 ıC) in an inert atmosphere. for a catalyst), by catalyst-enhanced thermal cracking Facets allow the graphenes to resume a flat arrangement of gaseous hydrocarbons, or by CO disproportiona- of atoms (except at the junction between neighboring tion (Sect. 8.2). There can be any number of walls (or facets) which allows the specific stacking sequence of coaxial tubes), from two upwards. The intertube dis- graphite to develop. tance is approximately the same as the intergraphene Another frequent inner texture for MWNTs is the distance in turbostratic, polyaromatic solids, 0:34 nm so-called herringbone texture (h-MWNTs), in which (as opposed to 0:335 nm in genuine graphite), since the graphenes make an angle with respect to the na- the increasing radius of curvature imposed on the notube axis (Fig. 8.6). The value of this angle varies concentric graphenes prevents the carbon atoms from with the processing conditions (such as catalyst mor- being arranged according to the Bernal sequence as phology or composition of the atmosphere), from 0 (in in graphite. However, two cases allow a nanotube to which case the texture becomes that of a c-MWNT) to reach – totally or partially – the 3-D crystal periodic- 90ı (in which case the filament is no longer a tube, see ity of graphite. One is to consider a high number of below), and the inner diameter varies so that the tubu- concentric graphenes, where the more external concen- lar arrangement can be lost [8.15], meaning that the tric graphenes may have a long radius of curvature. latter are more accurately called nanofibers rather than In this case, the shift in the relative positions of car- nanotubes. h-MWNTs are exclusively obtained by pro- bon atoms from superimposed graphenes is so small cesses involving catalysts, generally catalyst-enhanced with respect to that in graphite that some commensu- thermal cracking of hydrocarbons or CO dispropor- rability is possible over distances long enough to make tionation. One long-debated question was whether the Bernal stacking possible over a large enough area. This herringbone texture, which actually describes the tex-

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright may result in MWNTs where both structures are as- ture projection rather than the overall three-dimensional sociated; in other words they have turbostratic cores texture, originates from the scroll-like spiral arrange-

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. After 5 nm ) 50 nm b ( ), closing high-resolution arrow mboo) multiwall ) b ( ]); Low magniﬁcation of ) 18 Some of the earliest ], and depend on the pro- a ( ]) ic multiwall nanotube (bc- 20 14 C heat treatment. Both the ı multiwall nanotube (bh-MWNT) As-grown. The nanotube surface is ) ]) a Fig. 8.6a,b herringbone and the bamboo textureshave become obvious. Graphene edges from the surface havewith buckled their neighbors ( off access to the intergraphene(after space [8. high-resolution TEM images of a herringbone (and ba nanotube (bh-MWNT, longitudinal view) prepared by COtionation dispropor- on an Fe-Co( catalyst. 2900 made of free graphene edges. 19 TEM images from bamboo multiwall na- 10 nm a) b) image of aMWNT)(after[8. bamboo-concentr entation of the graphenes inhelicity the angles of tube the (for nanotubes example,has constituting the c-MWNTs little importance). Graphene orientationof is texture, a whereas matter graphenenanotexture, perfection which both is are a commonly used matter tographene-based describe materials of [8. cessing conditions. While texture is a permanent fea- Fig. 8.7a,b a bamboo-herringbone showing the nearly periodicoccurs nature very of frequently the (after texture, [8. which notubes (longitudinal views).

in ). The bamboo 8.7 ) will ob- 8.4 and 8.6 b) platelet nanofibers ]. 17 10 nm , in the literature. 16 texture. It has now been demon- ]. 15 nanofibers cup-stack ), which grow in a catalyst-free process, na- 8.5 The properties of the MWNT (Sect. Unlike SWNTs, whose aspect ratios are so high that One nanofilament that definitely cannot be called Another common feature is the occurrence, to some a) notube tips are frequentlythe found catalyst to crystals be from associated which with they were formed. it is almost impossibleratios to for find MWNTs the (and tubeally carbon tips, lower nanofibers) the and are aspect often gener- TEM. allow Aside one to from image c-MWNTsarc tube (Fig. derived ends from by an electric viously largely depend on the perfection and the ori- the literature [8. a nanotube is built fromular graphenes to oriented the perpendic- filament axisSuch and filaments stacked are as referred piled-up to plates. as degree, of a limited amountpendicular of to the graphenes nanotube oriented axis, per- thus formingtexture. a This is notit a texture affects that either canMWNT the exist (bh-MWNT) on c-MWNT textures its (Figs. (bc-MWNT) own; or the h- is no longer open allfor the a way genuine along tube. the These filamentreferred are as to therefore it as sometimes is also question is whethershould such still filaments, be although called nanotubes, hollow, since the inner cavity ment of a singleof graphene independent ribbon truncated cone-like or graphenes in from whatalso the is called stacking a strated that both exist [8. Nanomaterial and Nanostructures Part B

198 Part B | 8.1

Created from viennaut on 2018-11-17 04:18:29. Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Carbon Nanotubes 8.2 Synthesis of Carbon Nanotubes 199 atB|8.2 | B Part la

lc N

L2 L1

Fig. 8.8 Sketch explaining the various parameters obtained from high-resolution (lattice fringe mode) TEM, used to quantify nanotexture: L1 is the average length of perfect (distortion-free) graphenes of coherent areas; N is the number of piled-up graphenes in coherent (distortion-free) areas; L2 is the average length of continuous though distorted graphenes within graphene stacks; ˇ is the average distortion angle. L1 and N are related to the la and lc values obtained from X-ray diffraction

ture (unless subjected to severe degradation), nanotex- name should be vapor-grown carbon nanofilaments ture can be quantified (Fig. 8.8), as it can be improved (VGCNF). Whether or not the filaments are tubular is by subsequent thermal treatments at high temperatures then a matter of inner morphology description [8.20], (such as > 2000 ıC) and potentially degraded by chem- which can be further refined by considering textural ical treatments (such as slightly oxidizing conditions). features such as bamboo, herringbone, and concentric To summarize, because work in the field started (see above). In the following, we will therefore use more than a century ago, the names of filamentous MWNTs for any hollowed nanofilament, whether they carbons have changed with time from vapor-grown contain graphene walls oriented transversally or not. carbon fibers, to nanofilaments, nanofibers, and eventu- Any other nanofilament (i. e., not hollowed) will be ally nanotubes. For all filamentous carbons, the generic termed a nanofiber.

8.2 Synthesis of Carbon Nanotubes

8.2.1 Solid Carbon Source-Based Synthesis formed on the cathode, Iijima [8.4] discovered the Techniques: The DC Electric Arc catalyst-free formation of perfect c-MWNT-type CNTs. Then, as mentioned above, the catalyst-promoted for- Principle mation of SWNTs was accidentally discovered after One route to produce CNTs is to vaporize a solid carbon amounts of transition metal were introduced into the source (usually graphite), which requires processes able anode in an attempt to ﬁll the c-MWNTs with metals to generate high temperatures (T > 5000 K). Various during growth [8.5, 6]. Since then, a lot of work has techniques have been employed for this (e.g., laser abla- been carried out by many groups using this technique in tion, DC electric arc, solar furnace). We will focus here order to understand the mechanisms of nanotube growth on the DC electric-arc technique, as the other methods in the synthesis of MWNTs and/or SWNTs [8.25–36]. have been almost abandoned for being less robust and The different mechanisms (such as carbon molecule versatile. Some information on the other techniques will dissociation and atom-recombination processes) in- be provided in Sect. 8.2.3. Further information can be volved in this high-temperature technique take place at found in the previous edition of this chapter [8.21]. different time scales, from nanoseconds to microsec- The DC electric-arc process is based on carbon onds and even milliseconds. The formation of nano- vaporization in an inert gas atmosphere at reduced pres- tubes and other graphene-based products occurs after- sure. The morphologies of the carbon nanostructures ward with a relatively long delay. and the SWNT yields can differ notably with respect The electric-arc method is based on the energy to the experimental conditions. It was (and still is) the transfer resulting from the interaction between the elec- ﬁrst method of producing fullerenes in relatively large trode and the plasma. This interaction causes anode quantities [8.22–24]. In the course of investigating other erosion, leading to the formation of a plasma, i. e.,

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright carbon nanostructures formed along with the fullerenes, an electrically neutral ionized gas, composed of neu- and more particularly the solid carbon deposit that tral atoms, charged particles (molecules and ionized

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ] 36 , ]. The ]. The 29 41 37 Window ]. Other authors Vacuum 28 Cathode Cathode holder Motor ]. The advantage of the latter is Anode 33 – 31 Gas inlet Gas Sketch of an electric-arc reactor the bottom alysts are used or not. SWNTs are found in the collaret and the web, yet The electrode diameter is a few millimeters but Two types of anode can be used, a graphite rod with Window Fig. 8.9 ing the plasma zone.different regions Carbon of nanoforms the are reactor: found in 1. The collaret,2. which forms around the The cathode weblike3. deposits found above the The cathode soot deposited all around the4. reactor walls and A hard deposit adherent to the cathode, whether cat- their formation isexperimental not conditions systematic (for instance and theywith do depends not a on form pressure the and of soot 40 kPa) are while obtainedgrowth systematically. the of The MWNTs cathode occurs catalyst-free in deposit the cathode deposit. varies from one authorcathode to has another. In a someder larger cases, to diameter the facilitate than their the alignment anode [8. in or- utilize electrodes of the same diameter [8. whole device can be designed horizontally [8. or vertically [8. the symmetry with respectcomputer to modeling (regarding gravity, convection which ﬂows, for facilitates instance). a coaxial hole (several centimeters ina length) ﬁlled mixture with of powdered catalyst(s),bly graphite, other and dopants possi- as needed,the or catalyst(s) are an homogeneously dispersed anode [8. within which former is by farfabrication. the most popular, due to their ease of . e

], n 8.9 40 , ]. Sub- 39 12 ), where / o C under inert n ı C e 1200 ] or water [8. =.n 1 Pa) of the chamber, e : 38 n ]. 37 are the electron and the neutral atom densities re- , or heat treatments in air) that are likely to 3 o n An example of a reactor layout is shown in Fig. Experimental Device One of the advantages of this synthesis technique but this adaptation hasburns remained between prospective. the The catalyst-doped arc a graphite graphite (or anode copper, for and instance)formed cathode: consists the plasma of thegas, mixture and of catalyst carbon vapors.sequence vapor, The of inert vaporization energy is transfer from theThe the importance con- arc of to the thethe anode power anode. of erosion the arc rate and alsoditions. depends on It other on is experimental con- worth noting thatdoes a not high necessarily anode lead erosion to rate a high CNT production. the other forsired filling working it pressure. withthrough Arc diametrically a opposed rare observation sapphire gas is windows fac- up possible to the de- Several elements such asboron, iron, nickel, gadolinium, cobalt, or yttrium, lysts, however cerium highest yields can weremetallic obtained be catalyst, using including a used a bi- transition asNi) metal (typically and cata- aatmosphere rare can earth be (typically composedhelium. yttrium); of Some argon work the was or also inert (preferably) performeddia, gas with such liquid me- as liquid nitrogen [8. It consists of aabout cylinder 1 m about in 30 height cming with in the two diameter valves, primary and one for evacuation perform- (0 sequent thermal treatments at atmosphere, however, succeed in somewhatstructural recovering quality [8. significantly affect the SWNT structure [8. and species), and electrons.plasma, defined The by the ionization ratio rate ( of this spectively, highlights the importance of energybetween transfer the plasma andtics the of this material. plasma and The notably theand characteris- ranges in temperature concentrations ofthe the plasma thereby various dependcomposition not species of only present the on anode the in butferred. nature also and on the energy trans- is the abilitywhich modify to the composition vary ofmedium the a high-temperature and large consequentlyplasma variety characteristics allow of to themal parameters be conditions most determined for relevant so thebe control that obtained. of However, opti- a CNT majornique formation drawback – can of and thisSWNTs tech- of – any other isthey technique are that used associated the with to othernants SWNTs produce carbon of phases formed the and are rem- catalyst.exist, Although they not purification are pure: processes allHNO based on oxidation processes (e.g., Nanomaterial and Nanostructures Part B

200 Part B | 8.2

The role of synthesis parameters is studied for pro- tion of telescope-like morphology, and the occurrence 8.2 | B Part cess optimization, in terms of nanotube yield and qual- of nested crystals (Gd, in the paper cited) [8.31, 33]. ity. They include the type of doped anode, the nature Generally speaking, the optimized result achieved us- and concentration of the catalyst(s), the pressure and ing bimetallic catalysts such as Ni+Y regarding SWNT nature of the plasmagen gas, the arc current intensity, or yield was proposed once to be due to the transitory for- the distance between electrodes. Experiment duration, mation of an yttrium carbide coating over the nickel however, is preferably short (in the range of a few min- particles whose lattice constants were somewhat com- utes) in order for the synthesis not to be significantly mensurable with that of graphene, thereby resulting in affected by the increasing pressure rise resulting from SWNT growth [8.45]. However, another explanation, anode vaporization. The plasma characteristics (species more plasma-related, could be that the presence of yt- concentrations and temperature) constitute the link be- trium increases the anode erosion rate and leads to tween input parameters and obtained products. Their higher plasma temperatures, which both are plasma fea- study as a function of operating parameters is impor- tures favorable to SWNT growth. tant for better understanding of the phenomena involved Surprisingly, loading heterogeneous anodes with di- during nanotube formation. However, few works are amond instead of graphite (with similar 1 m range dedicated to this; they are based on atomic and molecu- grain size) does not affect the plasma characteristics lar optical emission spectroscopy [8.31–34, 36]. (both graphite and diamond lead to the same plasma composition once carbon is vaporized at high tempera- Results ture, > 4000 K), nor the type and yield of the products The numerous results available in the literature regard- formed [8.34, 35], while changing graphite grain size ing the synthesis of CNTs by the DC arc process show from 1 to 100 m does ([8.43, 44] and Fig. 8.10a). This that both the morphology and yield strongly depend shows that thermal conductivity prevails over electrical on the experimental conditions. It is also worth not- conductivity as a leading parameter, and is driven by the ing that the products obtained do not consist solely porosity amount left when compacting the filler materi- of CNTs. In addition to catalyst remnants found in als into the anode cavity. Indeed, lower grain size led to various concentrations in all deposit areas, nontubular better compaction and powder homogeneity, hence to forms of carbon can be obtained [8.30, 32, 33]. They a steadier erosion of the anode, a feeding of the plasma include nanoparticles (NPs), fullerene-like structures with more constant carbon and catalyst proportions including C60, poorly organized polyaromatic carbons, which goes along with smoother radial temperature pro- nearly amorphous nanofibers, multiwall shells, single- files (see the previous version of this chapter in [8.21]). wall nanocapsules, and amorphous carbon. The nature, The consequence on the product is a lower variability proportion, and distribution of the catalysts in the an- in the carbon phases formed, finally resulting in an en- ode are particularly important. Optimized conditions hanced purity and yield of the SWNT phase. for high SWNT yields (with lengths in the microme- Finally, the chamber volume was also shown to be ter range and diameters typically around 1:4 nm, mostly an important parameter for SWNT growth [8.46]. The found in the collaret (5070%) and the web ( 50% volume must be limited to keep convection cooling effi- or less)) may correspond to a helium pressure of about cient and sustain a high thermal radial gradient which is 60 kPa, an arc current of 80 A, an electrode gap of favorable to SWNT growth. However, the volume has 1 mm, the use of a heterogeneous anode and Ni=Y to remain sufficient to ensure recirculation of catalyst as coupled catalysts [8.5, 29, 42], and graphite powder particles responsible for growing SWNTs. Therefore, grainsizeinthe1m range [8.43, 44]. Deviations from Fig. 8.10 shows that lower chamber volume and smaller those conditions can have significant consequences: grain size both generate hotter plasma and higher C2 using Ni=Co instead of Ni=Y as catalysts may pre- concentration, a set of conditions found to correspond vent the formation of SWNTs; Ni=Co catalysts in a to optimized SWNT growth. homogeneous instead of heterogeneous anode mostly The analysis of the plasma from the anode to the generate double-wall nanotubes (DWNTs), while de- cathode along the discharge axis shows a huge verti- creasing the ambient pressure from 60 to 40 kPa also cal gradient ( 500 K mm) close to it (probably due suppresses nanotube formation. It is worth noting that, to convection) along with a dramatic increase of the unlike SWNTs, MWNTs are formed as a cathode de- C2 concentration [8.21]. The latter demonstrates that posit almost systematically, i. e., it is less sensitive to C2 moieties are secondary products resulting from the parameter variations. However, although using a rare recombination of primary species formed from the an- earth as a single catalyst does not allow one to grow ode. It also suggests that C2 moieties may also be

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright SWNTs, it may affect MWNT growth by promoting the building blocks for MWNTs (formed at the cath- the closure of graphene edges, the preferred forma- ode) [8.33, 35]. A plausible reason is that the zone of

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. Time (s) ]) Radial temperature 46 ) a ( Radial coordinates (mm) coordinates Radial ) 2 s, either through a heteroge- /m 21 48]. , 47 m and two chamber volumes. A smaller volume V = 25 l V = 60 l Evolution with time of the gas temperature at the concentration 10 (nl 02468101214161820 2 0 0 0.5 1.0 1.5 2.0 2.5 C Instead, later attempts in the 1990s focused on the 5 100 700 500 300 200 800 600 400 900 10 15 30 25 20 Gas temperature (°C) temperature Gas 1000 b) limit of theaxis growth and zone 1 (1 cm cmsize above away of 1 the from arc the center) electrode for a graphite grain induces a lower temperatureconvection cooling, ramp which thanks seems to to beformation an favorable to enhanced SWNT Fig. 8.11 grown carbon ﬁbersCVD – processes [8. via thickening in catalyst-free synthesis of genuinewalled) CNTs by CCVD. (either Thisdecomposition single- method of involves a or the carbon-containing multi- catalytic metallic source particles on or small cluster neous (if a solid substrate is involved) or homogeneous

m) and two different chamber volumes (25 and 60 l). 1 μm μm100 = 25 l –V = 25 l –V 1 μm μm100 = 60 l –V = 60l –V Radial coordinates (mm) coordinates Radial shows an example of g. 8.11 90%-purified SWNTs at prices ], the catalyst-enhanced thermal 1 radial concentration ratio. Smaller grain size results in better anode compaction, hence in higher anode 2 Emission spectroscopy data obtained from experiments involving heterogeneous-type anodes, with two C ) b ( Synthesis Techniques 0 0.5 1.0 1.5 2.0 2.5 Temperature (K) Overall, the importance of the physical phenomena Although many aspects still need to be understood, 5000 3000 6000 4000 a) the evolution with timean of area. the gas temperature in such (charge and heat transfers) thating occur in the the anode arc dur- plasma clearly indispensable, an makes aspect which thein is many characterization still works. neglected of the the electric-arc methodrently is used to one produce SWNTs of as commercialalthough three products, it is methods progressively being cur- abandoneddifficulty due to to the reduce productionchemical vapor costs deposition down (CVD)-based processes, tocause be- of that the of subsequentand extensive the purification needed drawbackFor of instance, Nano-lab being (MA, a USA)til was discontinuous recently proposing (2016) un- process. 40 ranging from 225 to 2500 US $= thermal conductivity, and lower chamber volume enables more efficient convection cooling (after [8. 8.2.2 Gaseous Carbon Source-Based As mentioned in [8. actual SWNT formationoutside corresponds the to plasma. colder Figure areas, Fig. 8.10a,b cracking of aCO) – gaseous commonly referred carbon to as sourcedeposition catalytic chemical (CCVD) (hydrocarbons, vapor – hasbon been nanofilaments for known over to a produce century. However,works, in car- early carbon nanofilaments were mainlyact produced as to alarger core (micrometric) substrate carbon for the fibers subsequent – growth so-called of vapor- different graphite grain sizes (1 and 100 profiles; Nanomaterial and Nanostructures Part B

202 Part B | 8.2

process (if everything takes place in the gas phase). The ability of catalyst-enhanced CO disproportiona- 8.2 | B Part The metals generally used for these reactions are tran- tion to make carbon nanofilaments was reported by sition metals, such as Fe, Co, and Ni. CNTs prepared Davis et al. [8.55] as early as 1953, probably for the by this method are generally much longer (a few tens to first time. Extensive follow-up work was performed by hundreds of micrometers) than those obtained by arc Boehm [8.56], Audier et al. [8.14, 57, 58], and Gadelle discharge (a few micrometers). It is also possible to et al. [8.59, 60]. grow dense arrays of nanotubes. CCVD processes appear very sensitive to the nature and the structure of Experimental Devices. Although formation mecha- the catalyst used, as well as to the operating condi- nisms for SWNTs and MWNTs can be quite different tions [8.49]. This is a rather low-temperature process (Sect. 8.3, or refer to a review article such as [8.61]), typically between 6001000 ıC, which enables high many of the catalytic process parameters play similar selectivity for the production of MWNTs preferably roles in the type of nanotubes formed: the tempera- to graphitic particles and amorphous-like carbon, com- ture, the duration of the treatment, the gas composition pared to the solid carbon source-based methods such as and flow rate, and of course the catalyst nature and arc discharge. In turn, this lower reaction temperature size. At a given temperature, depending mainly on the does not allow any structural rearrangements therefore nature of the catalyst and the carbon-containing gas, leading to more structural defects (lower nanotexture) catalytic decomposition will take place at the surface for MWNTs produced by CCVD compared to arc dis- of the metal particles, followed by mass transport of the charge. These defects can be removed by subsequent freshly produced carbon by surface or volume diffusion heat treatments in vacuum or inert atmosphere. Whether until carbon concentration exceeds the solubility limit such a discrepancy is also true for SWNTs remains causing precipitation to start. questionable as CCVD SWNTs are generally gathered CCVD CNTs form on very small metal particles, into bundles of smaller diameter (a few tens of nm) typically in the nanometer range [8.61]. These catalytic than their arc discharge and laser ablation counterparts metal particles are prepared mainly by reducing transi- (around 100 nm in diameter). CCVD, specifically when tion metal compounds (salts, oxides) by H2 prior to the performed in a fluidized bed reactor [8.50](seenext nanotube formation step (where the carbon-containing section), provides reasonably good prospects for use in gas is required). It is possible to produce these catalytic large-scale and low-cost processes for the mass produc- metal particles in situ in the presence of the carbon tion of CNTs, a key point for their application at the source, allowing for a one-step process [8.62]. As con- industrial scale. trolling the metal particle size is the key issue, coalescence is generally avoided by using low concentrations Heterogeneous Processes of catalytic metal precursors or by placing metal parti- Heterogeneous CCVD processes simply involve pass- cles on an inert support such as an oxide (Al2O3,SiO2, ing a gaseous flow containing a given proportion of zeolites, MgAl2O4, MgO) or more rarely on graphite. a hydrocarbon (mainly CH4,C2H2,C2H4,orC6H6,usu- The easiest hence most frequent route is to use the ally as a mixture with either H2 or an inert gas such as supported catalysts as a static phase placed within the Ar) over small transition metal particles (Fe, Co, Ni) in gas flow. This is what most laboratories do, and also a furnace. The particles are deposited onto an inert sub- companies such as Nanocyl, the only CNT manufac- strate, by spraying a suspension of the metal particles turer in Belgium, which sells MWNTs (research grade on it or by another method. The reaction NC3100, 95% C, 10 nm average diameter) at 5 C=g for 500 g order (2016 data). The CCVD process can also y CxHy ! xC C H2 be coupled to a fluidization contactor by using catalytic 2 porous powders to maximize the catalyst specific sur- is chemically defined as catalyst-enhanced thermal face area. cracking and has been used since the late nineteenth In the fluidized bed (FB) reactor, gas-solid fluidiza- century. Extensive publications on this topic include tion consists in flowing a gas upwards through a vertical those by Baker et al. [8.3, 51], or Endo et al. [8.52, 53] bed of powders which form a suspension in the gas as well as several review papers published after 1990, (Fig. 8.12). Gaseous bubbles appear and rise through such as [8.54]. However, CO can be used instead of the powders, generating intense gas–solid mixing and hydrocarbons; the reaction is then chemically defined then high thermal and mass transfer rates between the as catalyst-enhanced disproportionation (the so-called gas, the powders, and the heated reactor walls [8.63]. Boudouard equilibrium) As a consequence, a fluidized bed is fully isothermal.

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright When coupled to CCVD, it maximizes the conver- 2CO • C C CO2 : sion rate of the gaseous carbon precursor, the catalyst

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. . 2 2 nm ]) (pure or salt were 66 2 2 (3) CNTs H 2 ] prepared nano- 67 containing gas over the ng gas, leading to the growth et al. [8. (2) -containing atmosphere to form Example of a bundle of double-wall 2 ) b Catalytical metal Catalytical particles ( Ivanov ]). bon-containi ) on well-dispersed transition metal par- 2 65 ], resulting in very finely dispersed metal Formation of nanotubes via the CCVD-based ) (1) 69 a , ( was found to be the best catalyst/support com- 2 68 Supported catalyst or solution solid the catalytic metal particles freshly prepared metal particles leading togrowth. nanotube For example, a) b) particles (from 1 to 50they nm diameter). reported In the the preparation lattereter of work, MWNTs around with 4 a nmrecently, diam- ethanol and solutions only containing a two NiCl or three walls. More impregnation technique. (1) Formationparticles by of reduction catalytic of metal position a of precursor; a (2) car catalyticof decom- CNTs; (3) removaltubes of (after the [8. catalyst to recover the nano- ticles (Fe, Co, Ni, Cu) supported on graphite or SiO then proposed the uselyst of [8. a zeolite-supported Co cata- bination for the preparationthe of other combinations MWNTs, led buttimes to covered most with carbon of amorphous-like filaments, carbon.improve some- In the order to dispersion ofveloped metals, a the precipitation-ion-exchange same method on group silica de- mixed with H used to impregnate a carbon fiber paper. After drying 4. Decomposition of a carbontubes through the decomposition of C nanotubes (DWNTs) prepared this way (after [8. Fig. 8.13 3. Reduction in a H Co-SiO

kg = C 50 drop sensor Pressure Pressure P Δ Distributor Thermocouples CNRS laboratory in collabo- Filter 4 2 2 H 2 N H C is a perforated plate supporting the pow- Toward exhaust ], it was selected by ARKEMA, the only ). Sketch of a typical lab-scale ﬂuidized bed CCVD Fluidized bed 64 The impregnation-based process generally in- Electrical furnace 8.13 distributor chloride) of the metal catalyst form the oxide of the catalytic metal chosen catalytic metalthermally stable in host oxide. a chemically inert and The catalyst is then reduced to form the metal There are two main ways to prepare the catalyst: the desired metal catalyst Mass flowMass controllers ders when at rest CNT manufacturer inMWNTs France, (Graphistrength C100 which grade) is at able to sell selectivity, and theCCVD product process uniformity. allows kilogramsto As to be the tons produced FB- ofscale from MWNTs [8. the lab scale to the industrial Fig. 8.12 The reactor as in use inration the with LGC- the LCC-CNRS laboratory, Toulouse (France). 1. Support impregnation by a2. salt solution Drying and (nitrate, calcination of the supported catalyst to the nanotubes can then(Fig. be separated from the catalyst Results with CCVDlysts. Involving Impregnatedvolves Cata- four successive steps: 2. Preparation of a solid solution of an oxide of the particles on whichcarbon the source catalytic will decomposition lead to of CNT the growth. In most cases, (2016 data). 1. Impregnation of a substrate with a salt solution of Nanomaterial and Nanostructures Part B

204 Part B | 8.2

and reduction under H2 at 1023 K, randomly orientated oxidants such as HNO3,KMnO4,H2O2) are thus re- 8.2 | B Part MWNTs with a diameter of 20 nm were grown on quired but inevitably result in low final yield of CNTs, the paper from a C2H4=H2 mixture, thus forming 3-D which are often quite damaged. Flahaut et al. were conductive layers for electrochemical capacitor appli- the first to use MgO-based solid solutions (for exam- cations [8.70]. ple MgxCoyOz) to prepare SWNTs and DWNTs that could be easily separated without incurring any damage Results with CCVD Involving Solid Solution-Based via fast and safe washing with an aqueous HCl solu- Catalysts. A solid solution of two metal oxides is tion [8.72]. formed when ions of one metal mix with ions of the In most cases, only very small quantities of catalyst other metal. For example, Fe2O3 can be prepared in (typically less than 500 mg) are used, and most claims solid solution in Al2O3 togiveaAl22xFe2xO3 solid so- for high-yield productions of nanotubes are based on lution. The use of a solid solution allows homogeneous laboratory experimental data, without taking into ac- dispersion of one oxide in the other to be obtained. count all of the technical problems related to scaling These solid solutions can be prepared in different ways; up to a laboratory-scale CCVD reactor. At the present coprecipitation of mixed oxalates and combustion syn- time, although the production of MWNTs is possi- thesis are the most common methods used to prepare ble on an industrial scale, the production of affordable nanotubes. Nanotube synthesis by catalytic decompo- SWNTs is still a challenge, and controlling the arrange- sition of CH4 over a Al22xFe2xO3 solid solution was ment of and the number of walls in the nanotubes is first developed by Peigney et al. [8.62] and then studied also problematic. For example, adding small amounts extensively by the same group using different oxides of molybdenum to the catalyst [8.74] can lead to dras- such as spinel-based solid solutions (Mg1xMxAl2O4 tic modifications of the nanotube type (from regular with M = Fe, Co, Ni, or a binary alloy [8.65, 71]) or nanotubes to carbon nanofibers – Sect. 8.1). Flahaut magnesia-based solid solutions [8.65, 72](Mg1xMxO, et al. have recently shown that the method used to pre- with M = Fe, Co, or Ni). The homogeneous dispersion pare a particular catalyst can play a very important of the catalytic oxide makes it possible to produce very role [8.75]. Double-walled CNTs (DWNTs) represent small catalytic metal particles at the high temperature a special case: they are at the frontier between single- required for CH4 decomposition (chosen for its greater (SWNTs) and multiwalled nanotubes (MWNTs). Be- thermal stability compared to other hydrocarbons). This cause they are the MWNTs with the lowest possible method involves heating the solid solution from room number of walls, their structures and properties are temperature to a temperature between 8501050 ıCin very similar to those of SWNTs. Any subsequent func- a mixture of H2 and CH4, typically containing 18 mol% tionalization, which is often required to improve the of CH4. The nanotubes obtained are typically gath- compatibility of nanotubes with their external envi- ered into small-diameter bundles (less than 15 nm) ronment (composites) or to give them new properties with lengths up to 100 m. The nanotubes are mainly (solubility, sensors), will partially damage the external SWNTs and DWNTs, with diameters between 13nm. wall, resulting in drastic modifications in terms of both Their properties depend upon the nature of the metal (or electrical and mechanical properties. This is a serious alloy) and the inert oxide (matrix); the latter because the drawback for SWNTs. In the case of DWNTs, the outer Lewis acidity seems to play an important role [8.73]. wall can be modified (functionalized) while retaining For example, in the case of solid solutions containing the structure of the inner tube. CCVD allows synthesis around 10 wt% of Fe, the amount of CNTs obtained de- of DWNTs on a gram-scale [8.66] with high purity and creases in the following order depending on the matrix high selectivity (around 80% DWNTs) (Fig. 8.13b). oxide: MgO < Al2O3 < MgAl2O4 [8.65]. Obtaining pure nanotubes by CCVD requires re- Homogeneous Processes moving the catalyst (as for all other techniques). In The homogenous route, also called the floating catalyst the case of catalysts supported (impregnated) in a solid method, differs from the other CCVD-based methods solution, the supporting – and catalytically inactive – because it only uses gaseous species as catalyst and car- oxide is the main impurity, both in weight and volume. bon precursors. The basic principle of this technique, Removing oxides such as Al2O3 or SiO2 requires ag- whose mechanisms are similar to the other CCVD pro- gressive treatments (hot caustic solutions of KOH and cesses, is to produce in situ the catalyst particles from NaOH for Al2O3, or an acidic solution of HF for SiO2). a gaseous precursor and then to decompose a gaseous However, such treatments have no effect on other im- carbon source in order to obtain CNTs. purities such as other carbon forms (amorphous-like

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright carbon, graphitized carbon particles and shells, and so Experimental Devices. The typical reactor used in on). Oxidizing treatments (air oxidation, use of strong this technique is a quartz tube placed in a furnace into

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ). , which is de- 100 nm large ]. Upon heat- 5 / 91 ]. Another bottle- CO . 80 g (2016 average ASI yr of = = 5$ : 40 t 0 , although this can be cut by g if purified (2016 data). Other Heterogeneous Processes , decomposes into atoms that condense 8.2.2 5 / ]. The current production yields approach CO . 91 g, or 800 $= , h and nanotubes typically have no more than 90 Templating The principle of this technique is to deposit the solid The company Continental Carbon Nanotechnolo- It should be emphasized that only small amounts of A significant breakthrough concerning this tech- MWNTs (Pyrograf-III), and Hyperionbridge, Catalysis USA), (Cam- which produces MWNT-based materials. Though prepared inprocesses, a similar MWNTs way remainSWNTs, by yet far CCVD-related over a less largemanufacturer, price the expensive range depending CNT than on typeetc.) the and (herringbone, quality, concentric and theprices amount to can be be ordered. as Hence, low as fare for Pyrograf-III grade) a factor of 10 for very large quantities. The templating technique is the only otherfrom method aside the electric-arc technique that isCNTs able without to a synthesize catalyst. Anotherapproach useful is aspect that of it this tained allows naturally, provided aligned the nanotubes substrate to is not be removed. ob- carbon coating obtained from the CVD methodwalls onto of the a porous substrate whose pores are arranged in gies Inc. (Houston,materials USA) currently prepared sells byof raw this 575 SWNT process, $= atcompanies a that specialize market in price Sciences MWNTs Inc. include Applied (Cedarville,a USA), production which facility currently has of 450 mg= 7 mol% of iron impurities.tubes In grow the in HiPco high-pressure, process, high-temperatureCO nano- flowing on catalytic clusterssitu of by thermal iron. decomposition Catalyst of Fe is formed in into large clusters. SWNTs nucleateparticles and via grow CO on disproportionation (the these Boudouardaction, re- see Sect. over MWNTs, because suppressing the carbon shellmation for- limits the formation of MWNTs too. CNTs have been produced sodustrial far, and levels scaling-up seems to quite in- the difficult. in One situ reason produced istor catalyst that particles wall stick so to thatlead the CNT reac- to growth clogging from of these the particles reactor may [8. neck is to beprecursors able fed to in increase theduction, without the reactor obtaining catalyst quantity in particles that of order arebig. gaseous too This to problem increase has not pro- yet been solved. nique couldRice be University, which produces therity SWNTs [8. of HiPco high pu- process developed at livered within a coldwith CO hot flow and CO then in rapidly the mixed reaction zone [8. ing, the Fe

]to ], or ]. ]. 87 ]have 76 82 60 84 ]. It is as- ][8. 5 89 / CO . ] and the liquid so- ], the presence and 81 77 , thereby enhancing the ]. An interesting result is ], the composition of the 2 88 86 , ], and MWNTs [8. 85 83 ] such as ferrocene, nickelocene, 79 – 77 , Ar, or He), is passed. The first zone ]. 2 85 ] or in benzene [8. C to form the CNTs. The metal precursor ı 80 This technique is quite flexible and SWNTs ], DWNTs [8. 81 1200 , The overall process can be improved by adding The main drawback of this process concerns the 80 is generally a metal-organic compound, suchvalent as carbonyl a zero- compound like [Fe purity; (ii) preventsencapsulated the in catalyst carbon particles shellsinactive), thereby from too enhancing the early being nanotube (making yield.over, it More- them was found to promote the formation of SWNTs of the reactor is keptthe at catalyst a particles, lower temperature and to700 the produce second zone is heated to which the gaseous feedstock, containingcursor, the metal the pre- carbona source, vector sometimes gas (N hydrogen, and a metallocene [8. or cobaltocene. In recentethanol works, ferrocene [8. is diluted in sumed that the oxygenorganized (i) carbon preferably out burns into the CO poorly be obtained, while the lattercrease in results productivity [8. in a significant in- the increase in yield and purity broughtinput about by of a small oxygen, asinstead achieved of by hydrocarbons using as alcohol feedstock vapors [8. Results. [8. other compounds such as ammonia orspecies sulfur-containing to thealigned reactive nanotubes gas and mixed phase. C–N nanotubes The [8. former allows difficulty to controlcles, the hence the size CNT formation of isthe often the production accompanied of by metal undesired nanoparti- carbon carbon forms or (amorphous polyaromatic carbonous phases phases or found as asforms coatings). have vari- been In found particular, as encapsulated themetal result particles of that the are formation of growth. too The large same to operating promotegeneous parameters nanotube CCVD as processes for must hetero- to be selectively obtain controlled the in desired order CNTsstructure, morphology and including thethe choice reaction of temperature [8. the carbon source, incoming gaseous feedstock [8. been obtained, in proportions dependingfeedstock on gas. the carbon The techniquefor some has time also in the beennanofibers production exploited [8. of vapor-grown carbon lution is vaporized just beforereactor or to at form the entrance ametal of gaseous and the the mixture carbon precursors. containing Thesuch both use as of the cobalt metal salts, nitrate, has also been reported [8. proportion of hydrogen, which cantation influence of the the orien- graphene with respect tothus the switching nanotube from axis, c-MWNT to h-MWNT [8. Nanomaterial and Nanostructures Part B

206 Part B | 8.2

parallel channels. The substrate can be alumina or ze- three-phase AC power supply being operated at 600 Hz 8.2 | B Part olite for instance, which present natural channel pores, and with arc currents of 250400 A. Carbon precur- while the whole system is heated to a temperature that sors, gaseous, liquid or solid, are injected at the desired cracks the hydrocarbon molecules selected as the car- (variable) position into the plasma zone. It has been bon source [8.92]. demonstrated that this plasma technology can be used Provided the chemical vapor deposition mechanism to produce a wide range of carbon nanostructures rang- is well controlled, the synthesis results in the chan- ing from carbon blacks to CNTs over fullerenes with nel pore walls being coated with a variable number a high product selectivity. of graphenes. Either MWNTs (exclusively concen- In solar furnace devices, solar rays are focused onto tric type) or SWNTs can be obtained. The smallest a graphite pellet containing catalysts in a neutral gas SWNTs (diameters 0:4 nm) ever obtained were ac- chamber. They have been used by several groups to first tually synthesized using this technique [8.9]. The na- produce fullerenes but the original devices were then notube lengths are directly determined by the channel modified to achieve CNT production [8.97, 98]. It was lengths, in other words by the thickness of the sub- demonstrated that solar energy-based synthesis is a ver- strate plate. One main advantage of the technique is satile method for obtaining SWNTs that could be scaled the purity of the tubes (no catalyst remnants and few up from 0:10:2to10g=h and then to 100 g=h produc- other carbon phases), and their well-calibrated, single- tivity using existing solar furnaces. A numerical reactor value diameters. Conversely, the nanotube structure is simulation was performed in order to improve the qual- open at one end or both, which can be an advantage ity of the product, which was subsequently observed to or a drawback depending on the application, and make reach 40% SWNT in the soot [8.99]. them more sensitive to chemical attacks. The porous MWNTs (including coiled MWNTs, a peculiar matrix can be kept or dissolved in order to recover the morphology resembling a spring) have been success- tubes, as needed. The method is not suitable for mass fully prepared by a catalyst-free (although Li was production. present) electrolytic method, by running a 35A current between a graphite crucible (as anode) and 8.2.3 Miscellaneous Techniques a graphite rod (as cathode) [8.100]. The graphite crucible was filled with lithium chloride, while the whole In addition to the major techniques described in system was heated in air or argon at 600 ıC. As with Sect. 8.2.1 and Sect. 8.2.2, other ways to produce na- many other techniques, by-products such as encapsu- notubes can be found in the literature. They can offer lated metal particles, carbon shells, amorphous carbon, alternatives such as a low-cost or a catalyst-free pro- and so on, are formed. duction. However, none has been convincing enough or A pure chemistry route has also been proposed, economically preferable so far with respect to the ma- using the polyesterification of citric acid onto ethy- jor processes described previously. Some examples are lene glycol at 50 ıC, followed by polymerization at provided in the following, the three first sharing simi- 135 ıC and then carbonization at 300 ıC under argon, larities (high temperature and solid carbon source) with followed by oxidation at 400 ıCinair[8.101]. Despite the dc arc process. the latter oxidation step, the solid product contains short For the laser ablation process a graphite pellet con- MWNTs, although they obviously have poor nanotex- taining catalysts is vaporized using a focused laser tures. By-products such as carbon shells and amorphous beam [8.93]. The carbon species, swept along by a flow carbon are also formed. of neutral gas, are then deposited as soot in different re- Short MWNTs have been obtained through gions: on a conical water-cooled copper collector, on a catalyst-free (although Si is present) pyrolytic the containment quartz tube walls, and on the back- method which involves heating silicon carbonitride side of the pellet. Improvements of this method include nanograins in a BN crucible to 12001900 ıCin the use of a second pulsed laser to get better pellet ir- nitrogen within a graphite furnace [8.102]. No details radiation [8.94] or the use of two pellets (one made are given about the possible occurrence of by-products, of graphite and one made of catalysts) simultaneously but they are likely considering the complexity of the irradiated [8.95]. Laser-based methods can lead to high- chemical system (Si-C-B-N) and the high temperatures quality SWNTs but are generally not considered to be involved. competitive in the long term for the low-cost production The catalyzed reaction between a solid car- of SWNTs. bon source and atomic hydrogen has been investi- Three-phase AC arc plasma has been used for the gated [8.103]. Graphite nanoparticles ( 20 nm) are

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright processing of carbon nanomaterials [8.96]. An electric sent with a stream of H2 onto a Ta ﬁlament heated at arc is established between three graphite electrodes, the 2200 ıC. The species produced, whatever they are, then

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ] , – ]. 123 129 118 125 , 83 ]. 8.14b), or 117 rticles onto a prepat- ]. 8.15c). The precursor ] or photolithography ]. ]. 112 116 89 ticles in mesoporous silica 110 ]. 8.14a), which are suitable for 113 ]. Combining e-beam lithography 8.15a,b) leads to densely packed ]. or quartz substrates under high vac- 2 122 115 , ]. ], due to a mechanism related to that pre- 114 124 126 ]. uum [8. minum oxide templates [8. and inductive plasma deep etching [8. photoresist polymer using conventionalwhite black films and as a mask [8. ticles with tailored diameters on a support [8. 121 Here is a list of the most common deposition meth- tion/reduction steps for thin filmmina substrates deposition [8. on alu- or atomictips force [8. microscope/microscopy (AFM) Depositing the catalyst nanopa and template methodslarge-scale has production also of ordered been MWNTs reported [8. for more generally to localizeual CNTs the [8. growth of individ- wafer has beennotubes parallel used to to the grow substrate networks (Fig. of na- alloys on SiO by sol–gel processes [8. The pyrolysis of hydrocarbons in the presence of ]. Important synthesis parameters include the heat- 5. Electrochemical deposition into pores in anodic alu- 4. Photolithographic patterning of metal-containing 6. Spin-coating colloidal suspensions of catalyst par- the nanotubes (of course,result removing in the loosing the substrate alignment). may ods: 1. Metal salt impregnation followed by oxida- 7. Stamping a catalyst precursor over a patterned Si 3. Thermal evaporation of Fe, Co, Ni, or Co-Ni metal 2. Embedding catalyst par terned substrate allowslocal control occurrence of andtube the bunches the formed. frequency arrangement Theconsist of of materials produced the of mainly aligned nano- arrayed, MWNTs (Fig. densely packed, freestanding, field emission-based applications for instance [8. SWNTs have also beenthat produced, and the it introduction was ofprocess reported water allows vapor during impurity-freesized the [8. SWNTs CVD to be synthe- viously proposed for the effect ofof using hydrocarbon feedstock alcohol [8. instead organometallic precursorlocene molecules or iron such pentacarbonyl,nace as operating system in metal- (Fig. avertically dual aligned MWNTs fur- (Fig. is first sublimed ator low temperature injected in as thefeedstock, a first and furnace solution then along thehigher with whole temperature the system in hydrocarbon is the pyrolyzed second at furnace [8. 130

]), ]and 112 105 C. SWNTs ı into SWNTs 2 C that supports ı 1200 ]. 107 ). Although this approach ini- ] or anodic alumina [8. 111 ]. The driving forces for this align- 8.2.2 , ) require that CNTs grow as highly 109 110 8.7 , of temperature 500 ] arrays can be selectively obtained. Gen- 108 4 g for an SWNT-grade product (TUBALL) = 106 ]. A regular gaseous hydrocarbon source 104 yr SWNT production complex, with prices as low = Diffusion flame synthesis was also attempt- Finally, a recent and original technology should be During CCVD growth, CNTs can self-assemble into by a high-temperature electrochemicalassisted reaction, by an likely iron catalyst.SiAl The is Russian company claiming OC- toa10t be the world’s largest facility with (ethylene, and others)passed along into with aair ferrocene laminar vapor and diffusion is CH flame derived from transition metal particles. Thein a whole dynamic chamber vacuum of isto 40 Torr. form kept SWNTs according are supposed toof the the authors. method, One besides major itsothers, drawback complexity is compared to that the from it the is Si substrates difficult tobonded. to which recover they seem the to nanotubes be firmly ed [8. Several applications (such as fieldplays, emission-based see dis- Sect. 8.2.4 Synthesis with Controlled Orientation hit a Si polished plate warmed to 900 are formed, together with encapsulatedsoot, metal and particles, so on.structure In is addition quite poor. to a low yield, the SWNT mentioned, called the Graphetronis 1.0 based process, on which the decomposition of CO as a few $ aligned individuals or bunches,rays, in or highly that ordered theythis case, ar- are the purpose located of the attion process is but specific not controlled mass positions. produc- growth In andcontrol purity, of with nanotube morphology, subsequent texture, andGenerally structure. speaking, the morethe synthesis promising of methods aligned nanotubes for areprocesses based (see on Sect. CCVD tially produced mainly MWNTs, DWNT [8. erally speaking, SWNTs and DWNTs nucleate at higher temperatures than MWNTs [8. nanotube bunches aligned perpendicularlystrate to if the the sub- catalystthickness film [8. on the substrate has a critical SWNT [8. ment are thenanotubes, van which der allow them Waalsto to interactions the grow between perpendicularly substrates. the Whendeposited the onto a catalyst mesoporous nanoparticles substrateporous are (such silica as [8. meso- containing 75% SWNT, 15% catalyst, and 10%carbon of forms, other including carbon shells encapsulatingcatalyst the (2016 data). the mesoscopic pores control the growth direction of Nanomaterial and Nanostructures

Part B

Part B | 8.2 208

a) b) 8.2 | B Part

2 μm

2 μm 2 μm

Fig. 8.14a,b Examples of directional growth of CNTs obtained from the pyrolysis of a gaseous carbon source over catalyst nanoparticles previously deposited onto a patterned substrate: (a) a controlled pattern of nanotube pillars grown perpendicular to the substrate: each pillar is made of thousands of DWNTs aligned vertically (after [8.127]); (b) suspended SWNTs grown parallel to the substrate interconnecting silicon pillars (after [8.128])

a) b) c)

Low-temperature oven High-temperature oven 50 μm

Fig. 8.15a–c Sketch of a double-furnace CCVD device used in the organometallic/hydrocarbon copyrolysis process. (a) Sublimation of the precursor. (b) Decomposition of the precursor and MWNT growth onto the substrate. (c) Example of the densely packed and aligned MWNT material obtained (after [8.129])

ing and feeding rate of the precursors, vector gas (Ar or of amorphous carbon [8.131]. The use of phthalocya- N2) and gaseous hydrocarbon flow rates, and the pyrol- nines of Co, Fe, and Ni has also been reported, and ı ysis temperature (6501050 C). Using [Fe.CO/5]as in this case the organometallic precursors pyrolysis is the catalyst source results in thermal decomposition at also the carbon source for the vertically aligned MWNT elevated temperatures, producing atomic iron that de- growth [8.132]. posits on the substrates in the hot zone of the reactor. Densely packed coatings of vertically aligned CNT growth occurs immediately after the introduc- MWNTs may also be produced over metal-containing tion of [Fe.CO/5] so the growth temperature depends deposits, such as iron oxides on aluminum [8.133]. mainly on the carbon feedstock used (from 750 ıCfor Well-aligned MWNT arrays can be produced on a large acetylene to 1100 ıC for methane). scale on ceramic spheres using the floating cata- The nanotube yield and quality are directly linked to lyst technique [8.134]. Finally, the Langmuir–Blodgett the amount and size of the catalyst particles, and since method can be used to produce densely packed mono- the planar substrates used do not exhibit high surface layers of aligned noncovalently functionalized SWNTs areas,the catalyst dispersion is a critical step in the pro- from an organic solvent [8.135]. This method seems cess. NH3-etching of the catalyst thin film provides the valid for bulk materials with various diameters and of- appropriate metal particle size distribution and may also fers the advantage that the SWNT monolayers are read-

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. tip- 8.16). orbitals are molten cata- D and scheme, where the car- ]. ratio between the amount 141 base-growth ]. 16 , graphenes), but there are no crystal faces 15 gaseous C species, liquid 50 nm onto which graphenes form and then D scheme: the catalyst moves forward while the 40 nm) have never been observed. The reasons D The bamboo texture that affects both the herring- This mechanism can therefore provide either c- gaseous moieties at the catalyst surface the catalyst, thus forming a solid solution walls. The texture isentation of then the determined crystalaxis by faces [8. relative the to ori- the filament If conditions are such that the catalyst is a liquid lyst, S to preferentially orient theminimization rejected requirements graphenes. will Energy concentric therefore and make parallel them tocatalyst the particles filament axis. (or With inthe large the mechanisms absence of above any will substrate), generally follow a growth rejected carbon formsthere the is a nanotube substrate behind, orConversely, when not. whether One the end catalyst might particlesthe be deposited substrate left onto open. are smallinteraction enough forces with to the be substrate,nism the held growth will in mecha- follow place a by bone and thetinguishing concentric aspect textures ofanism: may the the reveal dissolution-rejection mech- a periodic,phenomenon. Once dis- discontinuous the dynamics catalystration of threshold has in terms reached the of the itsit carbon satu- quite content, it suddenly. Then expels ita given becomes amount of able carbon to againalytic without incorporate having activity any for cat- a littlereached while. again, Then and so over-saturation on is [8. bon nanofilament grows away froming the the substrate, catalyst leav- nanoparticle attached to it (Fig. MWNT, h-MWNT, or platelethowever, are nanofibers. mainly The formed when latter, crystallized catalyst particles and are largeoped enough crystal to faces exhibitleast with fully 40 extensions devel- in the range of at pile up. Indeed,ters platelet (< nanofibersfor with this low are diame- relatedneed to graphene to energetics, reach suchof as the the edge optimal carbonner atoms carbon (with atoms (where dangling all of bonds) the and in- 1. Adsorption then decomposition2. of Dissolution C-containing then diffusion of the C species3. through Back-precipitation of solid carbon as nanotube shared). droplet, due to the use oflyst temperatures beyond melting the temperature, cata- adescribed mechanism above similar can to(vapor still that occur, which is really VLS

– 136 C is the most common ı species into the primary 2 1200 ]. ] mechanism, it is quite difficult to find C, yet 800 139 ı 140 ]. If the conditions are such that the catalyst is a crys- Low-Temperature Conditions temperature range fortubes growing with the well-structured usual nano- catalysts. tallized solid, the nanofilament isa probably mechanism formed via similarthree to steps a are defined: VLS mechanism, in which comprehensive and plausible explanations that areto able account for both thevarious various morphologies conditions observed. used What and follows the tempt is to an provide at- overall plausible explanationsof of the most phenomena, while remainingexperimental data. consistent From with various the results, itthe appears most that important parametersmodynamic ones are (only probably temperature the willhere), be ther- considered the catalysta substrate. particle size, and the presence of In CCVD, nanotubes arebelow frequently 1000 found to grow far 8.3.2 Catalytically Activated Growth Although growth mechanismsclude involving catalysts a in- aVLS[8. more or less extensive contribution from In additionmerely to a chemical vapor the infiltrationrolytic mechanism templating for carbon, py- the technique,on growth which of the c-MWNT cathode is example as in of a catalyst-free the deposit The carbon electric-arc nanofilament driving method growth. force isone is electrode a to related rare thein to other the charge via plasma. transfer thecleus It particles from is contained is formed,direct not but incorporation clear once of it how has, the C it MWNT may nu- include the 8.3.1 Catalyst-Free Growth The growth mechanismsdebated of for CNTs the haveallow main been carbon reason nanofilaments highly that towhich grow the means are that conditions there very that areanisms. diverse, many related Another growth reason mech- occur is during growth thatobserve are the in pretty phenomena rapid situ. that growth and It occurs such difficult is that to the generallyis number minimized, agreed, of for energetic dangling however, reasons. bonds Much that mation related can infor- be found in review papers such as [8. 8.3 Growth Mechanisms of Carbon Nanotubes graphene structure, asfullerenes [8. was previously proposed for 138 Nanomaterial and Nanostructures Part B

210 Part B | 8.3

Fig. 8.16a–g High-resolution TEM images of several 8.3 | B Part a) b) c) d) g) SWNTs grown from iron-based nanoparticles using the CCVD method, showing that particle sizes determine SWNT diameters in this case (after [8.142]). Yet the catalyst crystal imaged (the dark spot at the bottom of each tube) is different for each ﬁgure, considering images back- ward from (f) to (c) illustrates what could be a sequence of growth of an SWNT from a single nanocrystal, as sketched e) in (g). (a) and (b) show additional examples of fully grown SWNT SWNTs, similar to (c) J

a carbon-rich feedstock, which is generally in excess, f) with a constant composition at a given species time of ﬂight. Roughly speaking, the longer the isothermal CH 4 CH 4 zone, the longer the nanotubes. This is why the lengths of the nanotubes can be much longer than those ob- Fe2O3 tained using solid carbon source-based methods. Scale bars = Substrate The comments above are summarized in Table 8.1, 10 nm compared with basic information relating to the high- temperature growth conditions (Sect. 8.3.2, High- Therefore, it is clear that 1 catalyst particle = 1 Temperature Conditions below). nanoﬁlament in any of the mechanisms above. This explains why achieving a narrow distribution of nanotube High-Temperature Conditions diameters in CCVD is quite challenging, particularly High-temperature conditions (several thousands of ıC) when nanosizes are required for the growth of SWNTs. are typically used in solid carbon source-based methods Only particles < 2 nm are useful for this (Fig. 8.16), such as the electric-arc method. Both the carbon source since larger SWNTs are not favored energetically [8.8]. and the catalysts are atomized. Of course, catalyst- Another distinguishing aspect of the CCVD method is grown SWNTs do not form in the plasma, where that growth can occur all along the isothermal zone temperatures are the highest whereas c-MWNTs do. of the reactor furnace as it is continuously fed with The plasma medium is a mixture of atoms and radicals,

Table 8.1 Guideline indicating the relationships between possible carbon nanoﬁlament morphologies and some basic synthesis conditions. Columns (1) and (2) mainly relate to CCVD-based methods; column (3) mainly relates to plasma-based methods Increasing temperature . . . Substrate Thermal gradient ! ...andphysicalstateofcatalyst Solid Liquid Liquid from Yes No Low High (crystallized) from melting condensing (1) (2) atoms (3) Catalyst particle size . 3nm SWNT SWNT – Base growth Tip growth Long length Short length & 3nm MWNT c-MWNT SWNT Tip growth Tip growth Long length Short length (c,h,b) platelet nanoﬁber Nanotube diameter Heterogeneous related to catalyst Homogeneous a particle size (independent of particle size) Nanotube/particle One nanotube/particle Several a SWNTs/particle

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ]. 41 10 nm ]. Con- ]) 8 18 b). This is C distance in TEM image of 8.17 ) b ( C bond increases as the ]. Hence, alternatively, Y could 145 35 nm is again a matter of energetic onditions (see text). : ), and the gas-phase composition sur- 1 b) 8.10 50 nm) catalyst particle (Fig. A major difference from the low-temperature mech- 10 graphene, could possibly playbilizing a beneﬁcial the role nanotube/catalyst inexplain sta- why interface, the which SWNTlic yield could alloys is (as enhanced opposed by toBut bimetal- single this metal catalysts) needs [8. CNT the growth, catalyst whichas to is SWNTs be not only grow crystallized ascertained. asthose during For bundles, could it result instance, was from proposedturation the that occurrence phenomenon of of ato the cell struc- liquid the catalyst so-calledity according mechanism solutal [8. Bénard–Marangonimostly instabil- play a majorthe role favorable in thermal properties. providing the plasma with anisms described fornanotubes CCVD are formed methods( from is a that single,why many relatively the large diameters ofture SWNTs are much grown more homogeneous at thanwith high those associated CCVD tempera- methods. The reason thatdiameter the most frequent is surface layer ofcontaining yttrium catalyst carbide core), the (ontois lattice the commensurable distance main of with which Ni- that of the C changes. This explains why nanotubes from arcerally are gen- shorter thanmass nanotubes production by from CCVD is CCVD, favored. and why compromise. Larger SWNTs are lessversely, stable the [8. strain onradius of the curvature decreases. C Anotherthe difference low-temperature from mechanism for CCVDperature is that gradients tem- inhuge (Fig. high-temperature methodsrounding the are catalyst droplets is also subjected to rapid igh-temperature c

car- SWNT growth SWNT External C supply outer T° occurs for the ) which also will 2 8.3.2 ], and from the outer ]. In the latter, carbon carbon atoms reach the 143 144 inner SWNT nucleation SWNT Internal C supply SWNTs) (to nucleate supply + external C (to close tips) et al. [8. et al. [8. T° a), according to the VLS mechanism Saito Mechanism proposed for SWNT growth in h ]. Once the 8.17 ) Bernholc a to higher order molecules such as corannu- ( 143 2 M-C alloy Vaporisation a) surface of the catalyst particle,bon they species, meet including corannulene, the that willto contribute capping thecapped, merging nanotubes nanotubes. can grow Once both from formed theatoms inner and (Fig. carbon proposed by even in conditions that produce SWNTs.uration The same in sat- Ccarbon-metal alloy described droplets as in well, resulting Sect. cipitation in the of pre- excesseffect C of outside the thetor, decreasing particle which thermal decreases due the gradient to solubilitymetal threshold in the [8. of the C in reac- the tend to close intonot a energetically favored, these ring. cycles Since will be adjacent hexagons. Such pentagons a are molecule isfor thought fullerenes. to Fullerenes be are actually a always probable produced, precursor some of which are likely toliquid combine droplets. and At condense some into distancezone, from the the medium is atomization therefore madeloy of droplets carbon-metal and al- of secondary carbonfrom species that C range Fig. 8.17 SWNT growing radially from the surface of a large Ni catalyst particle in an electric-arc experiment (after [8. by ﬁve hexagons (asbonds the at fastest low way energetic to cost),tion limit thereby site providing dangling for a other carbon ﬁxa- atoms (or C lene, which is made of a central pentagon surrounded posed by carbon atoms, according to the adatom mechanism pro- atoms from the surrounding mediumattracted in then the stabilized reactor are face by at the the nanotube/catalyst surface carbon/catalyst contact,their inter- promoting subsequent incorporationgrowth at mechanism the therefore tubegrowth mainly base. scheme. follows The The the occurrence base of a nanometer-thick Nanomaterial and Nanostructures Part B

212 Part B | 8.3

8.4 Properties of Carbon Nanotubes 8.4 | B Part

In MWNTs that consist of stacked graphenes, the bond However, the mesopores of the SWNT, obtained by strength varies significantly depending on whether the subtracting the micropore volume from the total, consti- in-plane direction (characterized by very strong co- tute the major fraction of the pores [8.154]. The pores valent and therefore very short – 0:142 nm – bonds) in MWNTs can be divided mainly into hollow inner or the direction perpendicular to it (characterized by cavities with small diameters (with narrow size distri- very weak van der Waals and therefore very loose – butions, mainly 310 nm) and aggregated pores (with 0:34 nm – bonds) is considered. Such heterogene- wide size distributions, 2040 nm), formed by inter- ity is not found in single SWNTs. However, the actions between isolated MWNTs. It is worth noting heterogeneity returns, along with the related conse- that opening or closing the central canal significantly quences, when SWNTs associate into bundles. There- influences the adsorption properties of CNTs. Open- fore, the properties – and applicability – of SWNTs may ing, closing, or cutting CNTs, as well as heating them also change dramatically depending on whether single can considerably affect their surface area and pore SWNTs or SWNT ropes are involved. structure. For instance, activating MWNTs with KOH In the following, we will emphasize the proper- or NaOH was shown to promote microporosity and ties of SWNTs, since their unique structures often lead reaching surface areas as high as 1050 m2 g1 [8.155, to different properties to regular polyaromatic solids. 156]. However, we will also sometimes discuss the properties of MWNTs for comparison. Adsorption Sites and Binding Energy of the Adsorbates 8.4.1 Overall Properties of SWNTs It is expected that adsorption properties of small- diameter CNTs such as SWCNTs are strongly affected With diameters in the nanometer range, and lengths by tube diameter and helicity, as the electronic struc- in the range of micrometer to hundreds of microme- ture is. Generally speaking, three types of sites exist ters, SWNTs exhibit huge aspect ratios. They are stable on a graphene lattice: top (T), bridge (B), and center up to 600700 ıCinairandupto 15001800 ıC (C) (Fig. 8.18a). Additionally, the possibility to adsorb in an inert atmosphere, beyond which they transform species on the convex (exohedral adsorption) or con- into regular graphene-based solids [8.146]. They have cave (endohedral adsorption) surface should be taken half the mass density of aluminum. The properties of into account [8.157]. For SWNT bundles, adsorption SWNTs, like any molecule, are heavily influenced by may occur onto the various types of surface available the way their atoms are arranged, hence by their helic- (Fig. 8.18b). For MWCNTs, adsorption can occur in ity [8.147]. the aggregated pores, inside the tube or on the external walls; in this latter case, the presence of structural de- 8.4.2 Adsorption Properties fects (vacancies, Dienes/Stone–Wales defects, dopants) plays a significant role in the adsorption as they can Accessible Specific Surface Area of CNTs be seen as islands with elevated reactivity. Addition- Various studies dealing with the adsorption of nitro- ally, modeling studies have shown that the CNT convex gen onto MWNTs [8.148–150] and SWNTs [8.150, (outer) surface is chemically reactive because the con- 151] have highlighted the porous nature of both materi- vex arrangement of pyramidalized sp2 carbon atoms als. CNTs present large surface areas because of their makes the formation of chemical bonds with reagent structure and physical form. Their actual surface ar- species possible. For a related reason, the concave (in- eas may be influenced by a variety of properties such ner) surface should be more inert and can withstand the as tube/fiber diameter, bundling and agglomeration, presence of highly reactive species encapsulated within purity, and surface functionalization [8.150]. The the- the nanotubes. This difference in reactivity between oretical surface area of CNTs has a broad range, from convex and concave surfaces increases as the tube di- 501315 m2 g1 depending on the number of walls, ameter decreases [8.158, 159]. the diameter, and the number of nanotubes in a bun- Generally speaking, the adsorbates can be either dle of CNTs [8.152]. Experimentally, the surface area charge donors or acceptors to the nanotubes. Trends of an SWNT is often larger than that of an MWNT. in the binding energies of gases with different van der The total surface area of as-grown SWNTs is typ- Waals radii suggest that the groove sites of SWNTs are ically between 400900 m2 g1 (micropore volume the preferred low-coverage adsorption sites due to their : : 3 1 2 1

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright 0 150 3cm g ), whereas values of 200400 m g higher binding energies (Table 8.2). In the ﬁrst stages for as-produced MWNTs are often reported (Table 8.2). of adsorption (occurring at the most attractive sites), it

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ]. Ad- ) a ( g) = 2 ] ]. The sta- 22 45 – 483 783 Surface area per site (m sketch of 153 173 ) b Fig. 8.18 sorption sites on graphene; ( an SWNT bundle cross-section, illustrating the four different adsorption sites Groove :049 :089 :062 :119 – 0 0 0 0 Attractive potential per site (eV) Pore ]. The chemical reaction of hydrogen with 171 Surface Groove Pore Interstitial Surface pore Aggregated pores Adsorption sites A limited number of theoretical as well as experimental studies on theCNTs binding exist. energies of Whilebinding gases most onto energies of on thesesorption, SWNTs, some studies consistent experimental report withhydrogen, results, low are in physi- still particularial. controvers Thedrogen for energetics chemisorption of hy- onmodeled a using (6,6) gradient-corrected nanotubetheory [8. density has been functional The adsorption ofand single metallic atoms SWNT onfor was a a studied semiconducting large from number ﬁrst of principles foreign atoms [8. carbon nanotubes is expectedexothermic to and become also increasingly coverages. to Oxygen gas proceed could be physisorbed more viasive disper- rapidly van der at Waals forces high orof chemisorbed a via chemical formation bond, and adsorptionther could on take perfect nanotube place walls ei- or at defect sites172 [8. ble adsorption sites, bindingelectronic energy, properties and were thethe analyzed. resulting bonding The and character associateddramatic physical of variations properties depending exhibit on theatom. type While the of atoms adsorbed of goodas conducting metals, Cu such andas Au, form Ti, very Sc, weakhigh binding bonding, Nb, energy. atoms Adsorption and geometries such ing and Ta afﬁnities bind- are ofalso metal adsorbed investigated nanoparticles through with DFT onto (density relatively CNTs functional thewere

). 8.2 ]. For hydro- Interstitial Surface b) 75% higher than 75% higher than graphene) 162 ]. Opening CNTs ]. Quantum chem- – Binding energy of the adsorbate Low, mainly physisorption (25 Physisorption 165 164 160 , ) adsorption within the 2 ]. B 163 ,N 2 900 400 g) ]. Finally, several studies have = 2 167 ]. Only a few studies deal with ad- Surface area (m 400 200 , C 169 166 , T :3) 0 g) 168 = 3 :15 Mesoporous Porosity (cm Microporous (0 Adsorption properties and sites of SWNTs and MWNTs. The data in the last two columns are from [8. a) shown that, at low coverage,adsorbate the on binding an SWNT energy is of between the 25 inner walls [8. the binding energy on a single graphene (Table seems that adsorption ortial channels condensation of in the SWNT the bundlesof intersti- depends the on molecules the (and/or size onon the their SWNT diameters) interaction and energies [8. ical calculations suggest thatchannels adsorption of in bundles interstitial NTs formed is of possible large-diameterbarriers, and SWC- a can result account oftween for strong neighboring high dispersion SWCNTs desorption interactions [8. be- gen and other small moleculesmethods like have CO, shown computational that,interstitial for open and SWNTs, groove the sitesvorable pore, than are surface sites energetically [8. more fa- favors gas (including O This discrepancy caneffective be coordination attributed at tobundles the [8. an binding increase sites of in SWNT sorption sites in MWNTs,butane adsorbs more but onto MWNTs it with smaller hasdiameters, outside been which shown is that consistentthat with the strain another on statement curved graphenetion. surfaces Most affects of sorp- the butaneof adsorbs to the the MWNTs external while surface condenses only in a the pores small170 [8. fraction of the gas Nanomaterial and Nanostructures MWNT SWNTs (bundle) Type of nanotube Part B Table 8.2

214 Part B | 8.4

ory) calculations [8.174]. Pd, Pt, and Ti nanoparticles jected to external pressure, the small interaction be- 8.4 | B Part strongly chemisorb to the CNT surface. Unlike the tween the tube walls results in the internal tubes ex- cases of atomic adsorptions, the aluminum particle has periencing reduced pressure [8.180]. The electronic the weakest binding affinity with the CNT. Aluminum transition energies are in the infrared and visible spec- or gold nanoparticles accumulated on the CNT develop tral range. The 1-D Van Hove singularities have a large the triangular bonding network of the metal surfaces in influence on the optical properties of CNTs. Visi- which the metal–carbon bond is not favored. ble light is selectively and strongly absorbed, which can lead to the spontaneous burning of agglomerated 8.4.3 Electronic and Optical Properties SWNTs in air at room temperature [8.181]. Strong Coulomb interaction in quasi-one dimension leads to The electronic states in SWNTs are strongly influenced the formation of excitons with very large binding ener- by their 1-D cylindrical structures. One-dimensional gies in CNTs (200400 meV), and degenerated states sub-bands are formed that have strong singularities in at the K, K0 points lead to multiple exciton states the density of states (Van Hove singularities) [8.175]. with dipole-allowed (bright) and dipole-forbidden tran- By rolling the graphene sheet to form a tube (n; m), sitions (dark) [8.182, 183]. Photoluminescence can be new periodic boundary conditions are imposed on observed in individual SWNT aqueous suspensions sta- the electronic wavefunctions, which give rise to one- bilized by the addition of surfactants. Detailed photoex- dimensional sub-bands: Ch K D 2q where q is an inte- citation maps provide information about the helicity- ger and Ch is the helicity vector defined in Sect. 8.1. dependent transition energies and the electronic band Much of the electronic band structure of an SWNT structures of CNTs [8.184]. The agglomeration of can be derived from the electronic band structure of SWNTs into bundles influences their electronic states. graphene by applying the periodic boundary conditions Photoluminescence signals are quenched for bundles. of the tube considered. The graphene conduction and CNTs are model systems for the study of 1-D trans- valence bands touch each other at six corners (K points) port in materials. Apart from the singularities in the of the Brillouin zone [8.176]. If one of these sub-bands density of states, electron–electron interactions are ex- passes through the K point, the nanotube is metallic; pected to show drastic changes at the Fermi edge; the otherwise it is semiconducting. This is a unique prop- electrons in CNTs are not described by a Fermi liq- erty that is not found in any other 1-D system, which uid, but instead by a Luttinger liquid model [8.185] means that for certain orientations of the honeycomb which describes electronic transport in 1-D systems. lattice with respect to the tube axis (chirality), some It is expected that the variation of electronic conduc- nanotubes are semiconducting and others are metallic. tance versus temperature follows a power law, with The band gap for semiconducting tubes is found to be zero conductance at low temperatures. Depending on inversely proportional to the tube diameter. As pointed how L (the coherence length) on the one hand and out in Sect. 8.1, knowing (n; m) allows – in princi- Lm (the electronic mean free path) on the other hand ple – prediction of whether the tube is metallic or not. compare to L (the length of the nanotube), different However, the gap energy of semiconducting SWNTs conduction modes are observed: ballistic if L L, decreases as their diameter increases, whatever their L Lm, diffusive if L Lm < L, and localization if (n; m) values, up to a value of 14 nm at which point Lm L L. Fluctuations in the conductance can be the gap energy approaches the energy range brought by seen when L L . For ballistic conduction (a small the room temperature [8.10]. Hence MWNTs with di- number of defects) [8.186–188], the predicted elec- ameters beyond this value are no longer semiconducting tronic conductance is independent of the tube length. and exhibit properties similar to other forms of regular, The conductance value is twice the quantum of conduc- polyaromatic solids. It has been shown that electronic tance (the fundamental conductance unit) G0 D 4e=h conduction mostly occurs through the external tube for due to the existence of two propagating modes. Be- MWNTs; even so, interactions with internal tubes often cause of the reduced electron scattering observed for cannot be neglected and they depend upon the helicity metallic SWNTs and their stability at high tempera- of the neighboring tubes [8.177]. tures, CNTs can support high current densities (max. The electronic and optical properties of SWNTs are 109 A=cm2): about three orders of magnitude higher considerably influenced by the environment [8.178], than Cu. Structural defects can, however, lead to quan- starting with the bundle configuration as compared to tum interference of the electronic wave function, which isolated. In such a case, due to the interactions be- localizes the charge carriers in 1-D systems and in- tween neighboring tubes, a bundle of identical, metallic creases resistivity [8.185, 189, 190]. Localization and

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright SWNTs can behave as a semiconducting object [8.179]. quantum interference can be strongly inﬂuenced by ap- When multiple-wall tubes such as DWNTs are sub- plying a magnetic ﬁeld [8.191]. At low temperatures,

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ]. 199 ]. 203 C bond an- C illustrates how 3 30 GPa [8. ]. The flexural mod- 8.19 198 aphene faces are chem- 3 TPa for both SWNTs : 1 C bonds between regular agons each, as opposed to the ]. Figure ]. However, that SWNTs can C bonds involved in heterocy- ], with a flexibility that decreases 202 90% filling rate suggests the oc- 204 – Accessible Specific Surface Area of 196 , 200 sites (C C bonds to undergo distortions, resulting 8.4.2 ) with C 2 weak fullerenes. Although gr 8.5.2 ). Although SWNTs belong to the graphene-based 150 GPa have actually been measured for perfect 60 The chemical reactivities of SWNTs (and c- hexagons) only deviates slightly fromfor 0 whereas C it is 1 cles) over strong sites (C currence of side defects (typically Dienes defects, oth- in bond angles that are closer to the sp 8.4.5 Reactivity CNTs have a large surface toment interact with (Sect. their environ- CNTs material family, unlike graphite,cally they active) have dangling bonds, no and (chemi- ratio unlike fullerenes, of the ically relatively inert, theon radius the graphene of in nanotubes curvature causesplanar imposed the sp three normally strength, provided the tube ends arewise, well concentric capped tubes (other- could glide relativeinducing to each high other, strain). Tensileas strength values as high gle in diamond as the radius ofthough curvature it shortens. is Even not enough to makeically the reactive, carbon one atoms consequence chem- iscreated that nesting at sites the are concaveare surface created and on physisorption the sites convextion surface, efficiency both with that an increases adsorp- decreases. as the nanotube diameter MWNTs) are believed tosince derive they mainly contain six from pent thetube caps, body, which supposedlyIndeed, only contains applying hexagons. oxidizingoxidation, treatments wet-chemistry oxidation) to selectivelythe CNTs opens nanotube (air tips [8. be filled with(Sect. foreign molecules such as fullerenes as the numbersurements of performed on wallsfrom defective increases. MWNTs CCVD Conversely, obtained mea- exhibit a range of 3 MWNTs from an electric arc [8. ulus of perfect MWNTs should logicallythat be for higher SWNTs than [8. Values of tensile modulusknown, are in also the the highest range values of 1 defect-free CNTs could spectacularlyfield revolutionize the of highals. mechanical However, performance making fibrouscarbon micrometer-sized materi- nanotubes fibers while maintaining outproperties the remains of ultimate an unaddressed CNT challenge dueproblem to of the creating covalent bondsthat between have the to CNTs be aswithout strong creating as defects that in of CNT the structure CNT [8. C–C bonds and MWNTs [8. ]

], C are ]. 196 195 ]. The 194 SWNT , 192 193 ). 1 Large circles ≈ 45 GPa K 154 nm for the C Tensile modulus (GPa) Tensile 1 K 1100 ]. In order to observe the P120 X70 190 hybridization) of the curved ]. Very high tensile strength are pitch-based carbon fibers P100 2 ons in the conductance as the 100 times that of steel [8. M60J 197 6000 W m 142 versus 0: P75 M50 X50 triangles M46J 0J X49 45 GPa [8. M40 400 600 800 1000 1200 P55 M4 T1000 T800 H T800 M5 T300 Nicalon Steel X20 hybridization; 0: As a probable consequence of both the small num- 3 T 400 H T 200 Titanium Plot of the tensile strength versus the tensile modulus for X24 bond length inThis graphene makes and CNTs diamond –larly SWNTs respectively). stable or against deformations. c-MWNTsof The – SWNTs tensile particu- can strength be 20 (while being 6 times lighter) andsured has actually as been mea- 8.4.4 Mechanical Properties CNTs are unique due to thebetween particularly the strong bonding carbons (sp the discrete energy spectrum leads toade a resulting Coulomb in block- oscillati gate voltage is increased [8. graphene sheet, which(sp is stronger than in diamond values areMWNTs, also since combining expected perfect tubesis concentrically for not ideal supposed to (defect-free) be detrimental c- to the overall tube different conductance regimes, itsider is the influence important of the to electrodes whereriers con- Schottky bar- are formed. Palladium electrodes haveto been form shown excellent junctions with nanotubes [8. influence of superconducting electrodesnetic electrodes or on ferromag- electronic transportspin in polarization CNTs has due also to been explored [8. ber of defectspose (at phonon transport) least and the theSWNTs cylindrical exhibit topography, kind a of large phononresults defects in mean a free that high path, thermal op- conductivity. The which ductivity thermal of con- SWNTs isisolated comparable graphene to layer or that high of purity diamond a [8. single, or possibly higher ( Nanomaterial and Nanostructures P25 5 Kevlar Glass 7 6 5 4 3 2 1 Tensile strength (GPa) strength Tensile Part B Fig. 8.19 various fibrous materials compared to SWNTs. PAN-based carbon fibers,

216 Part B | 8.4

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erwise wrongly named Stone–Wales defects [8.205]) method, because they grow very fast in nonsteady 8.5 | B Part able to be chemically attacked [8.206, 207], thereby conditions, are likely to contain more structural de- creating additional entry ports along the tube. An av- fects than CCVD-synthesized SWNTs. It is however erage of one Dienes defect every 5 nm along the tube the contrary for arc-prepared c-MWNTs, which exhibit length, involving about 2% of the carbon atoms in a reg- a perfect, defect-free nanotexture [8.20] as compared ular (10,10) SWNT has been estimated [8.207]. This to CCVD-prepared c-MWNTs. Finally, the reactivity of means that the overall chemical reactivity of CNTs h-MWNT-type nanotubes is intrinsically higher, due to should depend strongly on how they are synthesized. the occurrence of accessible graphene edges at the na- For example, SWNTs prepared by the arc-discharge notube surface.

8.5 Carbon Nanotube-Based Nano-Objects (Carbon Meta-Nanotubes)

Carbon nanotubes are beautiful objects exhibiting a va- bon occurs [8.215, 216]. An amazing result of such riety of amazing properties from a theoretical point attempts to synthesize hetero-MWNTs is the subse- of view or when investigated at lab-scale. However, quent formation of c-MWNTs made up of coaxial alter- as soon as actual devices and materials have to be nate carbon graphene tubes and boron nitride graphene prepared, and moreover made compatible with up- tubes [8.217]. Conversely, examples of hetero-SWNTs scaled processes, they more often than not need to be are few, although the synthesis of B- or N-containing modified. Several modification routes have been dis- SWNTs has recently been reported [8.213, 218, 219]. tinguished [8.208], which are listed in the following Only one successful synthesis of genuine BN-SWNTs sub-sections. As it is a very active, multiple-field re- has been reported so far [8.220]. search area, only the basis is provided here. Further information can be found in related chapters and review 8.5.2 Filled Carbon Nanotubes papers from the current literature, beginning with the book which was dedicated to it [8.209]. SWNTs or MWNTs can have their inner cavities filled (partially or entirely) with foreign atoms, molecules, 8.5.1 Heteronanotubes compounds, or crystals [8.207, 221]. The terminology X@SWNT (or X@MWNT, if appropriate, where X is It is possible to replace some or all of the carbon the atom, molecule and so on involved) has been used atoms in a nanotube with atoms of other elements – for such structures since 1999 [8.222]. The very small mostly boron and nitrogen [8.210], but also phospho- inner cavity of nanotubes is indeed an amazing tool for rus [8.211] and possibly sulfur – without affecting preparing and studying the properties of confined na- the overall honeycomb lattice-based graphene structure. nostructures of any type, such as salts, metals, oxides, Nanotubes modified in this way are termed heteronan- gases, or even discrete molecules like C60,forexam- otubes [8.210]. They can exhibit new behaviors (for ple. Because of the almost one-dimensional structure example, BN nanotubes are electrical insulators) or of CNTs (particularly for SWNTs), encapsulated ma- modified properties (e.g., enhanced resistance to oxi- terials might have different physical and/or chemical dation, modulation of electronegativity). This is indeed properties and stability with respect to the unencapsu- a way to enable better control over such properties. lated or bulk material. Indeed, if the volume available For instance, one current challenge in carbon-SWNT inside a CNT is small enough, the foreign material synthesis is to obtain selective formation of the de- is mostly made of surface atoms with reduced co- sired SWNT structure, as it drives the metallic or ordination. Filling material/nanotube interactions can semiconductor character. In this regard, it was demon- also result in the filled nanotube itself behaving dif- strated that replacing some C atoms with N or B atoms ferently from a pure nanotube. This the basis of the leads to SWNTs with systematic metallic electrical current efforts being made to develop SWNT-based ca- behavior [8.212, 213]. Most examples of heteronan- bles exhibiting electrical conductivity reaching that of otubes found in the literature are MWNTs. The het- metals such as copper, thanks to interactions of the eroatom usually involved is nitrogen, due to the ease SWNT bundle with iodine and sulfuric acid molecules with which gaseous or solid nitrogen- and/or boron- as dopents [8.223]. containing species (such as N2,NH3, BN, HfB2) can Because of the limitations of some desirable CNT

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright be passed into existing equipment for synthesizing ﬁlling materials, such as very high melting tempera- MWNTs [8.212, 214] until complete substitution of car- ture or poor solubility, it is also possible to ﬁll CNTs

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. 2 cm = 10 nm) are 200 N ]. As the precur- ]. The wet chem- 2 nm). In addition, 243 204 , 235 , -sealed in a silica ampoule. 233 ]. However, a related study inves- 237 ], although other groups have followed 242 – 238 Most of the works involving the application of Molten-State Filling Method was proposed [8. tigated MWNTs, whose inner diameters (5 generally larger than for SWNTs (1 a major problem is thatin related data the are literature, barely therefore available regarding a the lot of various uncertainties factorsa remain typical affecting filling experiment, filling the rates. MWNTswith are the In well desired mixed amount of filler bythe gentle mixture grinding, and is then vacuum The ampoule isabove then the slowly melting heatedcooled. point to This of a method the temperature doesnanotubes filler not are and always opened prior require thenmolten to that slowly heat the filling treatment, materials asact some (e.g., with halides) CNT are tipsthe and able presence open of to heterocycles them – re- (definitely pentagonswhich for thanks are example to more – reactive). this method tosity [8. SWNTs come from Oxford Univer- sors used were mainly metalmolten salts, halides the within crystallization small-diameter of SWNTs has been the same procedure [8. istry method initially looked promisingvariety because of a materials wide canin be this way introduced and into becauseare nanotubes it not operates much different at from temperatures roomthe that temperature, allowing filling of CNTsture stability. with However, materials close attention withthe must oxidation low be method tempera- paid that to isto used. nanotubes The by damage caused tric severe acid) treatments makes (such them unsuitable asMoreover, for the using use filling with ni- yield SWNTs. isbecause the not solvent very molecules also good, enter obviously hence the tube filled cavity, lengths rarely exceed 100 nm. The physical filling method involvingphase a liquid is (molten) morerials restrictive, can firstly because decomposebecause some the when melting mate- they point mustnanotubes, melt, so be the compatible and thermal with treatment temperature secondly the remain should below the temperature ofnanotubes transformation will or be the damaged.due Because the to filling capillarity occurs face hence tension obeying of the Jurin’s fillingprobably law, material important, and the in a the threshold sur- of molten 100 state is ple of a nonacidicIf liquid route a to dissolved opening form SWNT (suchsired metal tips. as is a introduced during salt theof or opening it oxide) step, some of will the getment de- inside (after the washing nanotubes. and An drying annealingmay treat- the then treated lead nanotubes) toon the the oxide or annealing to atmosphere the [8. metal, depending

– ], 226 224 ,andTiC. 2 m in length ] showed that ], a rare exam- 231 207 [8. [8. ], although other oxi- 3 235 ally achieved in published – Pascard ]. and ]. 225 ] or chlorocarbenes formed from the ]. This technique is no longer preferred 221 , 236 S[8. 2 Loiseau 232 207 ][8. or H 3 2 ] for heteroelements such as Pb, Bi, YC Generally speaking, it is difficult to estimate the It has to be pointed out that the driving forces In Situ Filling Method Wet Chemistry Filling Method CrO filling rate, and this is usu papers through TEMbarely observations, although based they on are ber reliable of statistics tubes regarding observed. Moreover,concerned, the as the far num- fact that as the SWNTs nanotubesbundles are are makes gathered it into difficult toof filled observe tubes, the as exact well number aseach to tube. estimate the However, filled an lengthalso for estimation be of obtained filling fromtroscopy. rates x-ray can studies and Raman spec- involved in fillingstood [8. events are not fully yet under- Initially, most hybrid CNTs synthesizedMWNTs were based prepared on using thewere electric-arc obtained method, directly and materials during were processing. easily Thedrilling a introduced filling central hole into in theheteroelement. the anode The and first system filling hybrid products it obtained with by this using the approach were all reported in the same year [8. with appropriate precursors (i. e.,or able to solubilize) sublime, which melt, willrequired later material by be a transformed physicalsuch into interaction as the mechanism electron beam irradiation for example [8. or by in situ chemical transformationsby such H as reduction because it is difficult to controland the to filling achieve ratio mass and production, and yield itfilling is not SWNTs, suitable for nor formetals filling as MWNTs this induces with the transition formationinstead. of Conversely, (empty) significant SWNTs in situduring filling CVD-based can occur processes, butlyst only that with helped thebut with cata- possibly MWNT Co and growth Ni as (most well). often Fe, For the wet chemistry method the nanotubeopened tips must by be chemical oxidationThis prior is to generally the achieved fillingin by step. dilute refluxing the nitric nanotubes acid [8.233 MWNTscouldalsobefilledtoseveral by elements suchnanoparticles as of Se, elements Sb, suchSulfur S, was as and suggested Bi, to Ge, B,the play but an Al, in only important and situ role for formation Te. charge during of [8. filled MWNTs using arc dis- dizing liquid media mayC work as well, such as [HCl Later on, photolytic dissociation of CHCl 230 Nanomaterial and Nanostructures Part B

218 Part B | 8.5

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studied in detail, and the resulting one-dimensional as indicated in Fig. 8.20g,h. However, as the diameter 8.5 | B Part crystals have been shown to interact strongly with of the encapsulating capillary increases, different pre- the surrounding graphene wall. For example, Sloan ferred orientations were frequently observed [8.238]. et al. [8.240] described two-layer 4 W 4 coordinated KI High-yield filling of CNTs by the capillary method crystals that formed within SWNTs that were 1:4nm is generally difficult but fillings of more than 60% have in diameter. These two-layer crystals were all surface been reported for different halides, with filling lengths and had no internal atoms. Significant lattice distor- of up to several hundred nm [8.244]. Results from the tions occurred compared to the bulk structure of KI, imaging and characterization of individual molecules where the normal coordination is 6 W 6(meaningthat and atomically thin, effectively one-dimensional crys- each ion is surrounded by six identical close neighbors). tals of rock salt and other halides encapsulated within Indeed, the distance between two ions across the SWNT SWNTs were reviewed by Sloan et al. [8.245]. capillary is 1.4 times as much as the same distance along the tube axis. This suggests an accommodation Sublimation Filling Method of the KI crystal into the confined space provided by This method is more restrictive than the previous one, the inner nanotube cavity in the constrained crystal di- since it is only applicable to compounds able to sub- rection (across the tube axis). This implies that the limate within the temperature range of thermal stabil- interactions between the ions and the surrounding car- ity of the nanotubes. Examples are therefore scarce. bon atoms are strong. The volume available within the The first and still most successful example published nanotubes thus somehow controls the crystal structures so far is the formation of C60@SWNT (nicknamed of inserted materials. Taking the example of PbI2,the peapods), reported for the first time in 1998 [8.246], structures and orientations of encapsulated PbI2 crystals where regular 1:4 nm-large SWNTs were filled with were found to depend on the diameter of the confining C60 fullerene molecule chains. On the basis of this nanotubes [8.238]. For SWNTs, most of the encapsu- work, many fullerene-related molecules have been suc- lated one-dimensional PbI2 crystals obtained exhibited cessfully encapsulated as well, e.g., C70 (Fig. 8.21a), a strong preferred orientation, with their (110) planes or endofullerenes (La2@C80 [8.247], Gd @C82 [8.248], ı aligning at an angle of around 60 CtotheSWNT and ErxSc3xN@C80 [8.249] among other examples). axes, as shown in Fig. 8.20a,b. Because of the extremely Other attempts have followed, for instance involving small diameters of the nanotube capillaries, individ- ZrCl4 [8.241], selenium [8.250], or iodine [8.243, 251] ual crystallites are often only a few polyhedral layers (Fig. 8.21b). Of course, the process requires that the thick, as outlined in Fig. 8.20d–h. The unusual lattice SWNTs are opened by some method, as discussed pre- terminations enforced by capillary confinement, cause viously, typically by either acid attack [8.252] or heat the edging polyhedra to be of reduced coordination, treatment in air [8.253]. The opened SWNTs are then in-

a) b) 0.36 nm

Fig. 8.20a–h High-resolution transmission electron microscope - . - 110 c)110 (HRTEM) images and corresponding structural model for PbI2-filled SWNTs. (a) Image of a bundle of - . - 110 110 SWNTs, all of them being filled with PbI . (b) Enlargement of the portion 2 nm 2 d) e) framed in (a). (c) Fourier transform h) obtained from (b) showing the 110 distances at 0:36 nm of a single PbI2 f) crystal. (d) Image of a single PbI2- filled SWNT. (e) Enlargement of the portion framed in (b). (f) Simulated HRTEM image, corresponding to (e). g) (g) Structural model corresponding to (f). (h) Structural model of an SWNT filled with a PbI2 crystal as

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ] 257 )are )per- 4 3 5 nm 5 . Depending on 2 ), hydrogen perox- 7 O molecules (image by L. 2 70 Cr 2 ] or nitric acid vapors [8. 256 l in most cases), but oxidants such , = 227 ), or potassium permanganate (KMnO 2 O 2 for industrial use. Gas-phase oxidationeither oxygen of [8. CNTs using ide (H often used as well. HCl,notubes because like it HF, is does not notwastes oxidizing. damage generated However, na- by the the liquid wetnecessity oxidation methods of and the filtration/drying steps are not well suited the process they wereresistance synthesized of with, the nanotubes oxidation achieved can using a vary. gas When phase, thermogravimetric(TGA) analysis oxidation is is of great helpat for which determining the the treatment should temperature apply (attentionpaid should be to the use of low heatingoxidation rates temperatures so that are overestimated notin provided). the Differences presence ofrarely, oxides) catalyst and remnants other (metals by-products,type or, variations of in more nanotube-oxidizing the agent and(heating TGA rate, conditions flowdifficult rate) to used compare. makethat It amorphous published carbon is burns results first, generally followedand by SWNTs agreed, then however, multiwallif materials TGA (shells, is MWNTs),idation often even steps unable clearly. to Aqueousreagents solutions separate are of the oftenmain oxidizing different used reagent ox- for is nanotubeluted nitric (around oxidation. acid, 3 mol The eitheras concentrated potassium or dichromate di- (K using either wet chemistry oroxygen gaseous oxidants (typically such air), as ozone, or CO at moderate orcarbon high but temperature can removes leadof disordered to nanotube outer weight walls. loss Asmaterials a due consequence, are to high obtained, purity the but etching Conversely, gas-phase the oxidation yield from is ozone generally (O low. b)

]. 253 10 nm 10 ates to capillary condensa- eating dangling bonds). The ]. It must be noted that these chem- 255 Annular dark-field mode TEM image of an example of DWNTs filled with iodine chains. The specific , ) 100% with this filling route [8. b ( HRTEM image of an example of so-called peapods, here SWNTs filled with C 254 ) a ( C). As gaseous molecules are involved, the fill- ı Oxidation of Carbon Nanotubes 350 a) > CNTs are often oxidizedchemical and therefore functionalization opened in before chemical order reactivity (by to cr chemical increase oxidation of their nanotubes is mainly performed viewed in [8. ical reactions also affect any graphene-basedmaking impurities, quantification difficult, eitherpure because CNT materials raw barely exist, yet orprocedures because induce purification their own functionalization. then used for additional reactions,or to polymeric attach functional oligomeric entities; (ii)to the the graphenic surface direct (without any addition intermediate step). Examples of the latterfluorination (an important reactions first include step for oxidation furtheralization function- with or other organic groups). The propertiesapplications and of functionalized nanotubes have been re- 8.5.3 Functionalized Nanotubes Nanotube functionalization reactionsinto can two main be groups: (i) divided tips the chemical and oxidation of structural the defectsbonyl, and/or leading hydroxyl to functions. carboxylic, These car- functions are heated above the sublimation( temperature for fullerite serted into a glass or quartzpowder, tube together which with fullerene is sealed and placed into a furnace Fig. 8.21 imaging mode used preventsatom. the The carbon iodine wall chains of aremodel the twinned by host and J. nanotubes Sloan helically (University arranged from of in being Warwick) the seen. DWNT Each cavities white (image dot by is C. a Nie, CNRS). single Inserted iodine ing mechanism somewhat rel tion instead of capillary wetting,no meaning filling that there limitations are relatedence to of Jurin’s solvent. Consequently, law filling efficiency or maytually the ac- reach pres- Noé, CNRS). Nanomaterial and Nanostructures Part B

220 Part B | 8.5

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formed at ambient temperature is an environmentally of chemical groups through reactions onto the - 8.5 | B Part friendly and low cost route to form oxygen-containing conjugated skeleton; and ii) the noncovalent adsorption groups on the whole CNT surface without too much or wrapping of various functional molecules [8.261, structural damage. It is suited for mass treatment since 269]. Covalent functionalization is based on the forma- it can be performed in a fluidized bed [8.258, 259]. tion of a covalent linkage between functional entities and the carbon skeleton of nanotubes. It could also be Functionalization divided into direct covalent sidewall functionalization of Oxidized Carbon Nanotubes and indirect covalent functionalization with carboxylic The defects on CNTs created by oxidants are stabilized groups on the surface of CNTs (Fig. 8.22). Direct by bonding with carboxylic acid (–COOH) or hydroxyl covalent sidewall functionalization is associated with (–OH) groups. These functional groups have rich chem- a change in hybridization from sp2 to sp3 and a si- istry and the CNTs can be used as precursors for further multaneous loss of conjugation (e.g., fluorination of chemical reactions, such as silanation, polymer graft- nanotubes [8.270, 271]). Indirect covalent functional- ing, esterification, thiolation, alkylation, arylation, and ization takes advantage of chemical transformations of even some biomolecules. Oxidized nanotubes are usu- carboxylic groups at the open ends and holes in the ally reacted with thionyl chloride (SOCl2) to generate sidewalls (see above). The drawback of covalent func- the acyl chloride. The reaction of SWNTs with oc- tionalization is that the perfect structure of CNTs has to tadecylamine was reported by Chen et al. [8.260]after be destroyed, resulting in significant changes in their reacting oxidized SWNTs with SOCl2. Many other physical properties. Noncovalent functionalization is reactions between functionalized nanotubes (after re- mainly based on supramolecular complexation using action with SOCl2) and amines have been reported in various adsorption forces, such as Van der Waals force, the literature [8.261]. The common outcome of these hydrogen bonds, electrostatic force, and -stacking functionalizations is the increased solubility of CNTs interactions [8.269]. Compared to chemical functional- either in the organic solvent or water. Noncovalent ization, the advantages of noncovalent functionalization reactions between the carboxylic groups of oxidized are that it can operate under relatively mild reaction nanotubes and octadecylammonium ions are also pos- conditions and that the perfect graphene structure of sible [8.262], providing solubility in tetrahydrofuran CNTs can be maintained. (THF) and CH2Cl2. The attachment of proteins onto Numerous chemical reactions including hydrogena- CNTs using diimide-activated amidation (through dition, halogenation, esterification, amidation, cycloaddi- rect coupling of the carboxylic acid to proteins using tion, radical addition, azide chemistry, nucleophilic ad- a coupling agent) is possible [8.263]. DNA functional- dition, electrophilic addition, inorganic complex addi- ization of CNTs was also reported [8.264]. tion, ozonolysis, surface-initiated polymerization, and Functionalization with lipophilic (long alkyl chains) physical methods such as plasma treatment, – stack- and hydrophilic (oligomeric poly(ethyleneglycol) ing and solid-phase mechanical milling have been tried groups) dendra has been achieved via amination to functionalize CNTs, offering alternative approaches and esterification reactions [8.265]. In that case, to the solubilization of CNTs with desired functionality the functional groups could be removed simply by and surface characteristics [8.261, 269, 272–274]. modifying the pH of the solution [8.266]. The possible interconnection of nanotubes was reported by Chiu 8.5.4 Coated/Decorated Nanotubes et al. [8.267] using the acyl chloride method and a bifunctionalized amine to link the nanotubes through In contrast to functionalization, the decoration of the formation of amide bonds. CNTs consists in depositing solids, mainly nanopar- Finally, it has been discovered that imidazolium ticles (NPs), physi- or chemisorbed onto the nano- ion-functionalized CNTs are highly dispersible in ionic tube’s outer surface. Because of their interaction with liquids of analogous chemical structure and that mix- the nanotube structure, the deposited metals, semi- tures of functionalized CNT and ionic liquids can form conductors, oxides, or organic materials often present gels upon sonication or waxes that could find appli- unique properties [8.275]. Consequently, the coated cations as soft composite materials for electrochem- CNTs find numerous applications in catalysis, electron- istry [8.268]. ics, energy conversion and storage, environment, and medicine [8.275, 276]. Sidewall Functionalization Even if the outer surface of tubes and tube ends of Carbon Nanotubes present potential adsorption sites, numerous studies

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright There are two main approaches for the side-wall have shown that surface activation is essential to reach functionalization of CNTs: i) the covalent attachment a high coating density. Oxidation (Sect. 8.5.3, Oxida-

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. , ]. 259 281 n m ) 2 )[8. :Metal –(M n n nanoparticles ) ) 1 1 O–(M–M) Amidation ]. As an alterna- (M (M O 2 282 ]. CVD on MWNTs Metal ions (Au, Ag, etc.) (Au, Silanization 1 Esterification 275 3 ]. Such depositions can be and the good mechanical 2 NPsdepositedonMWNTs : defect functionalization) Thiolation NH–R–NH Si–R SH–R OR 2 B 283 O O O O from Grafting Grafting to Grafting Heterogeneous Processes Monomer 2 Monomer Monomer 1 Monomer , ]. The polyol route gave much better ]. The deposition of silicon layers on 8.2.2 280 275 grafting Polymer ]. The gas processes yield products often purer than OH have demonstrated excellent sensing responsesdetection for at gas room temperature [8. tive to oxidizinga pretreatments, titanium carbide the (TiC) layerface predeposition by functionalization CVD of acting has assurface a coverage successfully sur- of MWNTs increased byers Ni, the deposited Pd by and CVD Pt [8. thin lay- performed at large scaleprocess using (Sect. the fluidized bed CVD nanotubes [8. 284 dispersion of Pd on theparticle MWNTs with size smaller distribution. Pd nano- the wet methods.involve They high are coating single rates step [8. and generally has often beenRh) used or to semiconducting depositnanotubes (InP, [8. metallic CdSe) (Pt, nanoparticles Pd, on Ru, MWNT networks hasodes been of Li-ion explored batteries byenergy to combining capacity prepare the high of an- specific strength silicon and structural flexibility of nanotubes [8. Composites made of SnO O

: direct sidewall functionalization; B A : Degree polymerization. of , m n ]. It involves ]. Their choice CNTs R = alkyl, aryl, etc. 275 277 , A 275 ticles onto nanotubes, each ) is the most popular route to ]. H F 280 – n Cl Cl 278 , ]. As an example, Pd nanoparticles were R RMgBr/RLi Diels–Alder 275 278 R Amino substitution The wet impregnation method is the most widely Cycloaddition Hydrogenation T > 450 °C T > 450 Strategies for covalent functionalization of CNTs ( 2 often depends on the applicationof field and treatment. on They thegroups: scale the are wet methods generally including thesol-gel classified electrochemical, and into impregnation two cesses methods, such as and physical vapor deposition thelayer (PVD), deposition atomic gas (ALD), pro- and chemical(CVD) vapor [8. deposition tion of Carbon Nanotubes activate the nanotube surfacebonyl by and creating carboxyl surface groups.for the There car- deposition of are nanopar manyoffering methods different degreesdistribution of along control the of tubes [8. NP size and used technique evenof though its it simplicity is and multistep, because cheapness [8. the impregnation ofcursor nanotubes salt by or adrying, solution calcination, organometallic and of complex, reduction.of pre- followed the However, the coated by particles size cisely may [8. be difficult to control pre- deposited on MWNTsa functionalization by using poly-alcohol wet based ligands,order in impregnation to and increase the hydrogen by absorption properties of Nanomaterial and Nanostructures Radical (R∙) attachment (R∙) Radical Dehydrogenation Nitrene Carbene NH EtOOC EtOOC ROOC–N Fluorination and derivative reactions Nucleophilic 1 Carboxylic CNTs react with reactive polymers; 2 Functionalized CNTs act as initiators to initiate polymerization; 3 Living polimerization, CNT-copolymer can be obtained; cyclopropanation Part B Fig. 8.22

222 Part B | 8.5

Created from viennaut on 2018-11-17 04:18:29. Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Carbon Nanotubes 8.6 Carbon-Nanotube-Containing Materials (Composites) 223

8.6 Carbon-Nanotube-Containing Materials (Composites) 8.6 | B Part

Because of their unique and exceptional morphologi- DWNT-Cu composite macroscopic wires prepared us- cal characteristics and properties, CNTs make partic- ing a combination of SPS and room-temperature wire ularly promising component materials of composites drawing present an increase of ultimate tensile strength with metals, ceramics, or polymer matrices. Key is- by about 10% compared to the corresponding pure sues to address include the homogeneous dispersion of copper wires [8.295]. DWNT- and MWCNT-Cu com- the CNTs (without damaging the CNTs), the control posites also show a higher hardness and a lower friction of the CNT/matrix bonding, the densification of bulk coefficient and wear loss [8.296]. Hot-extruded CNT- composites, and the possibility of aligning CNTs. In Mg nanocomposites showed a simultaneous increase in addition, the CNT type (SWNT, DWNT, MWNT, etc.) yield strength, ultimate tensile strength and ductility, and production origin (arc, laser, CCVD, etc.) are also until a threshold of 1:3 wt% was reached [8.297]. Com- important variables that control structural perfection, pared to pure Mg, a 45% increase of tensile strength surface reactivity, and aspect ratio of the reinforcement. was obtained for 2:4 wt% MWNT-Mg composites pre- The application of CNTs in this field is expected to lead pared by in situ synthesis of the CNTs within the Mg to major advances in composites. powder followed by hot extrusion [8.298]. The Young’s modulus of nonpurified arc-discharge MWNT-Ti com- 8.6.1 Metal Matrix Composites posite is about 1.7 times that of pure Ti [8.299]. The formation of TiC, probably resulting from a reaction be- CNT-metal matrix composites are less studied despite tween amorphous carbon and the matrix, was observed, promising applications as structural materials in aero- but the MWNTs themselves were not damaged. An in- nautics, aerospace, and automotive fields. The main crease in the Vickers hardness by a factor of 5.5 over matrices are Al, Cu, Mg, Ti, and Ni. The materials that of pure Ti was associated with the suppression of are generally prepared by standard powder metallurgy coarsening of the Ti grains, TiC formation, and the ad- techniques [8.285]. The spark plasma sintering (SPS) dition of MWNTs. The addition of small MWNT load- technique is sometimes used to densify the compos- ings of 0:180:35 wt% also improves the yield stress ites whilst avoiding matrix-grain growth [8.286]. Other and tensile strength of Ti markedly [8.300]. Ni-plated techniques such as liquid metallurgy, thermal spray, MWNTs give better results than unplated MWNTs in and electrochemical deposition are also currently em- strength tests. Indeed, CNT coating is a promising ployed [8.287]. To achieve better dispersion of CNTs, way to improve the strength of bonding with the ma- new processing methods such as molecular level mix- trix [8.301]. Composite films and coatings deposited by ing and stir friction processing have been developed electroless or electrodeposition techniques on various in recent years [8.287]. The room temperature elec- substrates have also been studied. The addition of up trical resistivity of hot-pressed MWNT-Al composites to 15 vol:% purified SWNTs to nanocrystalline Al films increases slightly upon increasing the MWNT volume reduces the coefficient of thermal expansion by as much fraction [8.288]. The tensile strengths and elongations as 65% and the resulting material could be a promising of unpurified arc-discharge MWNT-Al composites are electronic packaging material [8.302]. CNT-Ni coat- only slightly affected by annealing at 873 K in contrast ings deposited on a carbon steel plate by electroless to those of pure Al [8.289]. The addition of 1 vol:% deposition show significantly increased resistance to MWNT to Al greatly enhances its tensile strength with- corrosion [8.303] and higher Vickers microhardness, out sacrifices to its tensile elongation [8.290]. The higher wear resistance, and lower friction coefficient elastic modulus, yield strength, and fracture toughness than SiC-reinforced composite deposits [8.304]. of 1:5, 3, and 4:5vol:% MWNT-Al composites increase with carbon content [8.291]. The coefficient of thermal 8.6.2 Ceramic Matrix Composites expansion (CTE) of 1 wt% MWNT-Al composite fabricated by cold isostatic pressing and the hot squeeze Many different ceramic matrices have been studied over technique is 11% lower than that of pure Al or 2024 the years, although oxides (in particular Al2O3) are still Al matrix, showing some promise as low-CTE materi- the most studied [8.305–307]. There are three main als. Associated with a high thermal conductivity, such methods for the preparation of CNT-ceramic nanocom- materials would be interesting for applications such as posite powders. One is mechanical milling which usu- packaging and space structures [8.292]. The stiffness, ally involves long times that could damage the CNTs. yield, and tensile strengths of spark-plasma-sintered Wet-milling is preferred but often requires the addi-

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright MWNT-Cu composites increase with increasing car- tion of organic additives to stabilize both the CNTs bon content up to 15 vol:%[8.293, 294]. 0:5vol:% and the ceramic powder. This is also true for a second

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. ]. ]. m ]. It 331 Ajayan 333 100 ]. The main et al. [8. 328 ]. 325 Gong ]. Defects are likely to ], with a low percolation 330 %) due to their very high as- : 324 – m[8. 321 ] showed that SWNT bundles were ]. The electrical conductivity can be ]. SWNTs longer than 10 ]. An anisotropic conductivity is ob- 332 322 329 ], are still being intensively studied, espe- 322 ]. It was proposed that all of the walls of ]. The ability of the polymer to form large- ]. In terms of mechanical characteristics, the 326 329 328 327 8.6.3 Polymer-Matrix Composites CNT-polymer composites, firstet al. reported [8. by cially epoxy- andmatrix polymethylmethacrylate composites. A (PMMA)- review on theing, chemistry, mechanical, process- and electrical propertiesin can be [8. found diameter helices aroundformation individual of CNTs a favors strong the bond with the matrix328 [8. three key issues thatpolymer affect composite the are performance of thethe a strength fiber- fibrous and toughness reinforcement,interfacial of its bonding, orientation, whichfer and [8. is good crucial to load trans- Isolated SWNTs may be moreor desirable bundles than MWNTs forweak dispersion frictional interactions in between layers a ofand MWNTs matrix between because SWNTs of the in bundles [8. nanocomposites [8. mechanisms ofinterlocking, load chemical transfer bonding,bonding and are between van the micromechanicalinterfacial CNTs der shear stress and Waals between the thewill fiber transfer and matrix. the the A matrix applieddistance high load to [8. the fiber over a short threshold (less than 1 vol would be neededin for the significant case ofwhereas load-bearing the nonbonded ability critical SWNT-matrix length interactions, the for matrix SWNTs is cross-linked only to 1 limit the working length of SWNTs, however [8. pect ratio [8. tailored within several ordersthe of magnitude CNT directly quantity by andof is the well percolation theory fitted with by thetheoretical exponent the close value scaling to characteristic the law ofnetwork a [8. three-dimensional the MWNTsonly are the stressed outerall in walls of the compression, are innerMechanical stressed tubes whereas are tests in sliding performed tension withincomposites on the because [8. outer 5 wt% tube. SWNT-epoxy was also reported that coating regularMWNTs carbon prior fiber to with their dispersion into an epoxy matrix The load transferresin to was MWNTs dispersed muchsion in higher [8. an in epoxy compression than in ten- pulled out of thematerial. matrix during The the influence deformationinteraction of of was the the demonstrated interfacial by CNT/matrix tained when the CNTs are alignedby within high-temperature extrusion the [8. composite

Xia mem- ]. Hetero- 3 , O 311 ], a strong 2 , ]. The mi- ]. Enhanced 313 8.2.2 310 318 – 314 315 ceramics [8. ]. By contrast, CNTs in- 3 ], but they were shown to be O 2 320 , 307 ], processing-induced changes in 319 . The densification of the nanocom- ]. Full densification can be reached 311 309 , ] reported microstructural investigations on 308 312 brane. Different possibleinduced by reinforcement the MWNTs mechanisms crack have been deflection, evidenced, crack such bridging,and as MWNT MWNT collapsing in pulling-out, shear bands. Indeed,so although far neither single-edge notched beam norV-notched single-edge beam results have evidencedsignificantly that reinforce CNTs Al can geneous Processes posite powders isinfluence of made the CNTs. difficult Thehot by most common pressing methods the are (HP) detrimental Most and of spark the plasmacontent works sintering inhibits report the (SPS). that densificationthe of increasing more the the composite, when carbon in all CNTs the are matrix.as homogeneously The an dispersed SPS efficient techniquetion method has of to been CNT-oxide achieve reported compositesCNTs the without [8. total damaging densifica- the with SPS atsubstantial shorter holding comparatively times. However, the lower successful temperatures densification with byfor SPS HP suggests at that matrix a grains areand lower nonagglomerated with temperature sizes than inters. the The range influence of ofproperties, a in CNT few particular on dispersion tens toughness, of on hasversial. been nanome- Indeed, mechanical contro- strong increasesfrom in the toughness measurement derived have of been reported Vickers [8. indentation cracks probably widely overestimated becauseare such very materials resistant to contact damage [8. method, i. e., the informed situ CNTs. synthesis of It the can matrixthe lead on to CNTs pre- a and good theto adhesion ceramic, implement. between A but third can methodthe be is CNTs the rather within in complex the situ ceramic synthesisclosely related of powder to using those procedures described in Sect. et al. [8. MWNTs well aligned in the pores of an Al and unambiguous increase intained toughness for DWNT-MgO has composites been inare which ob- the very CNTs homogeneously dispersed [8. tribological properties (lowcomposites friction have and/or been reported wear) [8. of crohardness is found to either increasethis or depends decrease, and greatly onAs the noted powder preparation in route. [8. crease the electrical conductivity of insulating ceramic the matrix may haveproperties greater than effects the on the actualing mechanical presence the of CNTs. thermaloften Regard- properties, show a CNT-ceramic lowerresponding composites thermal ceramics, conductivity probably caused than by the toomal high cor- contact ther- resistances at CNT-CNTgrain and CNT-ceramic junctions [8. Nanomaterial and Nanostructures Part B

224 Part B | 8.6

Created from viennaut on 2018-11-17 04:18:29. Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Carbon Nanotubes 8.6 Carbon-Nanotube-Containing Materials (Composites) 225

improves the interfacial load transfer, possibly via electrical characteristics, as well as the photoconduc- 8.6 | B Part local stiffening of the matrix near the interface [8.334]. tivity. A great deal of work has also been devoted DWNT-epoxy composites prepared by a standard to the applications of CNT-polymer composites as calendaring technique were shown to possess higher materials for molecular optoelectronics, using pri- strength, Young’s modulus, and strain to failure at marily poly[(m-phenylenevinylene)-co-(2,5-dioctoxy- a carbon content of only 0:1wt%[8.335]. Significantly p-phenylenevinylene)] (PmPV) as the matrix. This improved fracture toughness was also observed. The conjugated polymer tends to coil, forming a helical influence of the different types of CNTs (SWNTs, structure. The electrical conductivity of the composite DWNTs, and MWNTs) on the mechanical properties films (436 wt% MWNTs) is increased by eight orders of epoxy-matrix composites is discussed in [8.336]. of magnitude compared to that of PmPV [8.365]. Using The stiffness and damping properties of SWNT- and MWNT-PmPV composites as electron transport layers MWNT-epoxy composites were investigated for use in in light-emitting diodes results in a significant increase structural vibration applications [8.337]. It was shown in brightness [8.366]. The SWNTs act as a hole-trap- that enhancement in damping ratio is more dominant ping material that blocks the holes in the composites; than enhancement in stiffness, MWNTs making a bet- this is probably induced through long-range interac- ter reinforcement than SWNTs. Indeed, up to 700% tions within the matrix [8.367]. Similar investigations increase in damping ratio is observed for MWNT- were carried out on arc-discharge SWNT-polyethylene epoxy beam as compared to the plain epoxy beam. dioxythiophene (PEDOT) composite layers [8.368]and The outstanding potential of CNTs as reinforcements MWNT-polyphenylenevinylene composites [8.369]. in polymer composites is evident from the supertough To conclude, two critical issues must be consid- composite fibers fabricated by the groups of Baughman ered when using nanotubes as components for ad- et al. [8.338]andPoulin et al. [8.339]. By optimizing vanced composites. One is to choose between SWNTs, the coagulation spinning method [8.340, 341], they DWNTs, and MWNTs. The former seem more bene- spun several hundred meters of CNT-polyvinyl alco- ficial to mechanical strengthening, provided that they hol composite fibers, which have tensile properties are isolated or arranged into cohesive yarns so that the comparable to that of a spider silk. As for ceramic load can be conveniently transferred from one SWNT to matrix composites, the electrical characteristics of another. Unfortunately, despite many advances [8.340, CNT-polymer composites are well described by the 341, 370–373], this remains a technical challenge. The percolation theory [8.327, 342]. Polymer hosting CNTs other issue is to tailor the CNT/matrix interface with re- such as PMMA, epoxy, polyimide, and polystyrene spect to the matrix. In this case, DWNTs and MWNTs exhibit extremely low percolation threshold values may be more efficient than SWNTs. (much below 1 wt%) [8.327]. An ultralow electrical percolation threshold of 0:0025 wt% was reported 8.6.4 Composites as Multifunctional for aligned MWNT-epoxy composites [8.343]. The Materials thermal conductivity of composites can also be greatly enhanced by the alignment of CNTs [8.344]. Poly- One of the major benefits expected from incorporating mer composites with other matrices include CCVD- CNTs into other solid or liquid materials is that they prepared MWNT-polyvinyl alcohol [8.345], arc- endow the material with some electrical conductivity prepared MWNT-polyhydroxyaminoether [8.346], while leaving other properties or behaviors unaffected. arc-prepared MWNT-polyurethane acrylate [8.347, As already mentioned in the previous section, the per- 348], SWNT-polyurethane acrylate [8.349], SWNT colation threshold is reached at very low CNT loadings. polycarbonate [8.350], MWNT-polyaniline [8.351], Tailoring the electrical conductivity of a bulk material MWNT-polystyrene [8.352], CCVD double-walled is then achieved by adjusting the CNT volume frac- nanotubes-polystyrene-polymethylacrylate [8.353], tion in the formerly insulating material while making MWNT-polypropylene [8.354, 355], SWNT-polyethy- sure that this fraction is not too large. According to lene [8.356–358], SWNT-poly(vinyl acetate) [8.357, Maruyama [8.374], there are three areas of interest re- 358], CCVD-prepared MWNT-polyacrylonitrile garding the electrical conductivity: [8.359], SWNT-polyacrylonitrile [8.360], MWNT- oxotitanium phthalocyanine [8.361], arc-prepared 1. Electrostatic discharge (for example, preventing fire MWNTpoly(3-octylthiophene) [8.362], SWNT-poly- or explosion hazards in combustible environments (3-octylthiophene) [8.363], and CCVD MWNT- or perturbations in electronics, which requires an poly(3-hexylthiophene) [8.364]. These works deal electrical resistivity of less than 1012 cm)

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright mainly with ﬁlms 100200 m thick, and aim to study 2. Electrostatic painting (which requires the material the glass transition of the polymer, its mechanical and to be painted to have enough electrical conductiv-

eue ircakn aaei composites in damage microcracking Reduces

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plctoso aouebsdmliucinlmtras(rm[8. (from materials multifunctional nanotube-based of Applications ) oyih .Mrym WAB atn Ohio) Dayton, (WPAFB, Maruyama B. copyright ]), 374 al 8.3 Table Nanomaterial and Nanostructures Part B

226 Part B | 8.6

Created from viennaut on 2018-11-17 04:18:29. Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Carbon Nanotubes 8.7 Current Applications of Carbon Nanotubes (on the Market) 227

6 ity – an electrical resistivity below 10 cm – to properties of CNTs make them likely to be a perfect 8.7 | B Part prevent the charged paint droplets from being re- multifunctional material in many cases. For instance, pelled) materials used in satellites are often required to be 3. Electromagnetic interference shielding (which is electrically conductive, mechanically self-supporting, achieved for an electrical resistivity of less than able to transport away excess heat, and often to be ro- 10 cm). bust against electromagnetic interference, while being of minimal weight and volume. All of these properties Materials are often required to be multifunctional; should be possible with a single nanotube-containing for example, to have both high electrical conductivity composite material instead of complex multimateri- and high toughness, or high thermal conductivity and als combining layers of polymers, aluminum, copper, high thermal stability. An association of several materi- and so on. Table 8.3 provides an overview of various als, each of them bringing one of the desired features, ﬁelds in which nanotube-based multifunctional materi- generally meets this need. The exceptional features and als should ﬁnd application.

8.7 Current Applications of Carbon Nanotubes (on the Market)

Perfect CNTs exhibit high aspect ratio, high tensile Companies also (or instead) sell CNT master strength, low mass density, high heat conductivity, large batches, i. e., premixed CNT-polymers for instance, surface area, poor chemical reactivity, and versatile or transformed products containing nanotubes (e.g., electronic behavior, including high electron conductiv- sheets, tapes, yarns, etc.) to be subsequently used by ity. However, while these are the main characteristics the buyer as starting materials for fabricating parts and of individual nanotubes, many of them can form sec- devices for their own uses or for final products to ondary structures such as ropes, fibers, papers, and sell. thin films with aligned tubes, all with their own specific properties. These properties make them potential 8.7.2 Near-Field Microscopy Probes candidates for a nearly infinite variety of applications, regardless of their cost [8.375]. Cost is an issue, though, The high mechanical strength and aspect ratio of car- which strongly depends in first place on both the CNT bon nanotubes makes them almost ideal candidates for type and quality and on the production process type use as force sensors in scanning probe microscopy (e.g., all semiconducting, high-quality SWNTs can cost (SPM). They provide higher durability, low sensitiv- 50 times more than gold to date (2016)!). Cost is also ity to electrostatic charges, and the ability to image strongly affected by the modifications to be brought to surfaces with a high lateral resolution, with respect to production lines for being nanocompatible, as well as conventional (ceramic-based) force sensors. The idea that of the specific studies for assessing potential pub- was first proposed and tested by Dai et al. [8.377]us- lic health issues all along the material/device life (i. e., ing c-MWNTs. Although it was extended to SWNTs from production to waste and recycling). All this can by Hafner et al. [8.378], commercial nanotube-based prevent a CNT-based material or device, although capa- probes use MWNTs for processing convenience. CNT- ble of superior performance, from reaching the market. based SPM tips also offer the potential to be func- Because of this, we only list below CNT-based applica- tionalized, leading to the prospect of selective imaging tions which actually are on the market, and readers who based on chemical discrimination in chemical force mi- are interested in the vast potentiality of CNTs may refer croscopy (CFM), allowing the chemical mapping of to other literature sources [8.375, 376]. molecules [8.379, 380]. CNT-based SPM tips are not drawback-free, however. They may generate specific 8.7.1 Carbon Nanotubes and Master Batches image artifacts (e.g., ringing effect), and exhibit highly variable geometry and alignment from a tip to another Carbon nanotubes have become commercial products even within the same probe batch and brand. Current by themselves, for supplying research laboratories and nanotube-based SPM tips or high-resolution AFM tips start-ups. Table 8.4 provides a list of CNT-selling com- can be quite expensive, in the range of 450 $/tip on panies around the world. This list was probably nonex- the average, depending on the geometrical characteris- haustive, and is certainly already partly obsolete, and tics and the supplier (CDI, NanoSensors). The market

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright partly incomplete. Examples of current price ranges are for nanotube AFM tips is growing, and was estimated provided in the various sub-sections of Sect. 8.2. to reach 150 MC=yr in 2016.

com

ei aeilSltos(USA) Solutions Material Helix http://nanomastech.com (USA) Technologies NanoMas http://Helixmaterial.

many) nanotubes

uueCro mH(Ger- GmbH Carbon Future http://nanoledge.com (Canada) Inc Nanoledge http://future-carbon.de http://ytca.com/carbon_ (USA) Inc America, YTC

group/labs/en

uis aoaois(Japan) Laboratories Fujitsu http://nano-lab.com (USA) Inc NanoLab, http://jp.fujitsu.com/ http://xintek.com (USA) Inc Xintek,

rnirCro op(Japan) Corp Carbon Frontier http://nanointegris.com (USA) NanoIntegris http://f-carbon.com http://unidym.com (USA) Inc Unidym

uot(USA) DuPont http://nanocyl.com (Belgium) SA Nanocyl http://dupont.com http://thomas-swan.co. (UK) Co and Swan Thomas

com com

(USA) de many) continentalcarbon. surreynanosystems.

otnna abnCompany Carbon Continental http://nanocompound. (Ger- GmbH NanoCompound http:// http:// (UK) NanoSystems Surrey

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hnd rai hmcl Co Chemicals Organic Chengdu http:// (USA) Inc Nanocomposites http://timesnano.com http://sunnano.com (China) Co Nanotech Sun

com (USA) com (USA)

ha ue (USA) Tubes Cheap http://nanocomptech. Inc Technologies, Nanocomp http://Cheaptubesinc. http://swentnano.com Inc NanoTechnol., SouthWest

com

catalyticmaterials. cn (China) (NTP) Ltd

aayi aeil L (USA) LLC Materials Catalytic http://nanocs.com (USA) Nanocs http:// http://nanotubes.com. Co, Port Nanotech Shenzhen

com

abnSltosIc(USA) Inc Solutions Carbon http://nanocarblab.com (Russia) NanoCarbLab http://carbonsolution. http://sesres.com (USA) Research SES

com com (Cyprus)

abnN n (Austria) F and NT Carbon http://nano-c.com (USA) Inc Nano-C, http://carbon-nanoﬁber. http://e-nanoscience. Ltd Holdings Rossetter

(Canada)

-oyesGb (Austria) GmbH C-Polymers http://mtr-ltd.com (USA) Ltd MTR http://c-polymers.com http://raymor.com Inc Industries, Raymor

(USA)

http://buckyusa.com (USA) USA Bucky oeua aoytm Inc Nanosystems Molecular -e (Norway) N-Tec http://monano.com http://n-tec.no

com (Singapore) Ltd Pte

http://nanotech-now. Singapore Internat. BioNano kao(Canada) Mknano aua ao n (USA) Inc Nano, Natural http://mknano.com http://naturalnano.com

many) com

http://baytubes.com (Ger- Science Material Bayer isiCeias n (Japan) Inc Chemicals, Mitsui aohn A(Greece) SA Nanothink http://jp.mitsuichem. http://nanothinx.com

Kong)

http://arry-nano.com (Hong Group International Arry E oprto (USA) Corporation MER aoehas n (USA) Inc NanoTechLabs, http://mercorp.com http://nanotechlabs.com

etC.(China) Co. ment aeil,Ic(USA) Inc Materials, com

http://arknano.com Develop- Technology Arknano uaNnwrs(USA) Nanoworks Luna aotutrd&Amorphous & Nanostructured http://lunananoworks. http://nanoamor.com

is(India) gies com

http://arkema.com (France) Arkema noain nﬁdTechnolo- Uniﬁed Innovations aohlLC(USA) LLC Nanoshel http://iutechnologies. http://nanoshel.com

inl n (USA) Inc tional, sensors.com

ple cec n.(USA) Inc. Science Applied http://apsci.com yeinCtlssInterna- Catalysis Hyperion http://ﬁbrils.com aoeetIc(USA) Inc Nanoselect http://nanoselect-

(USA) (Japan)

mrcnDeSuc Inc. Source Dye American http://adsdyes.com oj hmclCorporation Chemical Honjo http://honjo-chem.co.jp aoBCr (Canada) Corp NanoNB http://nanonb.com

opn Name Company Website opn Name Company Website opn Name Company Website

itn fcmaisslignntbs(l t (all nanotubes selling companies of Listing psicue)aon th around included) ypes ol 21 data) (2015 world e al 8.4 Table Nanomaterial and Nanostructures Part B

228 Part B | 8.7

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8.7.3 Electron Emitter trical conductivities and flexibility but demonstrate 8.7 | B Part undesirable optical transmittance over the visible re- In a pioneering work by de Heer et al. [8.381], CNTs gion [8.386]. Owing to their very high aspect ratio, were shown to be efficient field emitters. Briefly, a po- CNTs increase the electrical conductivity of poly- tential difference is set up between the emitting tip(s) mer composites with a very low percolation thresh- and an extraction grid (or an anode) so that electrons old and allow the fabrication of transparent conduc- are pulled from the tip(s) onto an electron-sensitive tive CNT-polymer films. Commercial developments by screen layer. With respect to regular (Mo, doped-Si, Eikos resulted in SWNT-polymer films with optoelec- W) electron-emitting tips, the structural perfection of tronic performances (9097% visible-light transmit- CNTs is supposed to provide higher electron emission tance and 200500 =square sheet resistance) very stability, higher mechanical resistance, longer lifetimes, close to ITO [8.387]. Moreover, CNTs can be deposited and 1=3 1=10 lower energy consumption (for exam- by cost-effective solution-based processes, a supple- ple, nanotubes are able to produce a current density of mentary advantage over ITO coatings produced by 1mA=cm2 for a threshold voltage of 3 V=m, while sputtering at low pressure [8.388]. regular Mo or Si tips require 100 V=m). Generally speaking, the maximum current density that can be 8.7.5 Nonvolatile Random Access Memory obtained with CNTs ranges from 106 to 108 A=cm2 depending on the nanotubes involved (SWNT or MWNT, Nonvolatile random access memories (NRAM) have re- opened or capped, aligned or not, and so on) [8.382– cently been developed by Nantero, based on a concept 384]. Those properties have made CNTs potential can- by Rueckes et al. [8.389] which exploits a suspended didates for a variety of applications, yet comprising SWNT crossbar array for both I/O and switchable, two categories: (i) those in which electron emitters are bistable device elements with well-defined OFF and ON displayed by thousands according to a periodic pat- states. This crossbar consists of a set of parallel SWNTs tern, as for flat panel displays for television sets and on a substrate and a set of perpendicular SWNTs that computers, and (ii) those merely requiring a single are suspended on a periodic array of supports. Each electron-producing cathode, as for x-ray sources, and cross point in this structure corresponds to a device electron sources for electron microscopes. In spite of element with an SWNT suspended above a perpendic- the potentiality of CNTs in this field and the convincing ular nanowire. For practical manufacturing purposes, existence of demonstrators and prototypes (by Sam- the actual switches do not rely on single SWNTs but sung, for instance), no applications within the former rather on a random mesh of hundreds of SWNTs with categories have reached the market so far, indicat- many different intersection points (thin film of tangled ing that some cost and/or technological issues are yet CNTs patterned on silicon substrate). The devices reach to be fixed. Conversely, regarding the latter category, switching speeds of 100 to 200 GHz, operate at or- companies such as Oxford Instruments and Medirad ders of magnitude more cycles than flash memories, have commercialized miniature x-ray generators for and present lower power consumption compared to dy- medical applications which use nanotube-based cold namic random access memories (RAMs). cathodes developed by Applied Nanotech Inc. Also, a new cold-field emission gun for electron microscopes 8.7.6 Light Absorbants based on a single, small-diameter MWNT (yet thick- ened into a cone in order to prevent the CNT from Optical properties of carpet-like deposits of CNTs vibrating while emitting, which is a fatal drawback (Fig. 8.15c) are being used by Surrey NanoSystems to for the quality of the emitted beam) is currently un- create and sell a coating called Vantablack absorbing der development at Hitachi High Technologies (Japan) 99:6% of light, which is useful in optical devices for based on work carried out at the University of Toulouse instance. Hence it is not a painting, but it is claimed (France) [8.385]. to be the darkest black color available. This has attracted the interest of various artists to such an extent 8.7.4 Flexible and Touch-Screen Displays that a British (and rich) one, Anish Kapoor, bought in 2016 the exclusive rights to use Vantablack for artistic Nowadays, the majority of touch-screen displays in purposes. However, Frederic De Wilde, a Belgian artist, smartphones and tablets are made of Indium Tin Ox- claims anteriority with a coating named NANOblck- ide (ITO) transparent conductive electrodes which are Sqr#1, also based on CNTs, jointly developed by Rice brittle and thus unusable for flexible displays. Chem- University and NASA for the fabrication of materials

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. , 397 ions, the ]. For ex- C 395 ]. The addition of 394 ]. CNTs are thus widely ]. To overcome some of ]. Several CNT-producing 396 ]. The measured reversible ]. Li-ion storage capacity in 399 395 393 392 ions diffuse between the anode ]. Owing to their high aspect ra- C 391 sensors), CNT thin films with variable , which is a 3-fold improvement over [8. 1 1 microgun ) one obtains a theoretical maximal capacity of 6 ]. Different kinds of gas/chemical sensors, based resistance as aties function (chemiresistors), of and the(FET)-based CNT adsorbed sensors field-effect gas [8. proper- transistor cathode, and the electrolyte.charging During charging cycles and Li dis- and cathode through thea electrolyte lithium which salt is dissolved typically inhas long an been organic the solvent. preferred anode Graphite cial material for batteries commer- due tostorage its density, relatively good high capacity, cyclability, energy tential and a for low lithium. redox Thebatteries po- capacity is limited of by graphiteintercalate between the in individual graphene number layers. Li-ion Assum- ofing Li a maximum ions of that 1(LiC Li can atom for every 6 carbon atoms 398 on different working principles,thanks to have CNTs: been miniaturized ionizing fabricated gascalled sensors (also 8.7.10 Chemical Sensors The development of CNT-basedintensive sensors interest has in attracted their the excellent last sensing severalsponse years properties and because such high of selectivity aslytes for prompt with a detection re- wide limits variety reaching of ppb ana- levels [8. 8.7.9 Anodes for Li-Ion Batteries A Li-ion batteryponents, the is anode composed intercalated of with three Li main com- 372 mA hg conventional graphite anodes [8. tio, high specific surfacehave and been high shown conductivity, CNTs tofor be Li-ion excellent batteries conductive [8. additives CNTs results from theof availability the of tube, thethe the central interstitial core space interlayer betweensembled space CNTs in (for when bundles they MWNTs), [8. are and as- Li-ion capacities for1000 mA hg CNT-based anodes can exceed companies such as ANS, BlueNano, Showaand Denko Ube Industries K.K provide CNT-based powders for battery electrodes. ample, the cyclicmaintained efficiency of at a almostadding graphite 10 100% wt% anode MWNTs for [8. was up to 50 cycles by CNTs on theprove graphite rate anode can capabilityCNT-graphite also and composite efficiently cyclability electrodes im- of [8. the resulting used as anode additives inand commercial more than Li-ion 50% batteries of mobile phonesteries and notebook contain bat- CNTs [8.

]. 390 ]. Since 376 , CNTs increase the electrical 8.6.3 ]) is used to improve sporting goods like 337 Far from sport issues yet a serious matter nowadays, 8.7.8 High-Tech Goods and Clothes Enhancement in damping ratios ofposites CNT-polymer com- (upites to [8. 700% for MWNT-epoxy compos- AsreportedinSect. conductivity of polymer composites atlation very low threshold perco- (below 1 wt%)ratio. due In to the automotive their industry, this high property aspect enable is used electrostatic-assisted to painting ofsuch polymer as parts mirror housings and bumpers [8. 8.7.7 Automotive and Aeronautic Industry 2009, BASF hascomposite produced fuel a filter housing CNT-polyoxymethylene forThe high the conductivity Audi of the A4 compositesion and allows suppres- of A5. electrostatic charging andthrough sparking the as filter. Moreover, fuel this flows material is moreresistant creep- than conventional polyoxymethylene andcostly less than other conductive polymer composites. CNT- polymer composites are alsorosion coatings widely for used metals.and as CNTs tribological anticor- enhance properties mechanical ing of an electric coatings pathway for while cathodic protection provid- [8. Solvent-based zinc, aluminium andepoxy/polyamide magnesium paints CNT- for primer anticorrosionings were coat- designed by Tesla Nanocoatings. CNTare sheets used in thecomposites aerospace against industry to electrostaticprotect protect discharge electronic polymer components (ESD), against electromagnetic to interference (EMI), and to create honeycombwith structures higher stiffness thanthermal aluminum expansion, with reduced virtually weight, no brational and damping properties. improved vi- baseball bats, tennis andsticks, racing badminton bicycles, golf racquets, balls/clubs, hockey skis,rods, fly-fishing and archery arrows.of Easton Sports, sporting manufacturer goods,and steel moved sports equipment to new lightweight, high-strength CNT-polymer markets products. from Considering wood difficulty the of dispersing still-current CNTs inis polymers likely well, to which generatechanical point flaws of in view, the oneimprovement might material is wonder real, from whether or a the of whether me- CNTs is a merely minimized added toimpact amount take of benefit using of new the and mediatic high-tech materials. CNT sheets are appliedprotection in wearables reducing the light weight armors of the and finished products. projectile- For instance, bullet-prooftured vests as by manufac- ChinaCorp. (China) Xingxing or AR500 Guangzhou Armorless (USA) Imp. than can their weigh & Kevlar-based 25% equivalents, at Exp. lower cost. Nanomaterial and Nanostructures Part B

230 Part B | 8.7

Created from viennaut on 2018-11-17 04:18:29. Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Carbon Nanotubes 8.8 Toxicity and Environmental Impact of Carbon Nanotubes 231

the limitations posed by pristine CNT sensors (lack terial is based on CNTs, which are functionalized with 8.8 | B Part of specificity to different gaseous analytes, and low proprietary selector materials. Brewer Science (Rolla, sensitivity towards analytes that have no affinity to Missouri) developed a fully integrated temperature and CNTs), functionalization of CNTs with various meth- humidity sensor based on highly purified aqueous- ods was considered, and with a wide spectrum of based SWNT ink. It is capable of providing real-time materials such as conducting polymers and metal na- simultaneous measurement of the temperature and rapid noparticles [8.397]. fluctuations of humidity in a surrounding environment. The commercialization of nanoenabled sensors is in the early stages. Research efforts are still needed in 8.7.11 Catalyst Support particular to control the reproducibility and specificity (chirality, diameter, and length) of commercial CNT Carbon-based materials make good supports in hetero- batch characteristics [8.400, 401]. CNT-based sensors geneous catalytic processes due to their ability to be are currently being developed by large and small com- tailored to the specific needs, such as high surface area, panies, mainly in the USA. Nanomix Incorporated high amount of mesopores, good stability at high tem- (California, USA) has commercialized a CNT-based peratures (under nonoxidizing atmospheres), and the nanosensor for hydrogen detection (operating range of possibility of controlling the chemical nature of their 200020 000 ppm, which is 550% of the lower explo- surfaces [8.402]. Nanosized carbon fibrous morpholo- sive limit for hydrogen). NASA Ames Research Cen- gies have appeared over the last decade, which show ter is developing a low-power-consumption gas sensor great potential for use as supports [8.403] superior to based on coated (e.g., with chlorosulfonated polyethy- regular ones such as activated carbon, carbon blacks, lene) or decorated (e.g., with Pd, Pt, Au, Cu, and Rh or graphite [8.404]. The field of catalysis to which the nanoparticles) SWNTs, so far tested for NO2,NH3, specific features of CNTs could bring the most sig- CH4,Cl2, HCl, toluene, benzene, acetone, formalde- nificant advancements is perhaps the oxygen reduction hyde, and nitrotoluene. Northeastern’s Center for High- reaction in fuel cell electrocatalysis. Carbon materials rate Nanomanufacturing has developed a simple and with both high surface area and good crystallinity such highly sensitive multibiosensor containing semiconduc- as CNTs not only provide a high dispersion of the cata- tor SWNTs that are enzyme-immobilized for detecting lyst (Pt) nanoparticles, but also limit carbon oxidation D-glucose, L-lactate, and urea in sweat. The core tech- at high potentials, and facilitate electron transfer, re- nology platform developed by Nano Engineered Appli- sulting in better device performance [8.405]. Moreover, cations, Inc. (Riverside, California) is a gas sensor using CNTs have a positive effect on Pt structure, resulting SWNTs and solid-state electrical sensing, capable of in a higher catalytic activity and a higher stability than real-time detection of airborne gases at the ppb level. with carbon black supports [8.406]. In that sense, CNTs Sensigent (Baldwin Park, California) chemical sensing offer great promise for overcoming the problems of ex- technology includes CNT-based nanosensors with high isting fuel cells, such as Pt loading. However, a problem sensitivity and selectivity for small molecule gases. for the commercialization of CNT-based electrodes is Design West Technologies, Inc., (Southern Califor- their higher cost compared to that of carbon blacks. nia) proprietary CNT technology can be incorporated Currently, Bing Energy Inc. (Tallahassee, Florida) into existing chemical detector products as standalone has commercialized a proton-exchange membrane fuel chemical sensors or as a supporting orthogonal tech- cell, comprised of highly conductive CNT buckypaper nology to detect various chemical vapors. C2Sense coated with Pt nanoparticles, which was developed at (Cambridge, MA) aims to provide sensors for meat Florida State University to improve membrane manu- spoilage detection in smart packaging. The sensing ma- facturing processes, fuel cell efficiency, and lifetime.

8.8 Toxicity and Environmental Impact of Carbon Nanotubes

It is ﬁrst very important to consider that the large vari- impossible [8.407]. CNTs are mostly found as bun- ety of CNTs (SWNT, DWNT, MWNT, hetero-CNTs, dles rather than as individual objects, or more likely hybrid CNTs, etc.) and of synthesis routes (arc dis- as large micrometric agglomerates. All CNT materials charge, laser ablation, CCVD, :::) as well as the lack contain various levels of residual catalyst(s), depending of standardized testing procedures make the investi- on the synthesis route and puriﬁcation steps they have

Copyright © 2017. Springer. All rights reserved. rights All Springer. 2017. © Copyright gation of the toxicity of CNTs very difﬁcult, and the been subjected to. Usual puriﬁcation treatments involve comparison of the already published results almost the combination of acids and oxidizing agents, which

Springer Handbook of Nanotechnology, edited by Bharat Bhushan, Springer, 2017. ProQuest Ebook Central, http://ebookcentral.proquest.com/lib/viennaut/detail.action?docID=5131796. Created from viennaut on 2018-11-17 04:18:29. the ], etc.); ], and is 409 labeling 409 , 408 ], although about 600 papers have al- 407 ) begs the question of their fate at the end of 8.7 Toxicity can be assessed both by in vitro and in The potential use of CNTs in commercial products There is currently no consensus about the toxicity this adsorption can be very specific [8. CNTs (opsonization) and possibly generatingflammatory some reactions. The in- complement system strongly interacts with the lymphocytes. Theseena natural phenom- have deleterious consequences ontissues: the inflammation surrounding ingranuloma a (commonly observed first in the lungs instance, after exposure formation to of CNTs). Each target organcells has (Kupffer its own cells phagocyte in theskin, liver, etc.). Langerhans cells in the vivo experiments. In thecultures case (usually of immortalized inprimary cultures cancer vitro or even cells, assays, stem cells) cell pensions but are exposed of also to sus- CNTs. Inanimals the (mice, case rats, ofare worms, in exposed amphibians, vivo either assays, fishes,again to the etc.) to aerosols suspensions (inhalation)istrated of or according CNTs mainly to which differentthe will protocols study be depending admin- (intratracheal on with instillation, the injection, skin, contact from etc.). animals Extrapolating (or theis even toxicity very worse, results delicate fromfor but cells) the the sake to data of humans given comparison are experimental in conditions. however As a soon very given ascontact useful system CNTs with and are in a with biologicalis fluid, likely their to surface be chemistry proteins (complement modified system, surfactants very [8. quickly by adsorption of and thus release reactive oxygentokines species, (interferons), etc. enzymes, and cy- agglomerate around them to isolate them from the body.and Proteins most present of in the blood biological fluidsinnate (complement immunity) system will – play a similar role by likely to be dynamic and controlled bymolecules the for affinity of the the surface of thetionalized). It CNTs is (pristine thus or obvious func- thatof the the surface CNTs chemistry will play a very important role. (Sect. their lifecycle. If the impacthas of been under CNTs investigation for on a few human yearsnoteworthy health already, that it environmental is impact has only scarcely been taken into account. Onlythan a 80) few are publications available (less which to ecotoxic date effects and are themuch higher evidenced concentration than what is at could be in reasonablyenvironment found most in (unless the cases very localapply). and specific Because conditions ofsurface the area of potentially CNTs, very theylutants could high adsorbed act as on specific vectors their forhydrocarbons surface pol- or (polycyclic heavy aromatic metalif ions, themselves for do example), not show even any obvious sign of toxicity. of CNTs [8.

ginthecaseof = 2 1300 m ]. 408 ginthecaseofSWNTsandDWNTs(the = 2 g in the case of densely packed MWNTs to nearly The main exposure routes for dry CNTs are in- = 2 halation and dermal contactof (also suspensions). possible Ingestion in is the(would generally case be not accidental), considered less although related it to is inhalation.the in In main fact the issue more casehas concerns or been of their widely suspensions, studied stability. worldwideproach This and is the the question addition general of ap- athe surfactant in CNTs order to in stabilize thecommonly liquid. used The surfactants maintent are problem and toxic is thus to that cannotcells be a all or used certain animals in ex- the foror presence at in such of vivo low living concentrations or thatplay really the in they role vitro no they are longer investigations, natural supposed to surfactants play. have Although a been few of investigated, the the stability suspensions inis the presence often of very living organisms flocculation). different Injection in (fast the bloodstream destabilization isbut envisaged, leading would to notsuch be as imaging, accidental targetedetc.). (biological cell After the delivery, applications CNTs hyperthermia, have enteredtravel the following different body, routes they depending could on thepoint entry (movements from one organ totranslocation) another but are also called mainlycal on characteristics. Objects their recognized as physicochemi- nonself byimmune the system usually endneys up if in they can the be transported liver there,be or and could excreted the possibly (eliminated) kid- from thecase, body. CNTs In will just the accumulate general are (biopersistance). usually They intercepted byin macrophages all (cells tissues present andand then whose digest role – isand when pathogens this to as is well phagocyte possible) as (engulf other cellular to immune cells stimulate debris to lymphocytes respond and to theinto pathogens). account Taking the small size of macrophagesto as compared that ofCNTs, macrophages agglomerates, usually bundles doof or not the CNTs manage even by to phagocytose. However, they individual get try to rid do so individual closed SWNTs). This is arameter very important as pa- theto surface be area the has mostdifferent carbon recently relevant nanoparticles, even metric been with very for shown morphologies different [8. the comparison of leads to partial functionalization of theing outer the wall, treated mak- samples moreDWNTs hydrophilic. usually SWNTs form and longcally and hundreds flexible of bundles micrometers (typi- long)are whereas MWNTs generally shorterrigid. (tens MWNTs of micrometers) alsofects, and have which more generally enhances morespecific surface their surface de- chemical aream reactivity. can The range from a few tens of 1000 m theoretical limit being Nanomaterial and Nanostructures Part B

232 Part B | 8.8

ready been published on this topic within the last 5 sible attitude for people working on their synthesis or 8 | B Part years (2016 data). Despite the worldwide efforts de- manipulating them, and for industries willing to include voted to this field of research, the huge variety of CNT them in consumer products. Gloves should be worn at types, shapes, composition, etc. still makes it very dif- all times as well as an adapted (FFP3 (filtering face- ficult to answer this simple question: are CNTs toxic? piece protection class 3) type) disposable dust mask. The principle of precaution should not stop all research Wearing a lab coat is recommended to limit contami- in this area but only draw attention to a more respon- nation of clothes, and CNT wastes should be burnt.

8.9 Concluding Remarks Carbon nanotubes have been the focus of a lot of re- tion, carbon nanotubes have a supplementary drawback: search work (and therefore a lot of funding) for more they deal with a nano-world that most existing indus- than two decades now. Although some experts initially trial plants are not familiar with, and not designed for. predicted the same disappointment that followed the That is why most applications are currently being taken fullerene era (originally believed to be so promising, to the market by start-ups, and it will take time for those but which has resulted in no significant applications to to reach economic reliability and expand to become ma- date, in spite of a considerable investment of time and jor companies. But some will. money), it is clear that applications including carbon What are the perspectives for carbon nanotubes? nanotubes are now coming onto the market. It took time They are quite positive, and it is not being overop- indeed, but that is the price to pay when introducing timistic to say so: nanotubes exhibit an extraordi- a new material into technology. It is an almost general nary diversity of morphologies, textures, structures and rule, which accounts for the time needed for production nanotextures, far beyond that provided by fullerenes, lines to reach the requested mass-scale, reproducibility, and now graphene. As most of their properties have reliability, and economic viability according to indus- now been experimentally studied or predicted, research trial standards. Taking the example of carbon fibers, should focus on solving the problems related to their first developed in the 1960s, how long did it take to incorporation into the tremendous variety of devices see them in mass consumption, high-tech products (be- and materials that would benefit from the CNT tech- sides sporting goods, for which cost is less of an issue)? nology. In this regard, considering the nanotube-based It is happening only now, as commercial planes (A350 nano-objects and composites described in Sect. 8.5 and from Airbus, Dreamliner from Boeing) incorporate sig- Sect. 8.6 is of primary importance. Of course, this nificant amounts of carbon fibers in their structures, comes with some uncertainty regarding the potential whereas previously only the military field had been able toxicity related to CNTs at various points of their life to afford the benefits of such a technological jump. De- cycle, but this issue concerns all nanomaterials in gen- spite this, carbon fibers have not yet reached the general eral, and is the most critical challenge upon which the automobile field, except for luxury or race cars. In addi- future of nanotechnologies depends.

References

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