Carbon Nanotubes

Carbon, a group IV element, has two crystalline forms: diamond and

graphite. Carbon nanotubes (CNTs) are allotropes of carbon. These cylindrical carbon molecules ha e no el properties that ma!e them potentially useful in many applications in nanotechnology, electronics, optics and other fields of materials science, as well as potential uses in architectural fields. They e"hibit e"traordinary strength and uni#ue electrical properties, and are efficient conductors of heat. CNTs are members of the fullerene structural family, which also includes the spherical buc!yballs $. The ends of a CNT might be capped with a hemisphere of the buc!yball structure. Carbon nanotubes are one of the most commonly mentioned building bloc!s of nanotechnology. %ith one hundred times the tensile strength of steel, thermal conducti ity better than all but the purest diamond, and electrical conducti ity similar to copper, but with the ability to carry much higher currents, they seem to be a wonder material. &owe er, when we hear of some companies planning to produce hundreds of tons per year, while others seem to ha e e"treme difficulty in producing grams, there is clearly more to this material than meets the eye. Carbon nanotubes, long thin cylinders of carbon, were discovered in 1991 by Iijimas. Carbon nanotubes (CN s! are allotro"es of carbon which are members of the fullerene structural family, which also includes the s"herical buc#yballs. hese are large macromolecules which are uni$ue for there si%e, sha"e and remar#able "hysical "ro"erties. he nature of the bonding of a nanotube is described by a""lied $uantum chemistry, s"ecifically, orbital hybridi%ation. he chemical bonding of nanotubes is com"osed entirely of s"& bonds, similar to those of gra"hite. his bonding structure, which is stronger than the s" ' bonds found in diamond, "rovides the molecules with their uni$ue strength. Nanotubes naturally align themselves into (ro"es) held together by *an der +aals forces. ,nder high "ressure, nanotubes can merge together, trading some s"- bonds for s". bonds, giving the "ossibility of "roducing strong, unlimited/length wires through high/"ressure nanotube lin#ing. CNTs are named on the basis of deri ed from their si'e, since the diameter of a nanotube is on the order of a few nanometers, while they can be up to se eral millimeters in length CNTs are categori'ed as single(walled nanotubes ()%NTs) and multi(walled nanotubes (*%NTs) depending upon the number of walls. CNTs may consist of one up to tens and hundreds of concentric shells of carbons with ad+acent shells separation of ,.-. nm i.e. (,,/). The carbon networ! of the shells is closely related to the honeycomb arrangement of the carbon atoms in the graphite sheets. The ama'ing mechanical and electronic properties of the nanotubes stem in their #uasi(one

dimensional ($0) structure and the graphite(li!e arrangement of the carbon atoms in the shells. Thus, the nanotubes ha e high 1oung2s modulus and tensile strength, which ma!es them suitable for composite materials with impro ed mechanical properties. The nanotubes can be metallic or semi conducting depending on their structural parameters . The term nanotube is normally used to refer to the carbon nanotube, which has recei ed enormous attention from researchers o er the last few years and promises, along with close relati es such as the nanohorn, a host of interesting applications. There are many other types of nanotube, from arious inorganic !inds, such as those made from boron nitride, to organic ones, such as those made from self assembling cyclic peptides (protein components) or from naturally(occurring heat shoc! proteins (e"tracted from bacteria that thri e in e"treme en ironments). &owe er, carbon nanotubes e"cite the most interest, promise the greatest ariety of applications, and currently appear to ha e by far the highest commercial potential. 3nly carbon nanotubes will be co ered in this white paper.

N4N3T567) are the most successful materials that are now attracting a broad range of scientists and industries due to their fascinating physical and chemical properties. In this re iew, we enlighten you about this material. %e are introducing here, the structure, synthesis and the most important applications of carbon nanotubes in different fields. The session will feature technology that e"ploits no el electronic, electro(mechanical, transistors, and electrical circuits, optical and structural properties of a carbon nanotube for the solution of engineering problems.

Nanotubes are members of the fullerene structural family, which also includes the s"herical buc#yballs, and the ends of a nanotube may be ca""ed with a hemis"here of the buc#yball structure. heir name is derived from their long, hollow structure with the walls formed by one/atom/thic# sheets of carbon, called gra"hene.

8raphene0/

Graphene is an allotrope of carbon, whose structure is one(atom(thic! planar sheets of sp/(bonded carbon atoms that are densely pac!ed in a honeycomb crystal lattice, the term graphene was coined as a combination of gra"hite and the suffi1 /ene by 2anns/3eter 4oehm who described single/layer carbon foils in 195&. 6ra"hene is most easily visuali%ed as an atomic/scale chic#en wire made of carbon atoms and their bonds. he crystalline or 7fla#e7 form of gra"hite consists of many gra"hene sheets stac#ed together. he carbon/carbon bond length in gra"hene is about 8.19& nanometres. 6ra"hene sheets stac# to form gra"hite with an inter"lanar s"acing of 8.'': nm, which means that a stac# of three million sheets would be only one millimetre thic#. 6ra"hene is the basic structural element of some carbon allotro"es including gra"hite, charcoal, carbon and fullerenes. It can also be considered as an indefinitely large aromatic molecule, the limiting case of the family of flat "olycyclic aromatic hydrocarbons. 8raphene is a flat monolayer of carbon atoms tightly pac!ed into a two( dimensional (/0) honeycomb lattice, and is a basic building bloc! for graphitic materials of all other dimensionalities. It can be wrapped up into ,0 fullerenes, rolled into $0 nanotube or stac!ed into -0 graphite. 6ra"hene is an isolated atomic "lane of gra"hite. ;rom this "ers"ective, gra"hene has been #nown since the invention of </ray crystallogra"hy. 6ra"hene "lanes become even well se"arated in intercalated gra"hite com"ounds. In &889 "hysicists at the ,niversity of =anchester and the Institute for =icroelectronics echnology, Chernogolov#a, >ussia, first isolated individual gra"hene "lanes by using adhesive ta"e. hey also measured electronic "ro"erties of the obtained fla#es and showed their uni$ue "ro"erties. he Nobel 3ri%e in 3hysics for &818 was awarded to ?ndre 6eim and @onstantin Novoselov)for groundbrea#ing e1"eriments regarding the two/dimensional material gra"hene7.

he >oyal Awedish ?cademy of Aciences has awarded the Nobel 3ri%e in 3hysics for &818 to ?ndre 6eim and @onstantin

Novoselov, both of the ,niversity of =anchester, 7for groundbrea!ing e"periments regarding the two(dimensional material graphene.7

? thin fla#e of ordinary carbon, just one atom thic#, lies behind this yearBs Nobel 3ri%e in 3hysics. 6eim and Novoselov have shown that carbon in such a flat form has e1ce"tional "ro"erties that originate from the remar#able world of $uantum "hysics. 6eim and Novoselov e1tracted the gra"hene from a "iece of gra"hite such as is found in ordinary "encils. ,sing regular adhesive ta"e they managed to obtain a fla#e of carbon with a thic#ness of just one atom. his at a time when many believed it was im"ossible for such thin crystalline materials to be stable. 2owever, with gra"hene, "hysicists can now study a new class of two/ dimensional materials with uni$ue "ro"erties. 6ra"hene ma#es e1"eriments "ossible that give new twists to the "henomena in $uantum "hysics. ?lso a vast variety of "ractical a""lications now a""ear "ossible including the creation of new materials and the manufacture of innovative electronics. 6ra"hene transistors are "redicted to be substantially faster than todayBs silicon transistors and result in more efficient com"uters.

Aince it is "ractically trans"arent and a good conductor, gra"hene is suitable for "roducing trans"arent touch screens, light "anels, and maybe even solar cells. +hen mi1ed into "lastics, gra"hene can turn them into conductors of electricity while ma#ing them more heat resistant and mechanically robust. his resilience can be utili%ed in new su"er strong materials, which are also thin, elastic and lightweight. In the future, satellites, air"lanes, and cars could be manufactured out of the new com"osite materials.

Graphene formation0/
he =anchester grou" obtained gra"hene by mechanical e1foliation of gra"hite. hey used cohesive ta"e to re"eatedly s"lit gra"hite crystals into increasingly thinner "ieces. he ta"e with attached o"tically trans"arent fla#es was dissolved in acetone, and, after a few further ste"s, the fla#es including monolayers were sedimented on a silicon wafer. Individual atomic "lanes were then hunted in an o"tical microsco"e. ? year later, the researchers

sim"lified the techni$ue and started using dry de"osition, avoiding the stage when gra"hene floated in a li$uid. >elatively large crystallites (first, only a few micrometers in si%e but, eventually, larger than 1 mm and visible by a na#ed eye! were obtained by the techni$ue. It is often referred to as a scotch ta"e or drawing method. he latter name a""eared because the dry de"osition resembles drawing with a "iece of gra"hite. he #ey for the success "robably was the use of high/through"ut visual recognition of gra"hene on a "ro"erly chosen substrate, which "rovides a small but noticeable o"tical contrast. he C"tical "ro"erties section below has a "hotogra"h of what gra"hene loo#s li#e.

here were a number of "revious attem"ts to ma#e atomically thin gra"hitic films by using e1foliation techni$ues similar to the drawing method. =ultilayer sam"les down to 18 nm in thic#ness were obtained. hese efforts were reviewed in &88D. ;urthermore, a cou"le of very old "a"ers were recently unearthed in which researchers tried to isolate gra"hene starting with intercalated com"ounds. hese "a"ers re"orted the observation of very thin gra"hitic fragments ("ossibly minelayers! by transmission electron microsco"y. Neither of the earlier observations was sufficient to 7s"ar# the gra"hene gold rush7, until the Acience "a"er did so by re"orting not only macrosco"ic sam"les of e1tracted atomic "lanes but, im"ortantly, their unusual "ro"erties such as the bi"olar transistor effect, ballistic trans"ort of charges, large $uantum oscillations, etc. he discovery of such interesting $ualities intrinsic to gra"hene gave an immediate boost to further research and several grou"s $uic#ly re"eated the initial result and moved further. hese brea#throughs also hel"ed to attract attention to other "roduction techni$ues, such as e"ita1ial growth of ultra/thin gra"hitic films. In "articular, it has later been found that gra"hene monolayers grown on AiC and Ir are wea#ly cou"led to these substrates and the gra"hene/substrate interaction can be "assivated further.

he wea# van der +aals force that "rovides the cohesion of multilayer gra"hene stac#s does not always affect the electronic "ro"erties of the individual gra"hene layers in the stac#. hat is, while the electronic "ro"erties of certain multilayered e"ita1ial gra"henes are identical to that of a single gra"hene layer, in other cases the "ro"erties are affected as they are for gra"hene layers in bul# gra"hite. his effect is theoretically well understood and is related to the symmetry of the interlayer interactions. E1"erimental methods for the "roduction of gra"hene ribbons are re"orted consisting of cutting o"en nanotubes. In one such method multi walled carbon nanotubes are cut o"en in solution by action of "otassium "ermanganate and sulfuric acid. In another method gra"hene nanoribbons are "roduced by "lasma etching of nanotubes "artly embedded in a "olymer film.

Properties of graphene0/
?tomic structure0/
he atomic structure of isolated, single/layer gra"hene was studied by transmission electron microsco"y ( E=! on sheets of gra"hene sus"ended between bars of a metallic grid. Electron diffraction "atterns showed the e1"ected he1agonal lattice of gra"hene. Aus"ended gra"hene also showed 7ri""ling7 of the flat sheet, with am"litude of about one nanometer. hese ri""les may be intrinsic to gra"hene as a result of the instability of two/ dimensional crystals or may be e1trinsic, originating from the ubi$uitous dirt seen in all E= images of gra"hene. ?tomic resolution real/s"ace images of isolated, single/layer gra"hene on AiC& substrates were obtained by scanning tunneling microsco"y. 6ra"hene "rocessed using lithogra"hic techni$ues is covered by "hotoresist residue, which must be cleaned to obtain atomic/ resolution images. 6ra"hene sheets in solid form (density F 1 gGcm '! usually show evidence in diffraction for gra"hiteBs 8.'9 nm (88&! layering. his is true even

of some single/walled carbon nanostructures. ransmission electron microsco"e studies show faceting at defects in flat gra"hene sheets.

Electronic "ro"erty0/
6ra"hene differs from most conventional three/dimensional materials. Intrinsic gra"hene is a semi/metal or %ero/ga" semiconductor. ,nderstanding the electronic structure of gra"hene is the starting "oint for finding the band structure of gra"hite. It was reali%ed as early as 199D by 3. >. +allace that the E/# relation is linear for low energies near the si1 corners of the two/ dimensional he1agonal 4rillouin %one, leading to %ero effective for electrons and holes. Hue to this linear (or (conical7! dis"ersion relation at low energies, electrons and holes near these si1 "oints, two of which are ine$uivalent, behave li#e relativistic "articles described by the Hirac e$uation for s"in 1G& "articles. 2ence, the electrons and holes are called Hirac fermions, and the si1 corners of the 4rillouin %one are called the Hirac "oints. he e$uation describing the E/# relation is

he ;ermi velocity

I 185mGs

Thermal properties:The near-room temperature thermal conductivity of graphene was recently measured to be between (4.840.44 !"0 # to ($.#00.48 !"0#%m&"'&". These measurements( made by a non-contact optical techni)ue( are in e*cess of those measured for carbon nanotubes or diamond. +t can be shown by using the %iedemann,ran- law( that the thermal conduction is phonon-dominated. .owever( for a gated graphene strip( an applied gate bias causing a ,ermi energy shift much larger than /0T can cause the electronic contribution to increase and dominate over the phonon contribution at low temperatures.

1echanical properties:2raphene appears to be one of the strongest materials ever tested. 1easurements have shown that graphene has a brea/ing strength 300 times greater than steel( with a tensile strength of "#024a ("5(000(000 psi . 6sing an atomic force microscope (7,1 ( the spring constant of suspended graphene sheets has been measured. 2raphene sheets( held together by van der %aals forces( were suspended over 8i93 cavities where an 7,1 tip was probed to test its mechanical properties. +ts spring constant was in the range ":$ ;<m and the =oung>s modulus was 0.$ T4a( which differs from that of the bul/ graphite. These high values ma/e graphene very strong and rigid. These intrinsic properties could lead to using graphene for ;?18 applications such as pressure sensors and resonators.

HISTORY:
he history of carbon nanotubes is not entirely clear even for those in the science therefore giving "ro"er credit to the "erson that invented the carbon nanotube has been the subject of several high tech debates among the scientific communities. he initial history of nanotubes started in the 19D8s. ? "re"aration of the "lanned carbon filaments was com"leted by =orinobu Endo who was earning his 3h.H. at the ,niversity of Crleans, ;rance. his was still a highly im"ortant develo"ment in the history of carbon nanotubes, but it just wasnt the right time to be considered the first recogni%ed invention. 6iving the "ro"er credit to who invented carbon nanotubes would not come along for another &8 years. In 1991 the true first invention of nanotube was finally made. It seems as though there was a race between >ussian nanotechnologists and Aumio Iijima of I4=.

he first observation of the multiwalled carbon nanotubes was credited to Iijima.

here are some that hold the belief that in the 19:8s there was an initial discovery of what could have "ossibly been seen as the first carbon nanotubes had >oger 4acon had the high "owered electron microsco"e that would have been necessary. 2e was credited with the first visual im"ression of the tubes of atoms that roll u" and are ca""ed with fullerene molecules by many scientists in the field. Aome state that his discovery just wasnt ta#en very seriously at the time because science did not #now how this discovery could im"act scientific research.

It would be in 199' that Iijima and Honald 4ethune found single walled nanotubes #nown as buc#ytubes. his hel"ed the scientific community ma#e more sense out of not only the "otential for nanotube research, but the use and e1istence of fullerenes. +ith this information, the com"lete discovery of carbon nanotubes was reali%ed and Iijima and 4ethune were ultimately credited with their discovery

in their entirety. >ussian nanotechnologists were inde"endently discovering the same visual affirmation. hey were just a little bit later in their announcement and the "otential affect of this discovery. he continuation of research revealed a great deal about nanotubes and their "lace in scientific discovery. he research has indicated that there are three basic ty"es of nanotubes (%ig%ag, armchair, and chiral! as well as single walled and multiwalled nanotubes. here are buc#ytubes, which are com"letely hollow molecules that are crafted from "ure carbon and are bonded together in a "attern of s"ecific he1agon "atterns. he multiwalled nanotubes are li#ely to suffer from defects. hese defects ha""en in more than half of all multiwalled nanotubes. he multiwalled nanotubes have already made a""earances in "ractical a""lications li#e creating tennis rac#ets that are stronger than steel but are ultra light in weight. hese nanotubes are also res"onsible for creating sunscreen and other s#in care "roducts that are clear or able to be blended into the s#in without leaving behind residue as well as the creation of ,* "rotective clothing. ?s nanotechnologists continue to research nanotubes, there is still a race to discover something new within the science. Acientists are researching the "otential for life saving techni$ues as well as the "otential to create nanotubes that can be tailored toward s"ecific designated jobs. +ith the creation of s"ecified nanotubes, the "otential for their use will become unlimited and there will be a nanotechnology world hard at wor# crafting all #inds of "roducts from the convenient to the life saving.

TYPES OF CARBON NANOT BES!"

a 8+;2@?-%7@@?A B;TCs
hese are the stars of the nanotube world, and somewhat reclusive ones at that, being much harder to ma#e than the multi/walled variety. he oft/$uoted ama%ing "ro"erties generally refer to A+N s. ?s "reviously described, they are basically tubes of gra"hite and are normally ca""ed at the ends although the ca"s can be removed. he ca"s are made by mi1ing in some "entagons with the he1agons and are the reason that nanotubes are considered close cousins of buc#minsterfullerene a roughly s"herical molecule made of si1ty carbon atoms, that loo#s li#e a soccer ball

and is named after the architect 4uc#minster ;uller (the word fullerene is used to refer to the variety of such molecular cages, some with more carbon atoms than buc#minsterfullerene, and some with fewer!.

he theoretical minimum diameter of a carbon nanotube is around 8.9 nanometers, which is about as long as two silicon atoms side by side, and nanotubes this si%e have been made. ?verage diameters tend to be around the 1.& nanometer mar#, de"ending on the "rocess used to create them. A+N s are more "liable than their multi/walled counter"arts and can be twisted, flattened and bent into small circles or around shar" bends without brea#ing. =ost single/walled nanotubes (A+N ! have a diameter close to 1nm, with a tube length that can be many thousands of times longer. A+N s are very im"ortant carbon nanotube because they e1hibit im"ortant electric "ro"erties that are not shared by the multi/walled carbon nanotubes (=+N ! variants. A+N s can be e1cellent conductors and the most building bloc# of A+N system is the electric wires. Cne useful a""lication of A+N s is in the develo"ment of the first intramolecular field effect transistors (;E s!.

STR CT RE:
he bonding in carbon nanotubes is s"-, with each atom joined to three neighbours, as in gra"hite. he tubes can therefore be considered as rolled/ u" gra"hene sheets (gra"hene is an individual gra"hite layer!. here are three distinct ways in which a gra"hene sheet can be rolled into a tube, as shown below. he terms (armchair) and (-ig--ag) refer to the arrangement of he1agons around the circumference. he third class of tube, which in "ractice is the most common, is #nown as chiral, meaning that it can e1ist in two mirror/ related forms. ?n e1am"le of a chiral nanotube is as shown in fig. below.

In the ideal case, a carbon nanotube consists of either one cylindrical gra"hene sheet (single/wall nanotube, A+N ! or of several nested cylinders with an interlayer s"acing of 8.'9 J 8.'5 nm that is close to the ty"ical s"acing of turbostratic gra"hite (multiwalled nanotube, =+N !.

here are many "ossibilities to form a cylinder with a gra"hene sheet0 the sim"lest way of visuali%ing this is to use a 7de .eer abacus70

? (de 2eer abacus)0 to reali%e a (n,m! tube, move n times a1 and m times a& from the origin to get to "oint (n,m! and roll/u" the sheet so that the two "oints coincide... 4asically, one can roll u" the sheet along one of the symmetry a1is0 this gives either a %ig/%ag tube or an armchair tube. It is also "ossible to roll u" the sheet in a direction that differs from a symmetry a1is0 one obtains a chiral nanotube, in which the e$uivalent atoms of each unit cell are aligned on a s"iral. 4esides the chiral angle, the circumference of the cylinder can also be varied. In general, the whole family of nanotubes is classified as %ig%ag, armchair, and chiral tubes of different diameters0

=odels of different single wall nanotubes (generated with =athematica on the left, and ta#en from Aaito et al., ?3K 58, &&89 (199&! on the above!. his diversity of "ossible configurations is indeed found in "ractice, and no "articular ty"e is "referentially formed. he lengths of A+N s and =+N s are usually well over 1 Lm and diameters range from I1 nm (for A+N s! to I:8 nm (for =+N s!. 3ristine A+N s are usually closed at both ends by fullerene/li#e half s"heres that contain both "entagons and he1agons. ?s shown in the electron microsco"y images below, a A+N has a well/defined s"herical ti", whereas the sha"e of a =+N ca" is more "olyhedral than s"herical. ?n o"en =+N , as the name im"lies, doesnBt have a ca" and the ends of the gra"hene layers and the internal cavity of the tube are e1"osed.

ransmission electron microsco"y ( E=! "ictures of the ends of different nanotubes. Each blac# line corres"onds to one gra"hene sheet viewed edge/ on.

Hefects in the he1agonal lattice are usually "resent in the form of "entagons and he"tagons. 3entagons "roduce a "ositive curvature of the gra"hene layer and are mostly found at the ca". 2e"tagons give raise to a negative curvature of the tube wall. Hefects consisting of several "entagons andGor he"tagons have also been observed.

A simple model indicates that the diameter and/or chirality of the tube are changed from one side of the defect to the other. Such an arrangement forms therefore a link between two different tubes and is accordingly called a junction.

b 16@T+-%7@@?A B;TCs:
=ulti/walled nanotubes (=+N ! consist of multi"le rolled in on themselves to form a tube sha"e. here are two models which can be used to describe the structures of multi/walled nanotubes. In the >ussian Holl model, sheets of gra"hite are arranged in concentric cylinders. In the 3archment model, a single sheet of gra"hite is rolled in around itself, resembling a scroll of "archment or a rolled u" news"a"er. he interlayer distance in multi/walled nanotubes is close to the distance between gra"hene layers in gra"hite, a""ro1imately 8.'' nm.

?lthough it is easier to "roduce significant $uantities of =+N s than A+N s, their structures are less well understood than single/wall nanotubes because of their greater com"le1ity and variety. =ultitudes of e1otic sha"es and arrangements, often with imaginative names such as bamboo/trun#s, sea urchins, nec#laces or coils, have also been observed under different "rocessing conditions. he variety of forms may be interesting but also has a negative sideM=+N s always (so far! have more defects than A+N s and these diminish their desirable "ro"erties. =any of the nanotube a""lications now being considered or "ut into "ractice involve multi/walled nanotubes, because they are easier to "roduce in large $uantities at a reasonable "rice and have been available in decent amounts

for much longer than A+N s. In fact one of the major manufacturers of =+N s at the moment, 2y"erion Catalysis, does not even sell the nanotubes directly but only "re/mi1ed with "olymers for com"osites a""lications. he tubes involved ty"ically have N to 1: walls and are around 18 nanometres wide and 18 micrometers long. Com"anies are moving into this s"ace, notably formidable "layers li#e =itsui, with "lans to "roduce similar ty"es of =+N in hundreds of tons a year, a $uantity that is greater, but not hugely so, than the current "roduction of 2y"erion Catalysis. his is an indication that even these less im"ressive and e1otic nanotubes hold "romise of re"resenting a si%able mar#et in the near future.

SYNTHESIS:here are a number of methods of ma#ing CN s and fullerenes. ;ullerenes were first observed after va"ori%ing gra"hite with a short/"ulse, high/"ower laser, however this was not a "ractical method for ma#ing large $uantities. CN s have "robably been around for a lot longer than was first reali%ed, and may have been made during various carbon combustion and va"or de"osition "rocesses, but electron microsco"y at that time was not advanced enough to distinguish them from other ty"es of tubes. he first method for "roducing CN s and fullerenes in reasonable $uantities J was by a""lying an electric current across two carbonaceous electrodes in an inert gas atmos"here. his method is called p#asma ar$ing. It involves the eva"oration of one electrode as cations followed by de"osition at the other electrode. his "lasma/based "rocess is analogous to the more familiar electro"lating "rocess in a li$uid medium. ;ullerenes and CN s are formed by "lasma arcing of carbonaceous materials, "articularly gra"hite. he fullerenes a""ear in the soot that is formed, while the CN s are de"osited on the o""osing electrode. ?nother method of nanotube synthesis involves "lasma arcing in the "resence of cobalt with a 'O or greater concentration. ?s noted above, the nanotube "roduct is a com"act cathode de"osit of rod li#e mor"hology. 2owever when cobalt is added as a catalyst, the nature of the "roduct changes to a web, with strands of 1mm or so thic#ness that stretch from the cathode to the walls of the reaction vessel. he mechanism by which cobalt changes this "rocess is unclear, however one "ossibility is that such metals affect the local electric fields and hence the formation of the five/membered rings. )ynthesis of carbon nanotubes can be done by different methods:( $) 4rc discharge method /) :aser ablation method -) Chemical apour deposition method a) plasma enhanced chemical apour deposition b) Thermal chemical apour deposition c) Vapour phase growth

a) 4;C 0I)C&4;87 *7T&30

Nanotubes were observed in 1991 in the carbon soot of gra"hite electrodes during an arc discharge, by using a current of 188 am"eres that was intended to "roduce fullerenes.

he carbon arc discharge method, initially used for "roducing C58 fullerenes, is the most common and "erha"s easiest way to "roduce CN s, as it is rather sim"le. 2owever, it is a techni$ue that "roduces a com"le1 mi1ture of com"onents, and re$uires further "urification / to se"arate the CN s from the soot and the residual catalytic metals "resent in the crude "roduct. his method creates CN s through arc/va"ori%ation of two carbon rods "laced end to end, se"arated by a""ro1imately 1mm, in an enclosure that is usually filled with inert gas at low "ressure. >ecent investigations have shown that it is also "ossible to create CN s with the arc method in li$uid nitrogen. ? direct current of :8 to 188 ?, driven by a "otential difference of a""ro1imately &8 *, creates a high tem"erature discharge between the two electrodes. he discharge va"ori%es the surface of one of the carbon electrodes, and forms a small rod/sha"ed de"osit on the other electrode. 3roducing CN s in high yield de"ends on the uniformity of the "lasma arc, and the tem"erature of the de"osit forming on the carbon electrode. he carbon contained in the negative electrode sublimates because of the high tem"eratures caused by the discharge. 4ecause nanotubes were initially discovered using this techni$ue, it has been the most widely used method of nanotube synthesis.

he yield for this method is u" to '8 "ercent by weight and it "roduces both single/ and multi/walled nanotubes with lengths of u" to :8 micrometers.

b) :4)7; 46:4TI3N <;3C7))

In the laser ablation "rocess, a "ulsed laser va"ori%es a gra"hite target in a high tem"erature reactor while an inert gas is bled into the chamber. he nanotubes develo" on the cooler surfaces of the reactor, as the va"ori%ed carbon condenses. ? water/cooled surface may be included in the system to collect the nanotubes. In 1995 CN s were first synthesi%ed using a dual/"ulsed laser and achieved yields of FD8wtO "urity. Aam"les were "re"ared by laser va"ori%ation of gra"hite rods with a :80:8 catalyst mi1ture of Cobalt and Nic#el at 1&88PC in flowing argon, followed by heat treatment in a vacuum at 1888PC to remove the C58 and other fullerenes. he initial laser va"ori%ation "ulse was followed by a second "ulse, to va"ori%e the target more uniformly. he use of two successive laser "ulses minimi%es the amount of carbon de"osited as soot. he second laser "ulse brea#s u" the larger "articles ablated by the first one, and feeds them into the growing nanotube structure.

he material "roduced by this method a""ears as a mat of (ro"es), 18/&8nm in diameter and u" to 188Lm or more in length. Each ro"e is found to consist "rimarily of a bundle of single walled nanotubes, aligned along a common a1is. 4y varying the growth tem"erature, the catalyst com"osition, and other "rocess "arameters, the average nanotube diameter and si%e distribution can be varied. ?rc/discharge and laser va"ori%ation are currently the "rinci"al methods for obtaining small $uantities of high $uality CN s. 2owever, both methods suffer from drawbac#s. he first is that both methods involve eva"orating the carbon source, so it has been unclear how to scale u" "roduction to the industrial level using these a""roaches. he second issue relates to the fact that va"ori%ation methods grow CN s in highly tangled forms, mi1ed with unwanted forms of carbon andGor metal s"ecies. he CN s thus "roduced are difficult to "urify, mani"ulate, and assemble for building nanotube/device architectures for "ractical a""lications

his method has a yield of around D8O and "roduces "rimarily single/walled carbon nanotubes with a controllable diameter determined by the reaction tem"erature.

c) C&7*IC4: V4<35; 07<3)ITI3N

Chemical va"or de"osition of hydrocarbons over a metal catalyst is a classical method that has been used to "roduce various carbon materials such as carbon fibers and filaments. ;or over twenty years. Karge amounts of CN s can be formed by catalytic C*H of acetylene over Cobalt and iron catalysts su""orted on silica or %eolite. he carbon de"osition activity seems to relate to the cobalt content of the catalyst, whereas the CN s selectivity seems to be a function of the "2 in catalyst "re"aration. ;ullerenes and bundles of single walled nanotubes were also found among the multi walled nanotubes "roduced on the carbonG%eolite catalyst. Aome researchers are e1"erimenting with the formation of CN s from ethylene. Au""orted catalysts such as iron, cobalt, and nic#el, containing either a single metal or a mi1ture of metals, seem to induce the growth of isolated single walled nanotubes or single walled nanotubes bundles in the ethylene atmos"here. he "roduction of single walled nanotubes, as well as double/ walled CN s, on molybdenum and molybdenum/iron alloy catalysts has also been demonstrated. C*H of carbon within the "ores of a thin alumina tem"late with or without a Nic#el catalyst has been achieved. Ethylene was used with reaction tem"eratures of :9:PC for Nic#el/cataly%ed C*H, and 988PC for an uncataly%ed "rocess. he resultant carbon nanostructures have o"en ends, with no ca"s. =ethane has also been used as a carbon source. In "articular it has been used to obtain Qnanotube chi"s containing isolated single walled nanotubes at controlled locations. 2igh yields of single walled nanotubes have been obtained by catalytic decom"osition of an 2&GC29 mi1ture over well/dis"ersed metal "articles such as Cobalt, Nic#el, and Iron on magnesium o1ide at 1888PC. It has been re"orted that the synthesis of com"osite "owders containing well/dis"ersed CN s can be achieved by selective reduction in an 2&GC29 atmos"here of o1ide solid solutions between a non/reducible o1ide such as ?l&C' or =g?l&C9 and one or more transition metal o1ides. he reduction "roduces very small transition metal "articles at a tem"erature of usually FN88PC. he decom"osition of C29 over the freshly formed nano"articles "revents their further growth, and thus results in a very high "ro"ortion of single walled nanotubes and fewer multi walled nanotubes. hese are the basic "rinci"les of the C*H "rocess. In the last decennia, different techni$ues for the carbon nanotubes synthesis with C*H have been develo"ed, such as "lasma enhanced C*H, thermal chemical C*H, alcohol catalytic C*H, va"our "hase growth, aero gel/su""orted C*H and laser/ assisted C*H. hese different techni$ues will be e1"lained more detailed in this cha"ter.

,sing C*H, a substrate is "re"ared with a layer of metal catalyst "articles, most commonly nic#el, cobalt, iron, or a combination. he diameters of the nanotubes that are to be grown are related to the si%e of the metal "articles. his can be controlled by "atterned de"osition of the metal, annealing, or by "lasma etching of a metal layer. he substrate is heated to a""ro1imately D88PC. o initiate the growth of nanotubes, two gases are bled into the reactor0 a "rocess gas (such as ammonia, nitrogen, hydrogen, etc.! and a carbon/containing gas (such as acetylene, ethylene, ethanol, methane, etc.!. Nanotubes grow at the sites of the metal catalystR the carbon/containing gas is bro#en a"art at the surface of the catalyst "article, and the carbon is trans"orted to the edges of the "article. C*H is a common method for the commercial "roduction of carbon nanotubes.. ;or this "ur"ose, the metal nano"articles will be carefully mi1ed with a catalyst su""ort (e.g., =gC, ?l&C', etc! to increase the s"ecific surface area for higher yield of the catalytic reaction of the carbon feedstoc# with the metal "articles. Cne issue in this synthesis route is the removal of the catalyst su""ort via an acid treatment, which sometimes could destroy the original structure of the carbon nanotubes. 2owever, alternative catalyst su""orts that are soluble in water have been shown to be effective for nanotube growth. If "lasma is generated by the a""lication of a strong electric field during the growth "rocess ("lasma enhanced chemical va"or de"osition!, then the nanotube growth will follow the direction of the electric field. 4y "ro"erly adjusting the geometry of the reactor it is "ossible to synthesi%e vertically aligned carbon nanotubes.

" 4lasma enhanced chemical vapour deposition

he "lasma enhanced C*H method generates a glow discharge in a chamber or a reaction furnace by a high fre$uency voltage a""lied to both electrodes.

;igure shows a schematic diagram of a ty"ical "lasma C*H a""aratus with a "arallel "late electrode structure.

9igure: )chematic diagram of plasma CV0 apparatus. ? substrate is "laced on the grounded electrode. In order to form a uniform film, the reaction gas is su""lied from the o""osite "late. Catalytic metal, such as ;e, Ni and Co are used on for e1am"le a Ai, AiC &, or glass substrate using thermal C*H or s"uttering. ?fter nanosco"ic fine metal "articles are formed, carbon nanotubes will be grown on the metal "articles on the substrate by glow discharge generated from high fre$uency "ower. ? carbon containing reaction gas, such as C&2&, C29, C&29, C&25, CC is su""lied to the chamber during the discharge. he catalyst has a strong effect on the nanotube diameter, growth rate, wall thic#ness, mor"hology and microstructure. Ni seems to be the most suitable "ure/metal catalyst for the growth of aligned multi/walled carbon nanotubes (=+N s!'5. he diameter of the =+N s is a""ro1imately 1: nm. he highest yield of carbon nanotubes achieved was about :8O and was obtained at relatively low tem"eratures (below ''8o C!.

3 Thermal chemical vapour deposition

In this method ;e, Ni, Co or an alloy of the three catalytic metals is initially de"osited on a substrate. ?fter the substrate is etched in a diluted 2; solution with distilled water, the s"ecimen is "laced in a $uart% boat. he boat is "ositioned in a C*H reaction furnace, and nanometer/si%ed catalytic metal "articles are formed after an additional etching of the catalytic metal film using N2' gas at a tem"erature of D:8 to 18:8 o C. ?s carbon nanotubes are grown on these fine catalytic metal "articles in C*H synthesis, forming these fine catalytic metal "articles is the most im"ortant "rocess. ;igure shows a schematic diagram of thermal C*H a""aratus in the synthesis of carbon nanotubes.

9igure: )chematic diagram of thermal CV0 apparatus. +hen growing carbon nanotubes on a ;e catalytic film by thermal C*H, the diameter range of the carbon nanotubes de"ends on the thic#ness of the catalytic film. 4y using a thic#ness of 1' nm, the diameter distribution lies between '8 and 98 nm. +hen a thic#ness of &D nm is used, the diameter range is between 188 and &88 nm. he carbon nanotubes formed are multiwalled.

# Dapour phase growth

*a"our "hase growth is a synthesis method of carbon nanotubes, directly su""lying reaction gas and catalytic metal in the chamber without a substrate '9. ;igure shows a schematic diagram of a va"our "hase growth a""aratus. wo furnaces are "laced in the reaction chamber. ;errocene is used as catalyst. In the first furnace, va"ori%ation of catalytic carbon is maintained at a relatively low tem"erature. ;ine catalytic "articles are formed and when they reach the second furnace, decom"osed carbons are absorbed and diffused to the catalytic metal "articles. 2ere, they are synthesi%ed as carbon nanotubes. he diameter of the carbon nanotubes by using va"our "hase growth are in the range of & / 9 nm for A+N s98 and between D8 and 188 nm for =+N s.

Bhemical =ethod 7rc method discharge @aser ablation vapour deposition (vapori-ation

+ho

Ebbesen and ?jayan,Endo, AhinshuAmalley, >ice, 199:19 NEC, Sa"an 199& 1: ,niversity, Nagano, Sa"an :' Connect two gra"hite3lace substrate in4last gra"hite with rods to a "oweroven, heat tointense laser "ulsesR su""ly, "lace them a588 oC, and slowlyuse the laser "ulses few millimeters a"art,add a carbon/rather than electricity to and throw the switch. bearing gas such asgenerate carbon gas ?t 188 am"s, carbonmethane. ?s gasfrom which the N s va"ori%es and formsdecom"oses it freesformR try various hot "lasma. u" carbon atoms,conditions until hit on which recombine inone that "roduces the form of N s "rodigious amounts of A+N s '8 to 98O &8 to 188 O ," to D8O

2ow

y"ical yield

A+N

Ahort tubes withKong tubes withKong bundles of tubes diameters of 8.5 / 1.9diameters ranging(:/&8 microns!, with nm from 8.5/9 nm individual diameter from 1/& nm. Ahort tubes withKong tubes withNot very much interest inner diameter of 1/'diameter rangingin this techni$ue, as it is nm and outerfrom 18/&98 nm too e1"ensive, but diameter of =+N synthesis is a""ro1imately 18 nm "ossible. Can easily "roduceEasiest to scale u"3rimarily A+N s, with A+N , =+N s.to industrialgood diameter control A+N s have few"roductionR longand few defects. he structural defectsRlength, sim"lereaction "roduct is $uite =+N s without"rocess, A+N "ure. catalyst, not toodiameter e1"ensive, o"en aircontrollable, $uite synthesis "ossible "ure ubes tend to beN s are usuallyCostly techni$ue, short with random=+N s and oftenbecause it re$uires si%es and directionsRriddled with defects e1"ensive lasers and often needs a lot of high "ower re$uirement, "urification but is im"roving

=/+N

3ro

Con

Table 2-2: A summary of the major production methods and their efficiency

Chara$teri%ation nanotubes:(

of

$arbon

he e1"erimental techni$ues used for growth and characteri%ation of carbon nanotubes are discussed. 3lasma enhanced chemical va"or de"osition (3EC*H! method was used for the de"osition of these films. Acanning electron microsco"y (AE=!, ransmission electron microsco"y ( E=!, Energy dis"ersive </ray s"ectrosco"y (EHA!, >aman s"ectrosco"y and </ray diffraction were used for the characteri%ation of carbon nanostructures and catalyst nano"articles.

8?1:? scanning electron microscope (8?1! is a ty"e of electron microsco"e that images a sam"le by scanning it with a high/energy beam of electrons in a raster scan "attern. he electrons interact with the atoms that ma#e u" the sam"le "roducing signals that contain information about the sam"leBs surface to"ogra"hy, com"osition, and other "ro"erties such as electrical conductivity. In a ty"ical AE=, an electron beam is thermionically emitted from an electron gun fitted with a tungsten filament cathode. ungsten is normally used in thermionic electron guns because it has the highest melting "oint and lowest va"our "ressure of all metals, thereby allowing it to be heated for electron emission, and because of its low cost. Cther ty"es of electron emitters include lanthanum he1aboride (Ka45! cathodes, which can be used in a standard tungsten filament AE= if the vacuum system is u"graded and field emission guns (;E6!, which may be of the cold/cathode ty"e using tungsten single crystal emitters or the thermally/assisted Achott#y ty"e, using emitters of %irconium o1ide.

he electron beam, which ty"ically has an energy ranging from 8.: #e* to 98 #e*, is focused by one or two condenser lenses to a s"ot about 8.9 nm to : nm in diameter. he beam "asses through "airs of scanning coils or "airs of deflector "lates in the electron column, ty"ically in the final lens, which deflect the beam in the " and y a1es so that it scans in a raster fashion over a rectangular area of the sam"le surface. +hen the "rimary electron beam interacts with the sam"le, the electrons lose energy by re"eated random scattering and absor"tion within a teardro"/ sha"ed volume of the s"ecimen #nown as the interaction volume, which e1tends from less than 188 nm to around : Lm into the surface. he si%e of the interaction volume de"ends on the electronBs landing energy, the atomic number of the s"ecimen and the s"ecimenBs density. he energy e1change between the electron beam and the sam"le results in the reflection of high/ energy electrons by elastic scattering, emission of secondary electrons by inelastic scattering and the emission of electromagnetic radiation, each of which can be detected by s"eciali%ed detectors. he beam current absorbed by the s"ecimen can also be detected and used to create images of the distribution of s"ecimen current. Electronic am"lifiers of various ty"es are used to am"lify the signals which are dis"layed as variations in brightness on a cathode ray tube. he raster scanning of the C> dis"lay is synchroni%ed with that of the beam on the s"ecimen in the microsco"e, and the resulting image is therefore a distribution ma" of the intensity of the signal being emitted from the scanned area of the s"ecimen. he image may be ca"tured by "hotogra"hy from a high resolution cathode ray tube, but in modern machines is digitally ca"tured and dis"layed on a com"uter monitor and saved to a com"uterBs hard dis#.

T?1:Transmission electron microscopy (T?1! is a microsco"y techni$ue whereby a beam of electrons is transmitted through an ultra thin s"ecimen, interacting with the s"ecimen as it "asses through. ?n image is formed from the interaction of the electrons transmitted through the s"ecimenR the image is magnified and focused onto an imaging device, such as a fluorescent screen, on a layer of "hotogra"hic film, or to be detected by a sensor such as a CCH camera.

E=s are ca"able of imaging at a significantly higher resolution than light microsco"es, owing to the small de 4roglie wavelength of electrons. his enables the instrumentBs user to e1amine fine detailMeven as small as a single column of atoms, which is tens of thousands times smaller than the smallest resolvable object in a light microsco"e. E= forms a major analysis method in a range of scientific fields, in both "hysical and biological sciences. E=s find a""lication in cancer research, virology, materials science as well as "ollution, nanotechnology, and semiconductor research.

EFA:E-ray scattering techni)ues are a family of non/destructive analytical techni$ues which reveal information about the crystallogra"hic structure, chemical com"osition, and "hysical "ro"erties of materials and thin films. hese techni$ues are based on observing the scattered intensity of an </ray beam hitting a sam"le as a function of incident and scattered angle, "olari%ation, and wavelength or energy.

In an </ray diffraction measurement, a crystal is mounted on a goniometer and gradually rotated while being bombarded with </rays, "roducing a diffraction "attern of regularly s"aced s"ots #nown as reflections. he two/ dimensional images ta#en at different rotations are converted into a three/ dimensional model of the density of electrons within the crystal using the mathematical method of ;ourier transforms, combined with chemical data #nown for the sam"le. 3oor resolution (fu%%iness! or even errors may result if the crystals are too small, or not uniform enough in their internal ma#eu". </ray crystallogra"hy is related to several other methods for determining atomic structures. Aimilar diffraction "atterns can be "roduced by scattering electrons or neutrons, which are li#ewise inter"reted as a ;ourier transform. If single crystals of sufficient si%e cannot be obtained, various other </ray methods can be a""lied to obtain less detailed informationR such methods include fiber diffraction, "owder diffraction and small/angle </ray scattering (A?<A!. If the material under investigation is only available in the form of nano/crystalline "owders or suffers from "oor crystallinity, the methods of electron crystallogra"hy can be a""lied for determining the atomic structure.

F717; 84?BTF98B94=:Faman spectroscopy (named after C. *. >aman! is s"ectrosco"ic techni$ue used to study vibrational, rotational, and other low/fre$uency modes in a system. It relies on inelastic scattering, or >aman scattering, of monochromatic light, usually from a laser in the visible, near infrared, or near ultraviolet range. he laser light interacts with molecular vibrations, "honons or other e1citations in the system, resulting in the energy

of the laser "hotons being shifted u" or down. he shift in energy gives information about the vibrational modes in the system. Infrared s"ectrosco"y yields similar, but com"lementary, information. y"ically, a sam"le is illuminated with a laser beam. Kight from the illuminated s"ot is collected with a lens and sent through a monochromatic. +avelengths close to the laser line, due to elastic >ayleigh scattering, are filtered out while the rest of the collected light is dis"ersed onto a detector. A"ontaneous >aman scattering is ty"ically very wea#, and as a result the main difficulty of >aman s"ectrosco"y is se"arating the wea# inelastically scattered light from the intense >ayleigh scattered laser light.

>aman s"ectra are ty"ically e1"ressed in wave numbers, which have units of inverse length. In order to convert between s"ectral wavelength and wave numbers of shift in the >aman s"ectrum, the following formula can be used0

+here Tw is the >aman shift e1"ressed in wave number, U8 is the e1citation wavelength, and U1 is the >aman s"ectrum wavelength. =ost commonly, the units chosen for e1"ressing wave number in >aman s"ectra is inverse centimeters (cmV1!. Aince wavelength is often e1"ressed in units of nanometers (nm!, the formula above can scale for this units conversion e1"licitly, giving

PROPERTIES:he most im"ortant "ro"erties of CN s are0/

a 8trength and elasticity0

CN s are the strongest and stiffest materials on earth, in terms of tensile strength and elastic modulus res"ectively. his strength results from the covalent s"- bonds formed between individual carbon atoms. he carbon atoms of a single sheet of gra"hite form a "lanar honeycomb lattice, in which each atom is connected via a strong chemical bond to three neighboring atoms. 4ecause of these strong bonds, the basal "lane elastic modulus of gra"hite is one of the largest of any #nown material. ;or this reason, CN s are e1"ected to be the ultimate high/strength fibers. Aingle walled nanotubes are stiffer than steel, and are very resistant to damage from "hysical forces. 3ressing on the ti" of a nanotube will cause it to bend, but without damage to the ti". +hen the force is removed, the nanotube returns to its original state. his "ro"erty ma#es CN s very useful as "robe ti"s for very high/resolution scanning "robe microsco"y. Wuantifying these effects has been rather difficult, and an e1act numerical value has not been agreed u"on. ,sing atomic force microsco"y, the unanchored ends of a freestanding nanotube can be "ushed out of their e$uilibrium "osition, and the force re$uired to "ush the nanotube can be measured. he current Xoungs modulus value of single walled nanotubes is about 1 era3ascal, but this value has been widely dis"uted, and a value as high as 1.N "a has been re"orted. Cther values significantly higher than that have also been re"orted. he differences "robably arise through different e1"erimental measurement techni$ues. Cthers have shown theoretically that the Xoungs modulus de"ends on the si%e and chirality of the single walled nanotubes, ranging from 1.&& "a to 1.&5 "a. hey have calculated a value of 1.89 "a for a generic nanotube. 2owever, when wor#ing with different multi walled nanotubes, others have noted that the modulus measurements of multi walled nanotubes using ?;= techni$ues do not strongly de"end on the diameter. Instead, they argue that the modulus of the multi walled nanotubes correlates to the amount

of disorder in the nanotube walls. Not sur"risingly, when multi walled nanotubes brea#, the outermost layers brea# first. CN s are not nearly as strong under com"ression. 4ecause of their hollow structure and high as"ect ratio, they tend to undergo buc#ling when "laced under com"ressive, tensional or bending stress.

b Thermal conductivity and e*pansion0

?ll nanotubes are e1"ected to be very good thermal conductors along the tube, e1hibiting a "ro"erty #nown as ballistic conduction, but good insulators laterally to the tube a1is. he tem"erature stability of carbon nanotubes is established to be u" to &N88 degrees Celsius in vacuum and about D:8 degrees Celsius in air. CN s have been shown to e1hibit su"erconductivity below &8P@ (a"ro1. &:'PC!. >esearch suggests that these e1otic strands, already heralded for their un"aralleled strength and uni$ue ability to ado"t the electrical "ro"erties of either semiconductors or "erfect metals, may someday also find a""lications as miniature heat conduits in a host of devices and materials. he strong in/"lane gra"hitic carbon / carbon bonds ma#e them e1ce"tionally strong and stiff against a1ial strains. he almost %ero in/"lane thermal e1"ansion but large inter/"lane e1"ansion of single walled nanotubes im"lies strong in/"lane cou"ling and high fle1ibility against non/a1ial strains. =any a""lications of CN s, such as in nanoscale molecular electronics, sensing and actuating devices, or as reinforcing additive fibers in functional com"osite materials, have been "ro"osed. >e"orts of several recent e1"eriments on the "re"aration and mechanical characteri%ation of CN / "olymer com"osites have also a""eared. hese measurements suggest modest enhancements in strength characteristics of CN /embedded matri1es as com"ared to bare "olymer matri1es. 3reliminary e1"eriments and simulation studies on the thermal "ro"erties of CN s show very high thermal conductivity. It is e1"ected, therefore, that nanotube reinforcements in "olymeric materials may also significantly im"rove the thermal and thermo mechanical "ro"erties of the com"osites.

c .igh aspect ratio0

CN s re"resent a very small, high as"ect ratio conductive additive for "lastics of all ty"es. heir high as"ect ratio means that a lower loading of CN s is needed com"ared to other conductive additives to achieve the same electrical conductivity. his low loading "reserves more of the "olymer resins toughness, es"ecially at low tem"eratures, as well as maintaining other #ey "erformance "ro"erties of the matri1 resin. CN s have "roven to be an e1cellent additive to im"art electrical conductivity in "lastics. heir high as"ect ratio, about 188801 im"arts electrical conductivity at lower loadings, com"ared

to conventional additive materials such as carbon blac#, cho""ed carbon fiber, or stainless steel fiber.

d ?lectrical Bonductivity0
He"ending on their chiral vector, carbon nanotubes with a small diameter are either semi/conducting or metallic. CN s can be highly conducting, and hence can be said to be metallic. heir conductivity has been shown to be a function of their chirality, the degree of twist as well as their diameter. CN s can be either metallic or semi/ conducting in their electrical behavior. Conductivity in =+N s is $uite com"le1. Aome ty"es of (armchair)/structured CN s a""ear to conduct better than other metallic CN s. ;urthermore, interwall reactions within multi walled nanotubes have been found to redistribute the current over individual tubes non/uniformly. 2owever, there is no change in current across different "arts of metallic single/walled nanotubes. he behavior of the ro"es of semi/ conducting single walled nanotubes is different, in that the trans"ort current changes abru"tly at various "ositions on the CN s. he conductivity and resistivity of ro"es of single walled nanotubes has been measured by "lacing electrodes at different "arts of the CN s. he resistivity of the single walled nanotubes ro"es was of the order of 18J9 ohm/cm at &DPC. his means that single walled nanotube ro"es are the most conductive carbon fibers #nown. he current density that was "ossible to achieve was 18/D ?Gcm&, however in theory the single walled nanotube ro"es should be able to sustain much higher stable current densities, as high as 18/1' ?Gcm&. It has been re"orted that individual single walled nanotubes may contain defects. ;ortuitously, these defects allow the single walled nanotubes to act as transistors. Ki#ewise, joining CN s together may form transistor/li#e devices. ? nanotube with a natural junction (where a straight metallic section is joined to a chiral semi conducting section! behaves as a rectifying diode J that is, a half/transistor in a single molecule. It has also recently been re"orted that single walled nanotubes can route electrical signals at s"eeds u" to 18 62% when used as interconnects on semi/conducting devices.

e ?lectronic properties:
he electronic "ro"erties of A+N s have been studied in a large number of theoretical wor#s. ?ll models show that the electronic "ro"erties vary in a "redictable way from metallic to semi conducting with diameter and chirality. his is due to the very "eculiar band structure of gra"hene and is absent in systems that can be described with usual free electron theory.

Electron motion in gra"hene is e$uivalent to that of a neutrino or a relativistic Hirac electron with vanishing rest mass. his causes the a""earance of a nontrivial 4errys "hase under &Y rotation in wave/vector s"ace, leading to the absence of bac#scattering and in the metallic carbon nanotube resulting in "erfect conduction even in the "resence of scatterers. he energy bands in carbon nanotubes are determined by "eriodic boundary conditions with a fictitious ?haronov/4ohm flu1 determined uni$uely by the circumferential chiral vector. ? nanotube becomes metallic when the flu1 vanishes and semiconducting when the flu1 is non%ero. he conductivity of gra"hene is essentially inde"endent of the ;ermi energy and the electron concentration as long as variations in effective scattering strength are neglected, and therefore gra"hene should be regarded as a metal rather than a %ero/ ga" semiconductor. *arious schemes are now being "ro"osed and tested for the "ur"ose of o"ening the band ga" in gra"hene. 4asically, all armchair tubes are metallic. Cne out of three %ig%ag and chiral tubes show a small very small band ga" due to the curvature of the gra"hene sheet, while all other tubes are semi/conducting with a band ga" that scales a""ro1imately with the inverse of the tube radius. 4andga"s of 8.9 J 1 e* can be e1"ected for A+N s (corres"onding to diameters between 8.5 and 1.5 nm!.

Cn the left0 band structure of the conduction band of gra"hene, which crosses the ;ermi level at the edges of the 4rillouin %one. Cn the right0 "redicted band/ga" as a function of A+N radius, re"roduced from @ane and =ele, 3>K DN, 19'& (199D!. hese theoretical "redictions made in 199& were actually confirmed in 199N by scanning tunneling s"ectrosco"y. Numerous conductivity e1"eriments on A+N s and =+N s allowed gaining additional informations. ?t low tem"eratures, A+N s behave as coherent $uantum wires where the conduction occurs through discrete electron states over large distances. rans"ort measurements revealed that metallic A+N s show e1tremely long coherence lengths. =+N s show also these effects in s"ite of their larger diameter and multi"le shells.

f 1echanical properties:
Carbon nanotube is the one of the strongest materials in nature. Carbon nanotubes (CN s! are basically long hollow cylinders of gra"hite sheets. ?lthough a gra"hite sheet has a &H symmetry, carbon nanotubes by geometry have different "ro"erties in a1ial and radial directions. It has been shown that CN s are very strong in the a1ial direction. XoungBs modulus on the order of &D8 / 9:8 63a and tensile strength of 11 / 5' 63a were obtained. Cn the other hand, there was evidence that in the radial direction they are rather soft. he first transmission electron microsco"e observation of radial elasticity suggested that even the van der +aals forces can deform two adjacent nanotubes. Kater, nanoindentations with atomic force microsco"e were "erformed by several grou"s to $uantitatively measure radial elasticity of multiwalled carbon nanotubes and ta""ingGcontact mode atomic force microsco"y was recently "erformed on single/walled carbon nanotubes. XoungBs modulus of on the order of several 63a showed that CN s are in fact very soft in the radial direction.

>adial direction elasticity of CN s is im"ortant es"ecially for carbon nanotube com"osites where the embedded tubes are subjected to large deformation in the transverse direction under the a""lied load on the com"osite structure. Cne of the main "roblems in characteri%ing the radial elasticity of CN s is the #nowledge about the internal radius of the CN R carbon nanotubes with identical outer diameter may have different internal diameter (or the number of walls!. >ecently a method using atomic force microsco"e was introduced to find the e1act number of layers and hence the internal diameter of the CN . In this way, mechanical characteri%ation is more accurate.

Bomparison of mechanical properties

1aterial =oung>s Tensile modulus (T4a strength (24a
I1 (from 1 to :! 1'J:'

?longation at brea/ (G
15

A+N ?rmchair A+N Zig%ag A+N Chiral A+N =+N

E

8.99

1&5.&

&'.1

8.99

99.:

1:.5J1D.:

8.9&

N?

N?

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APP&ICATIONS!"
Carbon nanotubes (4uc#ytubes! have e1traordinary electrical conductivity, heat conductivity and mechanical "ro"erties. hey are "robably the best electron field/emitter "ossible. hey are "olymers of "ure carbon and can be reacted and mani"ulated using the tremendously rich chemistry of carbon. his "rovides o""ortunity to modify the structure and to o"timi%e solubility and dis"ersion. *ery significantly, buc#ytubes are molecularly "erfect, which means that they are free of "ro"erty/degrading flaws in the nanotube structure. heir material "ro"erties can therefore a""roach closely the very high levels intrinsic to them. hese e1traordinary characteristics give buc#ytubes "otential in numerous a""lications.

a 8tructural

Blothes0 water"roof tear/resistant cloth fibers Bombat Hac/ets0 =I wearer. is wor#ing on combat jac#ets that use carbon nanotubes as ultra strong fibers and to monitor the condition of the

Boncrete0 In concrete, they increase the tensile strength, and halt crac# "ro"agation. 4olyethylene0 >esearchers have found that adding them to

"olyethylene increases the "olymerBs elastic modulus by '8O.

8ports e)uipment0 Atronger and lighter tennis rac#ets, bi#e "arts, golf balls, golf clubs, golf shaft and baseball bats.

8pace elevator0 his will be "ossible only if tensile strengths of more than about D8 63a can be achieved. =onoatomic o1ygen in the EarthBs u""er atmos"here would erode carbon nanotubes at some altitudes, so a s"ace elevator constructed of nanotubes would need to be "rotected (by some #ind of coating!. Carbon nanotubes in other a""lications would generally not need such surface "rotection.

6ltrahigh-speed flywheels0

he high strengthGweight ratio enables

very high s"eeds to be achieved. b! ?@?BTF9172;?T+B

0uc/ypaper0 It is a thin sheet made from nanotubes that are &:8 times stronger than steel and 18 times lighter that could be used as a heat sin# for chi"boards, a bac#light for KCH screens or as a faraday cage to "rotect electrical devicesGaero "lanes.

Bhemical nanowires0 Carbon nanotubes additionally can also be used to "roduce nanowires of other chemicals, such as gold or %inc o1ide. hese nanowires in turn can be used to cast nanotubes of other chemicals, such as gallium nitride. hese can have very different "ro"erties from CN s J for e1am"le, gallium nitride nanotubes are hydro"hilic, while CN s are hydro"hobic, giving them "ossible uses in organic chemistry that CN s could not be used for.

Bomputer circuits0 ? nanotube formed by joining nanotubes of two different diameters end to end can act as a diode, suggesting the "ossibility of constructing electronic com"uter circuits entirely out of nanotubes. 4ecause of their good thermal "ro"erties, CN s can also be used to dissi"ate heat from tiny com"uter chi"s.

Bonductive films0 CN s are also introduced in develo"ing trans"arent, electrically conductive films to re"lace indium tin o1ide(I C!.CN films are substantially more mechanically robust then I C films ,ma#ing them ideal for more reliability touch screens and fle1ible dis"lays. 3rintable water based in#s of carbon nanotubes are desired to enable the "roduction of these films to re"lace the I C. Nanotube films show "romise for use in dis"lays for cell "hones, com"uters, 3H?s, and ? =s.

?lectric motor brushes: Conductive carbon nanotubes have been used for several years in brushes for commercial electric motors.. he nanotubes im"rove electrical and thermal conductivity because they stretch through the "lastic matri1 of the brush. his "ermits the carbon filler to be reduced from '8O down to '.5O, so that more matri1es are "resent in the brush. Nanotube com"osite motor brushes are better/lubricated (from the matri1!, cooler/running (both from better lubrication and su"erior thermal conductivity!, less brittle (more matri1, and fiber reinforcement!, stronger and more accurately moldable (more matri1!. Aince brushes are a critical failure "oint in electric motors, and also dont need much material, they became economical before almost any other a""lication.

@ight bulb filament0 incandescent lam"s.

?lternative to tungsten filaments in

8olar cells0 Crganic "hotovoltaic devices (C3*s! are fabricated from thin films of organic semiconductors, such as "olymers and small/ molecule com"ounds, and are ty"ically on the order of 188 nm thic#. 4ecause "olymer based C3*s can be made using a coating "rocess such as s"in coating or in#jet "rinting, they are an attractive o"tion for ine1"ensively covering large areas as well as fle1ible "lastic surfaces. ? "romising low cost alternative to silicon solar cells, there is a large amount of research being dedicated throughout industry and academia towards develo"ing C3*s and increasing their "ower conversion efficiency. 6Es carbon nanotube diode has a "hotovoltaic effect. Nanotubes can re"lace I C (Indium tin o1ide! in some solar cells to act as a trans"arent conductive film in solar cells to allow light to "ass to the active layers and generate "hotocurrent.

CNTs in '(e"sensiti%e' so#ar $e##s!" Hue to the sim"le fabrication "rocess, low "roduction cost, and high efficiency, there is significant interest in dye/sensiti%ed solar cells (HAACs!. hus, im"roving HAAC efficiency has been the subject of a variety of research investigations because it has the "otential to be manufactured economically enough to com"ete with other solar cell technologies. itanium dio1ide nano"articles have been widely used as a wor#ing electrode for HAACs because they "rovide a high efficiency, more than any other metal o1ide semiconductor investigated. Xet the highest conversion efficiency under air mass (?=! 1.: (188 m+Gcm&! irradiation re"orted for this device to date is about 11O. Hes"ite this initial success, the effort to further enhance efficiency has not "roduced any major results. he trans"ort of electrons across the "article networ# has been a #ey "roblem in achieving higher "hoto conversion efficiency in nanostructured electrodes. 4ecause electrons encounter many grain boundaries during the transit and e1"erience a random "ath, the "robability of their recombination with o1idi%ed sensiti%er is increased. herefore, it is not ade$uate to enlarge the o1ide electrode surface area to increase efficiency because "hoto/generated charge recombination should be "revented. 3romoting electron transfer through film electrodes and bloc#ing interface states lying below the edge of the conduction band are some of the non/CN based strategies to enhance efficiency that have been em"loyed. +ith recent "rogress in CN develo"ment and fabrication, there is "romise to use various CN based nanocom"osites and nanostructures to direct the flow of "hoto generated electrons and assist in charge injection and e1traction. o assist the electron trans"ort to the collecting electrode surface in a HAAC, a "o"ular conce"t is to utili%e CN networ#s as su""ort to anchor light harvesting semiconductor "articles. 7Efficiencies reaching 9.9O have already been achieved and ho"efully 18/1:O efficiencies are feasible in the near/future u"on further o"timi%ation7 says @yma#is. 7Cnce this obstacle is tac#led, the lifetime issue, which is directly related to the cell tem"eratures, can be e1"lored. ? wor#ing environment combining the strengths of scientists and business leaders may soon result in ra"id commerciali%ation of this technology.7

8uperconductor0 Nanotubes have been shown to be su"erconducting at low tem"eratures.

6ltra capacitors0 Nanotubes, when bound to "lates of ca"acitors increase the surface area and thus increase energy storage ability.

Aisplays0 Cne use for nanotubes that has already been develo"ed is as e1tremely fine electron guns, which could be used as miniature cathode ray tubes in thin high/brightness low/energy low/weight dis"lays. his ty"e of dis"lay would consist of a grou" of many tiny C> s, each "roviding the electrons to hit the "hos"hor of one "i1el, instead of having one giant C> whose electrons are aimed using electric and magnetic fields. hese dis"lays are #nown as field emission dis"lays (;EHs!.

9thers0

?rtificial muscles, magnets, o"tical ignition etc.

c B.?1+B7@ 7ir pollution filter0 ;uture a""lications of nanotube membranes include filtering carbon dio1ide from "ower "lant emissions. 0iotech container0 Nanotubes can be o"ened and filled with materials such as biological molecules, raising the "ossibility of a""lications in biotechnology. .ydrogen storage0 >esearch is currently being underta#en into the "otential use of carbon nanotubes for hydrogen storage. hey have the "otential to store between 9.& and 5:O hydrogen by weight. his is an im"ortant area of research, since if they can be mass "roduced economically there is "otential to contain the same $uantity of energy as a :8K gasoline tan# in 1'.&K of nanotubes. Aee also, 2ydrogen Economy. %ater filter0 >ecently nanotube membranes have been develo"ed for use in filtration. his techni$ue can "ur"ortedly reduce desalination costs by D:O. he tubes are so thin that small "articles (li#e water molecules! can "ass through them, while larger "articles (such as the chloride ions in salt! are bloc#ed.

9scillator0

;astest #nown oscillators (F :8 62%!.

;anotube membrane0 Ki$uid flows u" to five orders of magnitude faster than "redicted by classical fluid dynamics. 8mooth surface0 Amoother than eflon and water"roof.

d 1?B.7;+B7@

9scillator0 fastest #nown oscillators (F :8 62%!. @i)uid flow array0 Ki$uid flows u" to five orders of magnitude faster than "redicted through array. 8lic/ surface0 slic#er than eflon and water"roof.

e B7F09; ;7;9T60? +;T?FB9;;?BT8 =etallic CN s have aroused a lot of research interest in their a""licability as *ery/large/scale integration (*KAI! interconnects of the future because of their desirable "ro"erties of high thermal stability, high thermal conductivity and large current carrying ca"acity. ?n isolated CN can carry current densities in e1cess of 1888 =?Gs$/cm without any signs of damage even at an elevated tem"erature of &:8 degrees C, thereby eliminating electromigration reliability concerns that "lague Cu interconnects. >ecent modeling wor# com"aring the "erformance, "ower dissi"ation and thermalGreliability as"ects of CN interconnect to scaled co""er interconnects have shown that CN bundle interconnects can "otentially offer more advantages over co""er. f TF7;8+8T9F8 Amaller silicon based integrated circuits result in both a higher s"eed and device density. ?s a result, downscaling of these devices has been very im"ortant since their first im"lementation. 2owever, at the moment it is generally acce"ted that silicon devices will reach fundamental scaling limits within a decade or so. his limit is caused by the minimum wavelength of light used in lithogra"hic techni$ues used for integrated circuit "roduction nowadays. ;or this reason a $uest for alternative, integrated circuits with smaller dimensions has started. ? major ste" in downscaling would be the a""lication of single molecules in electronic devices. Carbon nanotubes have already shown "romising results in single molecular transistors. ;or

successful im"lementation of molecular transistors in large and com"le1 logic systems, they must show signal am"lification. Aignal am"lification ma#es it "ossible to reference se"arate signals along a chain of logical o"erations. In addition, noise caused by thermal fluctuations and environmental disturbances is also reduced. hree terminal nanotransistors, in s"ecial, field/ effect/transistors show am"lifying behavior and have recently been investigated for this reason. g ?lectrical circuits Carbon nanotubes have many "ro"ertiesMfrom their uni$ue dimensions to an unusual current conduction mechanismMthat ma#e them ideal com"onents of electrical circuits. Currently, there is no reliable way to arrange carbon nanotubes into a circuit. he major hurdles that must be jum"ed for carbon nanotubes to find "rominent "laces in circuits relate to fabrication difficulties. he "roductions of electrical circuits with carbon nanotubes are very different from the traditional IC fabrication "rocess. he IC fabrication "rocess is somewhat li#e scul"ture / films are de"osited onto a wafer and "attern/etched away. 4ecause carbon nanotubes are fundamentally different from films, carbon nanotube circuits can so far not be mass "roduced. >esearchers sometimes resort to mani"ulating nanotubes one/by/one with the ti" of an atomic force microsco"e in a "ainsta#ing, time/consuming "rocess. 3erha"s the best ho"e is that carbon nanotubes can be grown through a chemical va"or de"osition "rocess from "atterned catalyst material on a wafer, which serve as growth sites and allow designers to "osition one end of the nanotube. Huring the de"osition "rocess, an electric field can be a""lied to direct the growth of the nanotubes, which tend to grow along the field lines from negative to "ositive "olarity. ?nother way for the self assembly of the carbon nanotube transistors consist in using chemical or biological techni$ues to "lace the nanotubes from solution to determinate "lace on a substrate. Even if nanotubes could be "recisely "ositioned, there remains the "roblem that, to this date, engineers have been unable to control the ty"es of nanotubesMmetallic, semiconducting, single/walled, multi/walledM"roduced.

? chemical engineering solution is needed if nanotubes are to become feasible for commercial circuits.

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CN s have also been im"lemented in nano electromechanical systems, including mechanical memory elements. CN s have also been "ro"osed as a "ossible gene delivery vehicle and for use in combination in radio fre$uency fields to destroy cancer cells. Nanomi1 Inc was the first to "ut on the mar#et an electronic device that integrated carbon nanotubes on a silicon "latform, in may &88:. It was a hydrogen sensor. Aince then nanomi1 has been "atenting many such sensor a""lications such as in the field of Carbon/di/o1ide, Nitrous C1ide, glucose, HN? detection etc. ?s a container for drug delivery0 4ecause of the versatile structure of the CN , it can be used for a variety of tas#s in and around body. Cften in the cancer related incidents, the CN is often used as a container for trans"orting drugs into the body. 2ere drugs can actually be "laced inside the nanotubes or can be attached to the side or trailed behind. 4oth of these methods are effective for the delivery and distribution of drug inside out of the body. CN s can be used as light emitting semiconductors.

CONC& SION
>ise in demand and "roduction, and ease of accessibility of carbon nanotubes would lead to the e1tensive use of carbon nanotubes in a wide variety of a""lications. he use of nanotechnology for human will become common need in &1st century. ?s world is suffering from serious "ollution "roblems, hydrogen will becoming need of &1st century [ carbon nanotubes "rovide better solution for hydrogen storage. Nanotubes mar#et, which was growing at a moderate rate till &885/&88D, is e1"ected to rise at a s#yroc#eting "ace in the coming years. 2ence we can conclude that most of the demands of human, in this and fore coming generation will be fulfilled by carbon nanotubes.