I. TNG QUAN V CARBON NANOTUBE 1.

1 Gii thiu S tin b vt bc trong nghin cu v pht trin vt liu, c bit l vt liu kch thc nano a cng ngh nano i u trong s pht trin khoa hc cng ngh. Trong s nhng vt liu lin quan n s khi u v tin trin ca cng ngh nano, fullerenes v carbon nanotube (CNTs) l hai vt liu quan trng v c ch nht [1]. Fullerenes l nhng cm/phn t carbon ln, trong hnh dng ca mt khi cu rng, elip hoc ng. ng nano l mt loi cu trc fullerene, trong cng bao gm c buckyball. Trong khi buckyball c dng hnh cu, mt ng nano li c dng hnh tr, vi t nht mt u c ph bi mt bn cu c cu trc buckyball [2].

Hnh 1.1. Cc dng th hnh ca Cacbon:

a) Kim cng ; b) than ch; c) Lonsdaleite kim cng hnh lc gic; d) C60 (Buckminsterfullerene or buckyball); e) C540; f) C70; g) Carbon v nh hnh; h) Carbon nanotube n vch. Cc ng nano carbon (CNTs), c coi nh mt dng th hnh mi ca carbon. Mt ng nano carbon n lp l mt tm than ch dy mt nguyn t cun trn li thnh mt hnh tr lin. Tn ca chng c t theo hnh dng, do ng knh ca ng nano vo c vi nanomet (xp x nh hn 50.000 ln mt si tc), trong khi di ca chng c th ln ti vi milimet. Vi t l chiu di/ng knh ln nh th nn c th xem CNTs l dng fullerenes mt chiu [3]. iu c bit CNTs l n c nhiu tnh nng khc thng, u vit hn hn cc loi vt liu khc nh bn hn thp nhiu ln, cng hn kim cng, dn in tt hn ng, dn nhit tt hn kim cng Vi nhng tnh cht c, nhit, in tuyt diu nh th, CNTs c tim nng ng dng to ln trong cc ngnh cng ngh nano, in t, quang hc, vt liu v y dc [4]. Hin nay, CNTs c ng dng rng ri nh cht ph gia tng cng tnh nng cho nhiu loi vt liu nh nha v si carbon Cc ng nano carbon c phn thnh 2 loi chnh l cc ng n vch (SWNTs) v a vch (MWNTs). 1.2 Lch s nghin cu Vo u thp nin 50 ca th k trc, hai nh khoa hc Nga, L. V. Radushkevich v V. M. Lukyanovich, tuyn b vic ch to ng than nano ln u tin trong bi bo co ng trn tp ch ha hc vt l ca Nga Soviet Journal of Physical Chemistry nm 1952. V vit bng ting Nga v nh hng chnh tr do chin tranh lnh ng thi, nn s giao lu thng tin khoa hc b gii hn khin bi bo chm vo qun lng [5]. Hn hai mi nm sau, Oberlin, Endo v Koyama ng hnh nh r rng ca si carbon rng vi ng knh c nanomet c tng hp bng cch s dng mt k thut pht trin pha hi (vapor-growth technique) trong Journal of Crystal Growth nm 1976 [5]. Cng trnh ca Endo nhm phn tch cu trc bn trong ca si carbon c ch to bng cch nhit phn benzene v ferrocene 1000 oC, v lm sng t c ch hnh thnh ca chng iu khin vic sn xut si carbon

quy m ln (loi si ny cn c gi l vapor grown carbon fibers; VGCFs). Nhiu iu kin tng hp c th nghim nhm to loi si mng (< 100 nm) c th chp c bng knh hin vi in t truyn qua phn gii cao (HRTEM). Vi nhng hnh nh t c, cho thy qu trnh nhit phn c th sn xut cc ng graphite kch thc nano, v cng l nhng hnh nh u tin v SWNTs v MWNTs (hnh 1.2). Mt ln na, bi bo khng to c s nh hng ln vo cng ng nghin cu khoa hc v lc h ang tp trung nghin cu vic ch to v sn xut i tr si carbon kch thc micron t s nhit phn ca polyacrylonitrile m hin gi l mt sn phm gia cng ph bin trn th trng cho cc loi composite [6]. Hnh 1.2 a) Hnh nh HRTEM ca hai SWNTs ct nhau vi lp ph carbon v nh hnh b) Hnh nh phng to ca mt ng graphene ring l v c cho l hnh nh u tin v SWNTs. ng knh ng khong 4 nm. c) Hnh nh HRTEM ca mt MWNTs bn trn cng vi mt SWNTs c ch th bng mi tn.

Sau , John Abrahamson trnh by bng chng ca ng nano carbon ti Biennial Conference of Carbon ln th 14 trng i hc Penn State nm 1979. Bo co m t cc ng nano carbon l nhng si carbon c sn xut trn cc cc dng bng carbon trong qu trnh phng in h quang [5]. Trong nm 1981, mt nhm cc nh khoa hc Nga ng kt qu nghin cu c tnh cu trc v ha hc ca cc ht nano carbon bng phng php oxy ha kh xc tc nhit (thermocatalytical disproportionation) vi carbon monoxide. Vi cc kt qu TEM v XRD, cc tc gi a ra gi thit nhng tinh th ng carbon a lp c to thnh bng vic cun cc lp graphene thnh hnh tr [5]. Ngoi ra, mt ng k pht minh ca H. G. Tennent thuc cng ty Hyperion Catalyst Intenational (M) nm 1987 tuyn b cch sn xut cc si carbon nh ri hnh tr "cylindrical discrete carbon fibrils" vi ng knh khong 3,5 70 nanomet v chiu di gp 100 ln ng knh. Cc ng than cng c cho l to nn bi cc tm graphene cun li hnh thnh mt vng bn ngoi gm nhiu lp lin tc c b dy c nguyn t carbon v mt li rng bn trong [5]. Nhng phn ln cc ti liu thng dng v hc thut u cng nhn s khm ph ra cc ng than graphite rng, kch thc nano l ca Sumio Iijima thuc cng ty in lc Nippon nm 1991 [5]. Iijima dng HRTEM v nhiu x electron a ra s tn ti ca vi ng carbon xon (nay gi l ng nano) bao gm cc ng graphene lng nhau.

Vt liu ny c to ra t qu trnh phng in h quang vi mc ch to cu trc fullerenes t carbon nguyn t. Nhng ng lng nhau ng trc ny c khong cch gia cc lp khong 3,4 ln hn khong cch gia cc lp graphite

khong 3,35 . Iijima lin h s khc nhau ny vi s kt hp ca vic un cong cc tm graphene v lc van der Waals yu hn gia cc ng lin k [6]. T , Ebbesen & Ajayan a ra phng php ch to CNTs quy m ln s dng k thut phng in h quang. Cc ng nano thu c t kt ta bn trong to ra bi in cc graphite phng h quang trong mi trng kh He iu kin ti u ca p sut v dng in DC [6]. Ngy nay, CNTs c th c sn xut bng cch s dng mt lot cc qu trnh nh phng in h quang, nhit phn hydrocarbon trn cc ht kim loi, ha hi cc i tng graphite bng laser, ha hi carbon bng bc x mt tri, v in phn ca in cc carbon trong cc mui ion nng chy [6]. 1.3 Phn loi v cu trc ca cc dng carbon nanotube Lin kt trong CNTs l sp2, vi mi nguyn t carbon lin kt vi 3 nguyn t carbon ln cn nh trong graphite. V th, ng nano carbon c xem nh nhng tm graphene cun li to thnh, mt dng fullerenes hnh tr. Cu trc lin kt ny mnh hn lin kt sp3 trong kim cng to cho CNTs cng c nht [5]. Cc ng nano carbon c nhiu hnh dng khc nhau nhng ch yu c phn lm hai loi chnh l ng n vch v ng a vch. 1.3.1. Nanotube n vch (Single walled) Mt ng carbon nano n vch c to thnh bi cc nguyn t carbon lin kt vi nhau sp xp trong mt mng li lc gic. Cc ng thng b gii hn t nht mt u bi mt na buckyball. Hu ht SWNTs v C60 fullerenes c ng knh khong 1 nm [1]. Mt s SWNTs c ng knh t 0,4 5 nm [7]. SWNTs khng tn ti ring l trong t nhin, lc van der Waals gia cc phn t khin chng kt t thnh chm hoc dy.

Hnh 1.3 (A) ng nano carbon n lp SWNTs; (B) Hnh nh SEM ca SWNTs (C) Hnh nh TEM ca SWNTs kt chm vi cc ht nano kim loi (D) Hnh nh TEM phn gii cao ca mt b SWNTs gm trn 25 ng v mt t carbon v nh hnh trn thnh Cch m tm graphene cun li theo cc hng khc nhau c biu din bi mt cp ch s nguyn (n,m) gi l vector chiral. Cc s nguyn n v m l s ca cc vector n v dc theo hai hng trong li tinh th hnh t ong ca graphene [6]. SWNTs vi cc vector i quang khc nhau c tnh cht c, in v quang hc khng ging nhau [3].

Cu trc ca SWNT c kho st da trn tm graphene dng 2D

a1 v a2 l cc vector n v ca graphene trong khng gian thc. Gi tr n,m c th tnh c u cui ca ng nano carbon.

Ch n a1 m a2
Nu m = 0, ng nano c gi l zigzag. Nu n = m, ng nano c gi l gh bnh armchair. Vi cc gi tr khc, chng c gi l dng i quang chiral. dng khng i quang (non-chiral) nh armchair v zig-zag, cc li t ong trn v di ca ng lun song song vi trc ng. Cn dng chiral th th nghing mt gc bng gc chiral [6].

Hnh 1.4: Cu trc armchair (m,m); zizag (n,0) v chiral (n,m) ca ng nano n vch

Cc ch s (m,n) cng c th c dng tnh ng knh ca ng nano carbon nh sau: vi a = 1,42 x l hng s li lc gic trong graphite. (1,42 l khong cch C-C cho lai ha sp2 carbon). Ngoi ch s (m,n) xc nh cu trc ng nano cn dng gc nghing . Vi = 0, (m,n) = (p,0), p l mt s nguyn, ng dng zigzag = 30o, (m,n) = (2p, - p) hoc (p,p), ng dng armchair

Gc chiral (gc gia Ch v hng zigzag) c xc nh nh sau [ ]

SWNTs l mt loi quan trng ca vt liu CNTs bi hu ht tnh cht ca n thay i mt cch ng k vi tr s (m,n), v s thay i ny khng bin i u theo (m,n). c bit l tnh cht in, SWNTs c nng lng vng cm band gap thay i t 0 2 eV v kh nng dn in c th l kim loi hoc bn dn. V th SWNTs ang c nghin cu c th ng dng trong vi in t. Hn na, vi kch thc ng knh ng c mt nanomet, SWNTs thch hp lm vi mch siu nh trong cng ngh vi mch in t. ng nano n lp c chi ph sn xut cao. Nm 2000, mi gam SWNTs c gi khong $1500. n nm 2007, mt vi nh cung cp phn phi SWNTs vo khong $50-100/g. Hin nay, gi 1 gram SWNTs hm lng 40 60% khi lng khong $50, cp nht thng 3 nm 2010 [8]. Vic pht trin cc phng php tng hp hiu qu hn l rt cn thit cho tng lai ca cng ngh nano. Nu khng th pht trin cc phng php tng hp r hn, n s tr thnh ro cn v mt ti chnh trn con ng a ng nano n lp ra ng dng trong thc t. 1.3.2. Nanotube a lp (Multi- walled) ng carbon nano a lp (MWNTs) gm nhiu lp than ch (graphite). C hai m hnh c s dng m t MWNTs. Trong m hnh th nht c tn gi:Russian doll, MWNTs gm nhiu ng SWNTs n lng vo nhau. Trong m hnh th hai: Parchment, MWNTs c m t nh mt tm n ca graphite c cun xung quanh chnh n, ging nh mt cun giy da hoc t bo cun trn li. Khong cch gia cc lp trong MWNTs tng ng khong cch cc lp graphite trong cu trc than ch, xp x 3.4 . Do , MWNTs c ng knh ln hn SWNTs (khong 1,5 100 nm hoc hn) [7], v c tr ha hc cao hn. C cu Russian doll c quan st thy ph bin hn. Tng lp v ca n c m t nh nhng SWNTs, c th mang tnh kim loi hoc bn dn. Bi xc sut thng k v s hn ch v ng knh tng i ca cc ng ring l, mt

trong nhng lp v, v v vy c MWNTs thng l mt kim loi c nng lng vng cm bng 0 (zero-gap) [8]. Ging nh SWNTs, MWNTs cng b lc van der Waals kt t nhng nh hng t hn. V th, cng vi cu trc khng ng nht ca mnh m MWNTs thng tn ti dng n ng v to rt t chm kt t [1].

Hnh 1.5: (F) Hnh nh SEM ca MWNTs kt t; (G) Hnh nh TEM ca MWNTs; (H) Hnh nh HRTEM ca MWNTs vi khong 20 lp trn mi thnh

Tuy nhin, hnh dng sn phm MWNTs v SWNTs ging nhau [1].

Hnh 1.6: (C) MWNTs dng bt c ch to phng php phng in h quang; (D) SWNTs dng bt c ch to bi phng php Rice HiPco.

MWNTs hai lp c gi l DWNTs, n l mt loi c bit ca carbon nanotube hai lp bi hnh thi v tnh cht ca n tng t nh SWNT nhng bn ha hc c ci thin ng k. iu ny c bit quan trng khi cn bin tnh (ghp cc chc nng ha hc ln b mt nanotube) thm cc thuc tnh mi cho cc CNTs. Trong trng hp ca SWNT, bin tnh cng ha tr s ph v mt s lin kt i C=C, li "l hng" trong c cu nanotube v do thay i cc thuc tnh c, in. Trong trng hp ca DWNT, ch c lp bn ngoi b sa i. Vic tng hp DWNTs trn quy m gram ln u tin c xut nm 2003 dng k thut CCVD, s dng qu trnh kh chn lc dung dch oxit trong metan v hydro [8].

Vi kh nng chuyn ng lng nhau co gin c ca cc lp v bn trong v c tnh c nht ca mnh, m ra kh nng dng MWNTs nh nhng cnh tay di ng trong cc thit b vi c tng lai [8]. Tuy nhin, MWNTs li t c ch hn SWNTs v s phc tp ca n, mi lp v c th mang cc tnh cht khc nhau v c s tng tc gia cc lp v [7]. *So snh SWNTs v MWNTs
nh chp ca carbon Nanotube nh chp S ca CN s kt t

1.3.3. Mt s dng nanotube khc Nanotorus

Mt nanotorus,v l thuyt c m t nh l mt carbon nanotube un cong thnh mt hnh xuyn. Nanotori c d on l c nhiu tnh cht c o, chng hn nh momen t ln hn 1000 ln so vi d kin trc cho m s bn knh c th. Nhng tnh cht nh momen t, bn nhit, thay i nhiu ty huc vo bn knh ca hnh xuyn v bn knh ca ng [8]. Nanobud Carbon nanobuds l mt vt liu mi c pht hin, to nn bi s kt hp hai dng th hnh ca cacbon l carbon nanotubes v fullerenes. Trong vt liu mi ny, fullerene ging nh "chi" l lin kt cng ha tr vi vch ngoi ca carbon nanotube c bn. Vt liu lai (hybrid) ny c cc tnh cht hu ch cho c hai fullerenes v carbon nanotubes. c bit, chng c kh nng pht x trng in t cc tt. Trong cc vt liu composite, s c mt ca cc phn t fullerene c chc nng nh cc mu neo phn t gi cc ng nano khng b trt, do ci thin c tnh ca vt liu [8]. Nanopeapod Carbon peapod l mt vt liu lai mi l, n cha cc phn t fullerene bn trong CNTs. N c th c cc tnh cht t l th vi vic un nng hoc chiu x. N cng c th c ng dng nh mt mch dao ng trong lc nghin cu l thuyt v d on [8].

 Carbon nanotubes xp chng ln nhau (Cup-stacked carbon nanotubes CSCNTs) oi ng carbon ny khc bit vi nhng cu trc carbon gi mt chiu (quansi1D) khc, nhng loi thng th hin tnh dn in ging kim loi. Cn CSCNTs biu hin tnh bn dn do vi kt cu xp chng ca cc lp graphene [8].

Carbon nanotubes Extreme Cycloparaphenylene

Cc hnh nh ca ng nano carbon di nht (18,5 cm) c bo co trong nm 2009. Cc ng ny c pht trin trn nn Si s dng k thut lng ng ha hc pha hi (CVD) c ci tin. Cc ng nano carbon ngn nht l hp cht hu c cycloparaphenylene c tng hp vo u nm 2009. Cc ng nano carbon mng nht l armchair (2,2) CNT vi ng knh 3 . ng nano ny c pht trin bn trong mt ng nano carbon a lp. Vic xc nh cc dng ca ng nano carbon c thc hin bng s kt hp cc phng

php HRTEM, ph Raman v tnh ton m hnh c hc lng t (thuyt mt chc nng - DFT). ng nano carbon n lp mng nht dng t do c ng knh khong 4,3. Cc nh nghin cu on rng n c th l (5,1) hoc (4,2) SWNTs, nhng chnh xc loi no vn cn nghi vn. Cn (3,3), (4,3) v (5,1) CNTs (u c ng knh khong 4 ) c xc nh r rng bng HRTEM c hiu chnh chnh xc hn. Tuy nhin, chng c tm thy bn trong cc ng nano carbon hai lp [8]. 1.4. Tnh cht ca carbon nanotube 1.4.1. c tnh c hc CNTs l vt liu bn nht v cng nht tng c khm ph trong cc th nghim v bn ko v moun n hi. Kh nng ny ca CNTs l do lin kt cng ha tr sp2 gia cc carbon nguyn t. Nm 2000, mt ng nano carbon a lp c th nghim c mt sc bn n 63 gigapascals (GPa). minh ha, sc bn ca CNTs c v tng ng mt si cp tit din 1 mm2 c th chu c sc cng 6422 kg. Nhng nghin cu tip theo tit l cc lp v CNT c sc bn ln n 100GPa, ph hp vi cc tnh ton l thuyt. V ng nano carbon c khi lng ring th rn thp khong 1,3 1,4 g/cm3 nn sc bn ca n ln ti 48000 kN.m/kg, l vt liu c bn cao nht tng bit. Nu so vi thp thng bn ch khong 154 kN.m/kg. Nu b s ko cng qu mc, cc ng s tri qua bin dng do , c ngha l cc bin dng vnh vin. Bin dng ny bt u vo khong 5%, v c th lm tng sc cng ti a cc ng phi chu trc khi b b gy bng cch gii phng nng lng bin dng. Bng 1 : C tnh v mt cu cc loi si Vt liu cng (GPa)* 203 bn (GPa)** 0.6 cng (%)*** Mt (kg/m3) 7.800

Thp

Nhm Si carbon #(HS) Si carbon #(HM) Si carbon #(UHS) Si aramid (Kevlar) Carbon nanotube Poly(methylmethacrylate)

75 240 310 825 180 ~ 1000 2,5

0.075 6.4 3.5 3.5 80 - 150 0,06

1.0 1.8 3.0 5 0.1 - 1

2.600 1.800 1.900 1.900 1.440 1.400 1.200

Gpa : giga pascal , 1 GPa = 109 Pa. Pa (= N/m2) l lc trn mt n v din tch. * cng (stiffness) cn gi l m-un Young (Young's modulus). ** bn im t (stress at break). *** cng im t (strain at break). Bng 1 cho thy d cc tr s khc nhau nhng c tnh ca ng than nano ni bt so vi thp v cc loi si gia cng (reinforcing fibres) hin c trn th trng. Nu ta ly tr s 1.000 GPa cho cng v 100 GPa cho bn, ta thy ng than nano cng hn thp 5 ln, bn hn thp 160 ln nhng li nh hn thp gn 6 ln. C th ni ng than nano l c c tnh cao nht so vi cc vt liu ngi ta bit t trc n nay. C tnh ca ng than nano trong Bng 1 l ca mt ng ring l. Trn thc t, cc ng nano carbon n vch khng tn ti tng ng mt m nhiu ng xon vo nhau thnh nhng cm hay b. Cn cc ng nano carbon a vch th b tng tc trt yu gia v v ng lin k lm gim ng k sc bn. Do , bn ca cc ng nano carbon a vch v b ng nano carbon n vch ch cn mt vi GPa. Mt vi k thut gn y to cu ni gia cc lp v v ng lm tng bn

vt liu ln ng k, khong 60 GPa i vi MWNTs v 17 GPa i vi cc b DWNTs. CNTs khng tht s bn nn. Bi c cu trc rng v h s co cao, nn chng c xu hng b bin dng cong khi chu ng sut nn, xon hay un. Cc n ng nano carbon n lp tiu chun c th chu p sut ln ti 24 GPa m khng b bin dng. Sau , chng cn tri qua s bin i thnh cc ng nano thi k siu cng. p sut ti a o c cho SWNTs khong 55 GPa. Moun n hi ca cc ng nano giai on siu cng vo khong 462 546 GPa, cao hn c kim cng 420 GPa. 1.4.2. Tnh cht in ng than nano c ng knh t vi nanomet n vi chc nanomet nhng c th di n micromet, thm ch milimet. V c kh nng dn in, cc ng nano carbon c th xem nh mt dy dn in c ng knh cc nh v l dy dn in l tng mt th nguyn, 1D (one dimension). Nanotube n lp l cht dn in hay cht bn dn ph thuc vo ng knh ng v gc chiral. Do tnh i xng v c cu trc in t duy nht ca graphene, cu trc ca nanotube l mt nh hng mnh m n tnh cht in ca n; tc ph thuc vo cp gi tr (m,n) - Nu m = n : CNTs c kh nng dn in nh kim loi (metallic) - Nu m - n = 3i : CNTs c kh nng nh cht bn kim loi (semimetallic) vi khong bandgap nh. i l mt s nguyn. - Nu m - n 3i: CNTs l cht bn dn (semiconducting)

V d: Vng cu trc my tnh s dng tnh rng buc cht ch tnh xp x khong (6,0) CNT (zigzag, kim loi), (10,2) CNT (bn dn) v (10,10) CNT (armchair, kim loi). Do tt c cc gh bnh (armchair) (n = m) nanotube l kim loi v nanotube (6,4), (9,1) l bn dn. Tuy nhin, nguyn tc ny c ngoi l, bi v hiu ng cong trong carbon nanotube c ng knh nh c th nh hng mnh m tnh cht in. Nh vy, (5,0) SWCNT li l kim loi bn dn trong thc t theo cc tnh ton. V ngc li, SWCNTs zigzag v dng khng i xng vi ng knh nh c th l kim loi c nng lng vng cm hu hn. Trong l thuyt, nanotubes kim loi c th mang mt mt in ca 4 10 9 A/cm2 l hn 1000 ln so vi cc kim loi nh ng. Carbon nanotube a lp vi lin kt cc lp v bn trong th hin tnh siu dn vi mt nhit qu tng i cao Tc = 12K. Ngc li, gi tr Tc li thp hn cho nhng b dy SWNTs hoc cho MWNTs cc lp v bnh thng, khng c ni lin kt.

Cch tnh kh nng dn in ca CNTs

Egap

2 y0 .aC C d

y0 = 2.7 ev : nng lng ca lin kt C-C aC-C :khong cch gn nht ca hai nguyn t cacbon trong ng nano [=0.142nm] d: ng knh ca ng carbon nanotube

Hnh dng ng li a n mt tnh cht c bit rt quan trng l s truyn in n o (ballistic conduction). "n o" y khng lin quan g n v kh m ch dng din t qu trnh truyn in trong in t (electron) di ng thng theo mt phng hng nht nh nh tn la, khng b vng mc v khng c s va chm n cc nguyn t ca vt liu. S truyn in thng thng trong kim loi thng gy ra nhit v khi di ng in t thng xuyn va chm vo nguyn t v nguyn nhn ca in tr v nhit. Ta c th mng tng s di chuyn "phi n o" ca cc in t trong kim loi l mt con ng ngon ngoo, b vo ngi ny chm vo ngi kia ca mt ngi chy b gia chn ng ngi. Truyn in n o khc s truyn in siu dn l truyn n o khng c hiu ng t tnh Meissner v khi tt ngun in dng in trit tiu, nhng trong cht siu dn dng in vn tip tc hin hu. Bng nhng thit k th nghim tinh vi v sng to, nhm de Heer (Georgia Institute of Technology, M) xc nh s truyn in n o trong SWNT v MWNT. im ni bt rt quan trng ca ng than nano l s truyn in n o c th xy ra nhit bnh thng, trong khi nhiu vt liu khc hin tng ny ch xy ra nhit m vi trm C. Mt im ni bt khc l ng than nano c th ti in mt rt cao 109 - 1010 Ampere/cm2, hay l 1000 ln cao hn ng.

iu ny cho thy mt tim nng ng dng rt a dng trong lnh vc in t, quang in t khi linh kin v mch in cng lc cng thu nh n mc nanomt. 1.4.3. Tnh cht nhit Nh cc cu trc nano khc, cc ng nano carbon c quan tm ln khng ch tnh cht c hc, tnh cht in, m cn cho cc thuc tnh nhit ca n. Do kch thc nh ca CNTs, tnh cht nhit c lin quan n cc hiu ng lng t v s cu trc ng 1D. Do kim cng v than ch graphite l nhng cht c kh nng dn nhit cao, nn c nhiu nghin cu v tnh cht nhit ca ng carbon nano. Tt c cc nanotube c cho l dn nhit dc theo ng rt tt, mt tnh cht c bit l dn n o nhng cch in tt theo chiu ngang vi trc ng. o lng cho thy mt SWNT c dn nhit nhit phng dc theo trc ca n l khong 3500 W.m-1 K -1; so snh vi ng, kim loi ni ting dn nhit tt ch c 385 W.m-1K-1. nhit phng, mt SWNT c dn nhit ngang trc ca n ch khong 1,52 W.m-1K-1, tng ng dn nhit ca t. bn nhit ca carbon nanotubes c c tnh ln n 2800C trong chn khng v 750C trong khng kh. 1.4.4. Tnh cht quang hc

Trong khoa hc vt cht, cc tnh cht quang hc ca carbon nanotube ch c bit hp thu, photoluminescence v quang ph Raman ca carbon nanotube.

Phng php quang ph cung cp kh nng m t tnh nhanh chng v ph hy khng s tng i ln ca cc cc carbon nanotube. S hp th quang hc, photoluminescence v quang ph Raman cho php c tnh nhanh chng v ng tin cy ca nanotube gii hn trong non-tubelur carbon, kt cu (chirality) ca cc sn phm nanotube v khim khuyt v cu trc. Nhng tnh nng xc nh gn vi cc tnh cht khc nh quang hc, c hc v tnh cht in. Cng ging nh my b m truyn v nhn sng v tuyn, cc ng nano carbon c th truyn v nhn nh sng cp nano, cc nh nghin cu Cornell pht hin ra. Cc ng nano cacbon, tm cun hnh tr ca cc nguyn t carbon, c th l dy tn x quang hc - nh, vi kh nng kim sot, hp th v pht ra mu sc ca nh sng cp nano, theo nghin cu do Jiwoong Park. Cc nh nghin cu s dng s tn x Rayleigh ca nh sng - hin tng tng t nh to ra bu tri xanh - t cc ng nano carbon c trng trong phng th nghim. H thy rng trong khi vic tuyn truyn ca tn x nh sng l ch yu l c in v v m, mu sc v cng ca bc x phn tn c xc nh bi cc thuc tnh lng t thc cht. H thy rng truyn dn nh sng ca ng nano c x nh mt phin bn thu nh ca tn s v tuyn antene tm thy trong my b m, ngoi tr vic chng tng tc vi nh sng thay v sng radio. Cc nguyn tc chi phi s tng tc gia nh sng v ng nano carbon cng ging nh gia cc ng-ten radio v cc tn hiu radio. Trong khi , tnh cht in v in ha (siu tch in) ca cc carbon nanotube cng c thit lp v c nhng ng dng ngay lp tc, vic s dng thc t ca tnh cht quang hc l cha r rng. Cc thuc tnh tunability l tim nng hu ch trong quang hc v lng t nh sng. c bit, it pht sng (LED v hnh nh pht hin da trn mt nanotube duy nht) c sn xut trong phng th nghim. Tnh nng c o ca n l khng hiu qu, l tng i thp, nhng chn lc hp bc sng pht x v pht hin ca nh sng v kh nng tinh chnh thng qua cu trc nanotube. Ngoi ra, vi nhit k v b nh quang in cc thit b c thc hin trn ensemble ca cc carbon nanotube n lp. 1.4.5.S truyn ti mt hng ( one-dimensional transport) v hu t t t

 Bi v cc kch thc l nano, in t ch tuyn truyn dc theo trc ca ng v vn chuyn in t lin quan n nhiu hiu ng lng t. Bi v iu ny, cc ng nano carbon thng c gi l one-dimensional hay 1-D Nh vi bt k vt cht no, s tn ti ca mt khim khuyt tinh th iu nh hng n cc tnh cht ca vt cht. huyt tt c th xy ra dng nguyn t ch trng. Mc ca khuyt tt cao c th gim sc bn ln n 85%. Mt dng khuyt tt ca carbon nanotube l khim khuyt Stone Wales, to ra mt ng gic v cp hnh by cnh bi s sp xp li cc lin kt. Do cu trc rt nh ca CNTs, cng chu sc cng - ko ca ng ph thuc vo phn khc yu nht ca n trong mt cch tng t mt chui, ni sc mnh ca lin kt yu nht s tr thnh sc mnh ti a ca chui.

Khuyt tt tinh th cng nh hng n tnh cht in ca ng. Mt kt qu chung l h thp tnh dn thng qua cc khu vc b li ca ng. Mt khuyt tt trong kiu gh bnh ng (c th dn in) c th gy ra cc khu vc xung quanh tr thnh bn dn, v mt nguyn t ch trng duy nht gy ra cc tnh cht t . Khim khuyt tinh th nh hng mnh m n c tnh nhit ng. Khuyt tt nh vy dn n tn x phonon, m cng ln lt tng t l phc hi ca cc phonon. iu ny lm gim tnh dn nhit ca cc cu trc nanotube. Cc li thay th nh nit hoc Bo ch yu s dn n s tn x phonon vi tn s quang hc

cao. Tuy nhin, quy m ln hn cc khuyt tt l Wales Stone defect lm tn x m t trn mt lot cc tn s, dn n cng gim tnh dn nhit nhiu hn. 1.4.6. c tnh Xc nh c tnh ca cc carbon nanotube l mt trong nhng cu hi bc xc nht trong cng ngh nano. Tht khng may nh nghin cu ch mi bt u v d liu vn cn ri rc v b ch trch. Kt qu s b nu bt nhng kh khn trong vic nh gi c tnh ca vt liu ny khng ng nht. Tham s nh c cu, kch thc phn phi, din tch b mt, ha hc b mt, tnh b mt,cng nh tinh khit ca mu, c tc ng ng k n phn ng ca cc carbon nanotube. Tuy nhin, d liu c cho thy rng, theo mt s iu kin, naotube c th vt qua ro cn mng, m cho thy rng nu nguyn liu t n mc no c th gy tc hi nh phn ng vim v x. Mt nghin cu dn u bi Alexandra Porter t i hc Cambridge cho thy CNTs c th nhp vo cc t bo con ngi v tch ly trong cc t bo cht, gy ra cc t bo cht. Kt qu ca nghin cu ng vt gm nhm chung cho thy rng bt k qu trnh m CNTs c tng hp v cc loi, cc gi tr kim loi, CNTs c kh nng gy ra s vim, cc khi u, x ha v sinh ha, thay i c tnh trong phi. Cc nghin cu c tnh so snh, nghin cu trn nhng con chut trng lng bng nhau cho thy SWCNTs c hi hn c thch anh, c coi l nguy him kh nghim trng i vi sc khe khi ht vo, gy ra cc bnh mn tnh. Cc hnh dng ging nh si kim ca CNTs, tng t nh si aming, lm tng lo ngi khi ph bin rng ri s dng carbon nanotube c th dn n u trung biu m, ung th mng phi thng do tip xc vi aming. t qu ngy hm nay r rng chng minh rng, trong iu kin nht nh, c bit l nhng lin quan ti phi nhim mn tnh, cc ng nano cacbon c th gy nguy him nghim trng cho sc khe con ngi.

II.

Cc phng php ch to Nano carbontube (CNTs) :

1. C ch pht trin ng nano Carbon : Hin nay c ch to thnh ca ng nano Carbon vn cha c hiu bit mt cch chnh xc.C nhiu gi thuyt c a ra gii thch cho c ch ny v gy nhiu tranh ci trong cng ng cc nh nghin cu.Nhng nhn chung c ch to thnh bao gm cc bc sau [1,2]: Bc 1 : Tin cht cho s to thnh ng nano carbon v fullerene l C2 s c to thnh trn cc tm xc tc kim loi c mang trn . Bc 2 : Qu trnh Graphit ha to thnh lp tng carbon xy ra vi tc chm.Mt s gi thuyt gi nh rng cc tm xc tc kim loi c gn trn cht nn c dng hnh cu hoc qu l v qu trnh lng ng ch xy ra trn mt na din tch b mt.Sau cc nguyn t carbon s khuch tn theo gradient nng v kt ta trn mt i din, xung quanh v c di ng knh phn i.Tuy nhin s kt ta ny li khng din ra nh ca bn cu ht xc tc v do to thnh cc ng rng tm c dng hnh si. Ty thuc vo tnh cht lin kt gia cc ht xc tc v hay cht mang m quyt nh c ch pht trin ca ng nano carbon: mc t nh ca ht ln( extrusion hoc base growth) hay mc t ln (tip growth) to thnh CNTs [1].

a) b) Hnh 2: nh SEM ca CNTs vi ht xc tc y ng(a) v u ng(b).

Trong khi ,vic c s dng hay khng cng vi kch thc ca ht xc tc kim loi v cc iu kin lin quan khc s quyt nh ng nano cacbon l n vch (SWCNTS) hay a vch (MWCNTS), cng nh l kch thc ca ng nano carbon c to thnh [1]. 2. Cc phng php ch to ng nano carbon CNTs : Hin nay, c bn phng php ph bin c s dng: - Phng php phng in h quang. - Phng php lng ng pha hi ha hc (Chemical vapor deposition :CVD). - Phng php dng ngun laser (laser ablation). - Phng php nghin bi v nhit. Ngoi ra cn c cc phng php khc nh : in phn, tng hp ngn la,tng hp CNTs t ngun nng lng mt triSau y, chng ta s tho lun k hn v cc phng php. 2.1 Phng php phng in h quang: Ban u phng php ny c dng ch to fullerene C60, k t sau khi khm ph ra CNTs th phng php ny cng c s dng rng ri ch to CNTs. Trong phng php ny hi cacbon c to ra bng cch phng mt lung h quang in gia hai in cc lm bng cacbon c hoc khng c cht xc tc. CNTs t mc ln t hi cacbon. Hai in cc cacbon t cch nhau 1 mm trong bung kh tr (He hoc r) p sut thp (t 50 n 700mbar). Mt dng in c cng 50 100 c iu khin bi in th khong 20V to ra s phng in h quang nhit cao ( khong 3000-4000oC) gia hai in cc cacbon. hi phng in,vng khng kh gia hai in cc than b ion ho tr thnh dn in, l plasma, v vy phng php ny cn gi l h quang plasma. ung h quang

ny lm bay hi mt in cc cacbon v lng ng trn in cc cn li, to ra sn phm l SWCNTs hot MWCNTs ty theo vic c cht xc tc kim loi (thng l Fe, Co, Ni, Y hay Mo) hay khng.

ch thc v hiu sut tng hp CNTs ph thuc vo n nh ca mi trng plasma gia hai in cc; mt dng; p sut kh tr; cu hnh ca in cc, bung chn khng;s lng v kch thc tm xc tc kim loi v mt vi yu t khc. Trong tt c cc loi kh tr, heli cho kt qu to CNTs tt nht v y l cht c kh nng ion ha cao[1]. Phng in h quang l mt phng php n gin cho CNTs cht lng kh cao v cu trc tng i hon ho.

Hnh 4: H thit b ch to CNTs bng phng php h quang in a) Tng hp Carbon nanotube n lp (SWCNTs) :

hi in cc anot c gn cc tm xc tc kim loi nh Fe, Co, Ni, Y hoc Mo th ta s thu c cc ng nano carbon n lp.S lng cng nh cht lng ca CNTs thu c ph thuc vo cc thng s nh: nng kim loi,p sut kh tr, loi kh, mt dng v cu to h thng.Thng thng th cc SWCNTs ny c ng knh khong 1.2 n 1.4 nm.Di y la mt s phng php ci thin c hiu qu cng nh cht lng ca CNTs. Tng hp trong mi trng kh tr (inert gas) : Cc CNTs c sn xut bng phng php h quang thng c ln nhiu tp cht nh kim loi lm xc tc hay b li trong cu trc.Cc khuyt tt v tp cht ny kh c x l mt cch hon ton.Tuy nhin c mt thun li l trong mi trng kh tr th ngi ta c th kim sot c kch thc ca cc ng nano carbontube bng cch thay i loi v dng kh tr qua lm thay i cc h s dn nhit v khuch tn. hi s ngng t ca cc nguyn t Carbon v kim loi gia plasma v khng gian xung quanh cathode s nh hng n kch thc ng nano to thnh.Thc nghim tng hp c ng CNTs c ng knh khong 1.2 nm trong mi trng kh tr l rgon, gim 10% so vi kch thc thng thng, vi kim loi xc tc l nickel/yttrium(t l C/Ni/Y l 94.8:4.2:1)[1]. Kim sot plasma quang hc (optical plasma control): Mt cch khc kim sot qu trnh to tnh CNTs l thay i khong cch gia anode v cathode (ACD).Khong cch ny c iu chnh nhm thu c nhng dng xoy mnh xung quanh quanh cathode, lm thc y s bay hi anode v tng s to thnh nanotubes.Mt s th nghim c tin hnh vi s thay i ACD mt cch ti u trong hn hp kh tr argon-helium, vi xc tc nickel/ yttrium (t l C/Ni/Y l 94.8:4.2:1), thu c cc nanotube c ng knh thay i trong khong 1.27 n 1.37 nm ti p sut 660 mbar i vi helium tinh khit v 100 mbar i vi argon tinh khit [1].

 S dng xc tc (catalyst): C hai phng php CVD v phng in h quang u s dng xc tc kim loi to c carbon nanotube n lp.Tuy nhin cn phi hiu rng khng phi kim loi no cng c th cho ra nanotube khi s dng trong c hai phng php.i vi phng php phng in h quang, khi dng hn hp nng cao ca hai kim loi l Co v Mo lm xc tc th ta s c th thu c CNTs c ng knh tng i nh so vi cc kim loi khc, t 0.6-1.2 nm. Tng kh nng chng oxy ha (Improvement of oxidation resistance): hi tng kh nng chng oxy ha trong qu trnh tng hp s lm gim c cc khuyt tt trong sn phm thu c.Phng php ny thch hp sn xut cc CNTs ng dng trong cc mn hnh in t.Nhng nghin cu gn y ch ra rng phng php h quang iu chnh s dng cathode c khot l dng phu (bowl-like) gim khuyt tt v to ra nanotube tinh khit[1].

Tng hp trong mi trng khng kh vi que hn h quang (Open air synthesis with welding arc torch) : Phng php ny s dng mt que hn h quang trong khng kh v qu trnh c bo v bi dng kh argon thi qua.Cathode v anode c lm t graphite

cha Ni v Y (tie l % Ni/Y l 3.6:0.8). Trong in cc lm bia c t c nh trn tm thp( cht nn) c lm mt bng nc.Que hn h quang s t ti cnh ca bia v mui carbon s lng ng trn cht nn nm sau bia.iu kin tin hnh vi dng in 100A v dng kh Argon thi qua to mi trng tr.Bng phng php ny cc nh nghin cu tng hp c CNTs c ng knh 1.32 nm[1].

b) Tng hp Carbon annotube a lp (MWCNTs) : Khi c hai in cc l graphite, th sn phm chnh l carbon nano a lp MWNTs.V khng s dng xc tc kim loi nn MWNTs tng hp c c t khuyt tt hn.Tuy nhin, sn phm li ln nhiu dng th hnh khc ca carbon nh fullerenes, carbon v dnh hnh,do cn phi tinh ch v lm sch sn phm.Hin nay cc nh nghin cu ang pht trin mt cng ngh thu c MWNTs tinh khit quy m ln m khng cn n qu trnh lm sch. Tng hp trong mi trng Nitrogen lng (Synthesis in liquid nitrogen): y l mt phng php phng in h quang trong Nitrogen lng, c th cho MWNTs vi kt tinh cao.Phng php ny khng i hi p sut thp v s dng kh tr.

 Tng hp trong trng in t (Magnetic field synthesis): Phng php ny cho php chng ta thu c cc MWNTs c tinh khit cao v hu nh khng c khuyt tt khi s dng in cc graphite tinh khit ( >99.999%).Trong k thut ny, qu trnh phng in h quang c kim sot bi trng in t xung quanh plasma.

Phng php phng in h quang bng plasma quay (Plasma rotating arc discharge) : Vic s dng k thut ny s gy ra lc ly tm lm xo trn v thc y s bay hi Carbon trn anode.Hn na, qu trnh quay s lm cho plasma tr nn n nh v tng th tch cng nh nhit ca plasma,qua lm tng hiu sut to thnh sn phm.Tc quay c th t 5000 vng/pht v nhit t 1000-1150oC.

2.2 Phng php lng ng pha hi ha hc ( CVD) : Lng ng pha hi ha hc (CVD) l mt trong nhng phng php lng ng mng c s dng ph bin nht hin nay.Lch s pht trin ca phng php ny c th c im qua mt s mc thi gian sau [2]: - Nm 1890,cc nh khoa hc ngi Php chng kin s to thnh si Carbon trong qu trnh thc nghim khi cho cyanogens i qua b mt s nng. - n gia th k 19, phng php CVD c ng dng iu ch vi si Carbon bng cch phn hy nhit cc Hydrocarbon vi s c mt ca kim loi lm xc tc. - Nm 1952, Radushkevich v ukyanovich cng b s tn ti ca cc si carbon hnh tr c ng knh 50-100nm to thnh t s phn hy nhit carbon monoxide trn xc tc kim loi st ti 600oC v ngh mt c ch ca s to thnh cc lp grapheme trong h Fe-C( st Carbide). - Nhiu nghin cu khc v phn ng CVD cng c cng b trong thi gian sau nh nghin cu ca Hofer v cng s (1955),Walker (1959), Baird v cng s (1971) CVD c rt nhiu im khc so vi phng php phng in h quang v phng php bc bay bng laser. Phng in h quang v bc bay bng laser l hai phng php thuc nhm nhit cao (>3000K), thi gian phn ng ngn (sms), cn phng php CVD li c nhit trung bnh (700-1473K) v thi gian phn ng di tnh bng pht cho n hng gi. Mt hn ch chnh ca hai phng php phng in h quang v bc bay bng laser chnh l CNTs c to ra khng ng u, sp xp hn n, c lp, khng theo mt quy tc cho trc hoc nh hng trn b mt.

Hin nay c nhiu phng php CVD s dng cc ngun nng lng khc nhau tng hp CNTs v d nh: phng php CVD nhit, phng php CVD tng cng plasma, phng php CVD xc tc alcohol, phng php CVD c laser h tr, qu trnh CoMoCat,phng php phn hy CO p sut cao ,v.v.[1]. H CVD nhit c cu to gm mt ng thch anh c bao quanh bi mt l nhit. Bn cht v hiu sut tng hp ca tin cht trong cc phn ng b nh hng ca rt nhiu yu t khc nhau nh bn cht t nhin ca xc tc kim loi v tc dng ca cc cht xc tc ny, ngun hydroccbon, tc kh, nhit phn ng, thi gian phn ng v.v Hu ht phng php CVD nhit thng c dng ch to MWCNTs vi ngun hydroccbon thng dng l acetylene (C2H2) hoc (C2H4) v cc ht nan Fe, Ni, Co nh l cc cht xc tc. Nhit mc CNTs thng thng nm trong di nhit 500-9000C. di nhit ny cc nguyn t ccbon b phn tn trn cc ht nan kim loi v cui cng tr thnh trung ha. Cc nguyn t ccbon ny sau lng ng li tr thnh dng CNTs, ng knh ca CNTs ph thuc vo kch thc ca cc ht xc tc kim loi.

S h thng phn ng CVD

Qu trnh pht trin ng nanocarbon trong phng php CVD b nh hng bi cc yu t s c ni r hn di y [2]: Vt liu xc tc v nng xc tc : Cc kim loi thng c s dng lm xc tc l cc kim loi chuyn tip nh Fe,Ni,CoTrong Fe c hot tnh xc tc v hiu sut cao nht nhng graphit ha li khng cao, trong khi Co li cho kt qu ngc li.V th gn y, ngi ta xut vic s dng h xc tc l hn hp ca cc kim loi nh h Fe-Co gim nhit phn ng v tng hiu qu sn phm.Bn cnh , nng xc tc cao s lm tng s pht rin CNTs.

 Nhit : Ti nhit thp, th c ch mc ng t di ln s chim u th v tng tc gia cht mang v kim loi cn mnh, trong khi nhit cao th c ch mc ng t trn xung loi chim u th, mc d c ch mc ng cn ph thuc vo c im ca xc tc v cht mang.Theo mt s nghin cu th ngi ta xut nhit ti u cho phn ng iu ch MWNTs l 650oC, cn cho SWNTs l 900 oC vi h xc tc Fe-Co trn zeolite. p sut bay hi :l mt yu t quan trng v cn c kim sot ty theo h phn ng. tng hiu sut mc CNTs, ngoi vic s dng thch hp cc iu kin nh: nhit , t l liu lng kh cng nh gia cht xc tc kim loi, cn s dng thm cht h tr xc tc chng hn nh CaCO3, MgCO3, v.vC th to lng ln ng nan ccbon bng cch cho acetylene ngng ng trn zolit c xc tc l Co v Fe. V zolit l cht c nhiu l trng cc nh, cc phn t d dng lt vo cc l trng nn khi cho acetylene ngng t trn Co/Zolit, ta c c ng nan ccbon nhiu vch nhng ng thi cng c fullerenes v ng nan ccbon n vch.

Hnh 14. nh TEM cc ng ccbon nan mc bng phng php CVD 2.3 Phng php dung ngun laser (laser ablation) : Phng php ny do nhm nghin cu ca Smalley ti trng i hc Rice (Hoa K) gii thiu ln u tin vo nm 1995.Phng php bc bay bng laser l mt phng php c hiu qu cao cho qu trnh tng hp b SWCNTs vi vng

phn b hp. Trong phng php ny, mt ming graphit dng lm bia b bc bay bi bc x laser di p sut cao trong mi trng kh tr. MWCNTs c to ra trn bia graphit sch. Cht lng v hiu sut ca sn phm to ra ph thuc vo nhit phn ng,trong cht lng sn phm tt nht nhit 12000C. nhit thp hn th cht lng cu trc gim v CNTs bt u xut hin nhng sai hng. Trong phng php bc bay bng chm laser, nng lng ca chm tia laser lm bay hi bia graphite c t trong l t bng in nhit khong 12000C. Lung kh Ar (p sut ~500 Torr) thi hi ccbon t vng nhit cao v in cc lng ng bng ng c lm lnh bng nc .Nu dng bia graphite tinh khit ta s thu c MWCNTs. Nu bia c pha thm khong 1,2% nguyn t Co/Ni vi khi lng Ni v Co bng nhau s thu c SWCNTs. Trong sn phm cn c cc dy nan to bi cc SWCNTs vi ng knh t 10 nm n 20 nm v di trn 100 m. Gi tr trung bnh ca ng knh ng v mt phn b ng knh ng tu thuc vo nhit tng hp v thnh phn xc tc. to SWCNTs, ngi ta cn dng phng php xung cc nhanh t laser in t t do (FEL) hoc phng php xung laser lin tc.

S h thng phn ng dng ngun laser

Phng php ny c u im l sn phm thu c c sch cao (trn 90%) so vi phng php h quang in. Tuy nhin, y cha phi l phng php c

li ch kinh t cao v kh tn km v yu cu ngun laser cng sut ln, in cc than cn c sch cao, lng sn phm to ra t... 2.4 Phng php nghin bi v nhit : Dng bnh thp khng r c cha cc bi thp khng r c cng cao v vo bnh thp bt graphite tinh khit (98%). Bnh thp khng r c thi kh rgon vi p sut 300kPa. Quay bnh bi thp khng r nghin bt graphite khong 15 gi. Sau khi nghin, bt c rt nhiu ng nano cacbon a vch. Ngi ta cho rng qu trnh nghin to ra cc ht graphite nhiu mm pht trin ng nano cacbon v khi nung nhit, cc mm pht trin thnh ng nano cacbon. 2.5 Phng php in phn (Electrolysis) :
Phng php ny ln u tin c nghin cu bi trng i hc Sussex vo nm 1995, m ra kh nng sn xut c CNTs nhit thp vi chi ph thp hn cc phng php khc.Tuy nhin, phng php ny ch sn xut c MWNTs ch khng cho ra SWNTs, cng vi s kh khn trong kim sot hiu qu to thnh sn phm l tr ngi khin n khng c p dng ph bin[3]. Qu trnh ny th bao gm cc in cc graphite nhng trong dung dich nng chy ca mui kim loi kim v halogen ( vd: LiCl,KCl, NaCl, LiBr) c cha trong b cha graphite, vi mi trng l kh Ar[3]. Cc thng s nh hng n qu trnh l loi mui nng chy v nhit tin hnh.

2.6 Phng php tng hp ngn la (Flame Synthesis Method): Phng php tng hp SWNTs ny da trn s kim sot trong mi trng ngn la,s dng ngun nhin liu hydrocarbon r tin v to thnh dng cc mng nh aerosol ca kim loi xc tc.Trn cc mng ny, SWNTs s pht trin ging nh trong phng php dung ngun laser v phng in h quang. Cc mng xc tc kim loi ny c th c to ra theo 3 cch : Cch 1 : Xc tc kim loi nh Co c ph ln mt mng li s c hnh dng ging cc git, bng s lng ng pha hi vt l.Sau , nhng mng ny s tip xc vi ngn la v tr thnh cc mng aerosol nh.

 Cch 2 : t chy giy lc nhng dung dch ion kim loi( v d st nitrat) to ra cc cu t aerosol kim loi nh. Cch 3 : dng k thut bay hi nhit vi bt kim loi( nh Fe hoc Ni) . 2.7 Phng php tng hp bng nng lng mt tri(Solar Production of Carbon Nanotubes) [3] : Phng php ny do aplaze v cc cng s xut tng hp SWNTs v MWNTs vi vic s dng nng lng mt tri tp trung trn bia Carbon-kim loi trong mi trng kh tr.Nng lng mt tri xp x gn 500 W/cm2 c kh nng lm bay hi bia carbon-kim loi.Gn y,ngi ta cn ch to ra c l nung s dng nng lng mt tri c cng sut t c 1000 kW,do lm tng ng k kh nng to thnh fullerence v nanotubes. Thng thng th ngun nguyn liu c s dng l CH4v C4H10 vi xc tc Ni/Al2O3 hoc Co/MgO.Tuy nhin, phng php ny cng cn c nghin cu thm xc nh kh nng nh hng ca cc yu t nh nhit , kh mang hay t l carbon-kim loi.

I. Qu trnh lm sch (purification): SWNTs c tng hp bng cc phng php tho lun trn u t nhiu c ln cc tp cht nh : graphite,carbon v nh hnh, kim loi xc tc v fullerenes.Do cn phi tin hnh lm sch tinh ch sn phm.Cc k thut ph bin c s dng trong cng nghip l oxy ha v hon lu acid. Cc k thut ny c chia thnh 2 loi chnh : phn tch chn lc cu trc (lm tinh khit CNTs thu c) v phn tch chn lc kch thc( nhm thu c cc CNTs c kch thc ng nht).Ngoi ra,cn c cc k thut khc cng thng dng l : , siu m, vi lc, ct, tch st t, gn nhm chc nng v k thut sc k. 1. Oxy ha (Oxidation): X l oxy ha SWNTs l mt phng php tt loi b cc tp cht cacrbon v lm sch b mt kim loi.iu bt li l trong phng php ny l khng nhng ch c cc tp cht b oxy ha m ngay c CNTs cng b oxy ha.Tuy nhin, s oxy ha CNTs th khng mnh m bng cc tp cht, v th m ra kh nng s dng k thut ny mt cch ph bin.Mt thun li na l thng thng cc tp cht thng gn trn cc cu t kim loi, trong khi cc kim li ny li ng vai tr nh xc tc trong phn ng oxy ha, lm tng kh nng oxy ha ca phn ng.Hiu qu ca k thut ph thuc vo kim loi ln vo,thi gian oxy ha, mi trng, tc nhn oxy ha v nhit . 2. X l acid (Acid treatment) : K thut x l acid nhm loi b cc tp cht kim loi trong qu trn tng hp.iu kin tin hnh l kim loi phi tri qua qu trnh oxy ha chuyn thnh dng oxit kim loi trc khi c ha tan trong dng acid, cn CNTs s

c thu hi di dng kt ta.Cc acid c dng c nng trung bnh v thng l HCl, HNO3Tuy nhin cng cn lu n kh nng nh hng ca acid n CNTs trong qu trnh x l. 3. Phng php (Annealing) : c tin hnh trong khong nhit 8731873 K, cc nanotube s c ti sp xp v do loi b c cc khuyt tt hnh thnh trong qu trnh tng hp trc v cc graphit carbon, fullerene cng b phn hy nhit.ng thi trong iu kin chn khng vi nhit cao (1873 K) th kim loa s b nng chy v b tch b. 4. Siu m (Ultrasonication) : Cc cu t s b dao ng di tc ng ca sng siu m, qua gip tch ri cc CNTs v cc tp cht.Phng php ny b nh hng ca cc yu t nh :Cht hot ng b mt, dung mi v tc cht s dng. 5. Tch t (Magnetic Purification) : CNTs c trn vi hn hp vt liu nano v c nh ZrO2 hoc CaCO3 trong mt b siu m ri tin hnh loi b tp cht st t vi mt nam chm vnh cu.

6. Vi lc (Micro filtration):
SWNTs v cc cu t carbon nano s b gi li trn mng lc, trong kh cc cu t nano khc ca kim loi xc tc v fullerene s i qua. Ngoi ra,c cch khc l SWNTs s c cho vo dung dch CS2.Fullerene b ha tan trong CS2 s i qua mng lc trong khi cc thnh phn khng tan s b gi li.

Ngoi ra cn c cc phng php khc nh :ct (Cutting), gn nhm chc (Functionalisation) v sc k (Chromatography). II. Gn nhm chc : Mt tr ngi k thut trong vic ng dng CNTs trong lnh vc y sinh v cc lnh vc lin quan khc l kh nng tan trong mi trng nc km.Do , vic chc ha b mt CNTs l mt cng vic cn thit khc phc tr ngi ny.Mt s phng php gn nhm chc vo CNTs s c tho thun di y. 1. Chc ha bng vic s dng nguyn t kim loi, hp cht v c, v cc hp cht Grignard: Cc CNTs c x l vi nguyn t kim loi kch thc nano (Au, Fe, Co) hoc vi cc dung dch trong ammonia (Alkali kim loi), thng qua vi cc cu ni hu c. Nh vy, cc sn phm sau x l ca MWNTS tan c trong dung mi nc, c iu ch thng qua phng php tng hp in-situ s dng hp cht hot quang in N, N'-bi (2-mercaptoethyl) - perylene-3, 4,9 ,10-tetracarboxylic diimide nh cht to cu ni v n nh lin kt.Sn phm sau x l ny pht hunh quang rt mnh khi chiu n UV. N c tim nng trong ng dng lm cht nh du sinh hc. Ht nano t tnh oxide st hoc cobalt v cobalt / platinum c bc ph v c gn ln ng nano carbon nanotubes nh phn t cu ni l dn xut carboxylic ca pyrene. H nano st t - ng nano carbon tan tt trong dung mi hu c nh Chloroform, toluene, v hexane.

Cc ng nano carbon tan c trong dung mi hu c c th c iu ch bng qu trnh alkylate hoc arylate ha cc mui Li , Na hoc K ca nano carbon trong dung dch ammonia v c gi l phn ng Billups. Phn ng Billup cn gip tng hp cc ng nano carbon tan c trong nc.Phng php ny cho php gn cc nhm alkyl hoc arylk bc nm, dng c cho c mui Li v Na to ra sn phm vi lng hng gam ng naono carbon alkylate ha.

2. Chc nng ha ng nano carbon trong mi trng acid mnh c cha cc cht cha. Cc acid mnh oxy ha b mt ng nano carbon to nhm chc COOH trn b mt ng. Sau cc nhm chc ny s phn ng tip vi cc cht cha oxy khc trong dung dch hnh thnh mui nano carbon tan. Trong hng tip cn khc, sn phm phenyl sulfonate ha ng nano carbon hnh thnh t vic x l bng benzoyl peroxide, oleum v xt Cc sn phm ng nano carbon bin tnh cha nhm chc phenyl sulfonate theo k thut to mui diazonium hon ton tan tt trong nc. Chng c th phc v nh cng ngh nn tng tip tc cho cc ng dng trong dc, in t, v nng lng. 3. Chc ha ng nano carbon bng cc hp cht cha nhm alkyl hoc vng thm:

Sn phm ng nano carbon n vch bin tnh bng cc alkyl hoc vng thm c th i t vic s dng k thut nghin rung tc cao gy phn ng cng hp. Sn phm t hng bin tnh ny cho tnh tan tt trong nhiu loi dung mi hu c. Ngoi ra, bng phn ng cng vng lng cc 1,3 cc oxide nitril ln thnh ng nano carbon n vch, ta cng c th thu c sn phm cha nhm chc pyridyl c tnh tan cao. Cc sn phm dng k thut cng hp 1,3 ni trn l loi c chc ha hai ln. hai u ng nano carbon, chng cha cc nhm chc pentyl ester cho tnh tan tt trong cc dung mi hu c. Trn thnh ng, chng cha cc nhm chc pyridyl isoxazoline cho kh nng kt hp tt vi cc porphyrin kim loi sau ny.

Tng t, sn phm ng nano carbon c bin tnh nh cng hp 1,3 nhm phenyl v trng hp nh phn ng trng hp gc truyn mch nguyn t ca cc nhm chc t-butyl acrylate cng cho tnh tan tt trong nhiu loi dung mi hu c khc nhau. 4. Chc ha ng nano bng cc hp cht cha nhm chc amin (amido) mch thng hay vng thm: Thng s chc ha cc ng nano carbon a vch c th lm tng s phn tn ca chng trong nc. Tuy nhin, cc phn ng khc trong qu trnh gn nhm chc amin ny cng c th xy ra v lm nh hng n s phn tn ng nano carbon trong cc dung mi hu c.

Cc hp cht amine c dng l octadecylamine (OD ), 2-aminoanthracene, 1-H,1-H-pentadecafluorooctylamine, 4-perfluorooctylaniline v 2,4bis(perfluorooctyl) aniline. S chc ha cc MWNTs vi octadecylamido (sSWNT-CONH-(CH2)17CH3), cng hnh thnh sn phm bin tnh tan c trong nc. Hm lng ca nhm chc octadecylamido trong MWNTs chim 50%. Ngoi ra , vic s dng phi hp hoc ring l cc polyimide vng thm khi bin tnh cng to ra cc sn phm nano carbon a lp c kh nng tan tt trong dung mi hu c.

Nhm dn xut aniline (4-pentylaniline, 4-dodecylaniline, 4-tetradocylaniline, 4-pentacosylaniline, 4-tetracontylaniline, 4-pentacontylaniline) cng nh cc amine(octadecylamine, nonylamine, dodecylamine, pentacosylamine, tetracontylamine, pentacontylamine), v hn hp t chng c s dng trong qu trnh chc ha ng nano carbon. Sn phm hnh thnh l mt hn hp c th tan tt trong carbon disulfide CS2 v nhiu loi dung mi hu c thng dng chlorobenzene, dichlorobenzene, trichlorobenzene, tetrahydrofuran (THF), chloroform, methylene chloride, diethylene glycol dimethyl ether, benzene, toluene, tetrachlorocarbon, pyridine, dichloroethane, diethyl ether, xylene, naphthalene, nitrobenzene, ether v cc hn hp dung mi khc. h nng tan ca ng nano carbon l 0.01-5.0 mg/ mL. 5. Chc ha ng nano carbon bng cc hp cht cha sulfur :

Trong s cc cht hot ng b mt hoc cht chc ha cha nhm sulfur, sodium dodecyl sulfate C12H25OSO3Na dng kt hp vi hydroxypropyl methyl cellulose hoc hn hp acid HNO3/H2SO4 gip h tr s phn tn cc ng nano carbon. 6. Chc ha ng nano bng hp cht vng c s lng phn t ln : Cc vng i phn t c in nh porphyrins v phthalocyanines c ng dng thnh cng nh l tin cht cho s ha tan cc ng nano carbon. Dung dch ng nano carbon porphyrin i t [meso-(tetrakis-4sulfonatophenyl) porphine dihydrochloride] c th tan trong nc v bn trong mt thi gian di. III. NG DNG CA CARBON NANOTUBE: Carbon nanotube (CNT) l mt thnh tu mi ca khoa hc ni chung v ngnh ha hc vt liu ni ring, vi nhiu c im u vit kch thc nh nhng l tnh v cng ng k - ha hn kh nng ng dng cao trong nhiu lnh vc, c bit l trong lnh vc in t, in ha, lm b phn chu lc trong cc chi tit my, u d trong o lng v lm tm nn trong nhiu lnh vc sinh ha. - Tuy mang nhng c tnh y ha hn, nhng vic ch to CNT cng phi ng u vi nhiu th thch v gi c, kh nng ch to v vn hnh. 1. ng dng trong lnh vc in t Kh nng ng dng lm cc pht dng trong cc thit b chiu sch tia cathode v ang c nghin cu. Nguyn tc ca ng dng ny c trnh by trong hnh 1.

Hnh 1 Hnh nh ngun pht x nh sng s dng CNTs lm cathode Nhng nguyn t pht sng s dng NCTs c thit k da trn nguyn tc ca n 3 cc. Trc y, trong nhng thit k s khai, nhng nhng que hnh tr cha CNTs a lp c ct thnh nhiu da mng v c dn vo thp khng g bng bt bc cn gn y, nanotubes c in ln b mt tm kim loi. Mt khc, mn phosphor th c in ln b mt tr ca tm knh. Bng vic s dng nhng vt liu hunh quanh khc nhau, mu sc thu c cng thay i theo. V d, sng ca mn phosphor o trn ng c gi tr trong khong 6.4 x 104 cd/cm2, cho nh scn xanh lc khi cng dng qua anode l 200 , cao hn gp 2 ln so vi nguyn t chiu sng Cathode Ray Tube nhit ion thong thng. Cng ngh hin th mn hnh phng Mn hnh hin th diode ma trn u tin c ch to bng vic s dng CNTs nh l ngun pht x electron. Mt cu trc c xy dng i hc Northwestern bao gm nhng di nanotube-epoxy trn mt knh phng anode v nhng di Indium-Tin-Oxide (ITO) c ph phosphor mt phng anode. Nhng

im nh c hnh thnh t vng giao nhau gia nhng di cathode v anode, nh c minh ha hnh 6:

(a) Hnh 2 (a) Hnh nh ca mn hnh pht x u tin (b) Mt mn hnh pht x 4.5 inch ca Samsung

(b)

Vi mt khe h anode-cathode khong 30 m, cn phi c 1 hu in th 230V to dng pht x cn thit hot ng mn hnh diode (khong 76 mA/mm2). Thit b c vn hnh bng vic s dng s half-voltage offpixel.Nhng xung in 150V c hon i gia 2 di anode v cathode to nn hnh nh. Gn y, mn hnh trng pht x kiu diode kch c 4.5 inch c Samsung ch to (hnh 2b) vi di nanotube n lp cathode v di ITO ph phosphor anode c sp vung gc vi nhng di cathode.

2.

ng dng trong d tr nng lng CNTs ang c nghin cu kh nng sn sinh v tn tr nng lng. Than

ch, vt liu t carbon v in cc si carbon c s dng trong pin nhin liu, pin v nhiu ng dng in ha khc trong nhiu thp k. NTs c bit hn v n c kch thc nh, mt b mt phng v nhng c trng b mt hon ho v ch c nhng lp than ch c bn l c phi ra trong cu trc ca NTs. Tc vn chuyn electron in cc carbon l yu t ch yu quyt nh hiu qu ca pin nhin liu v iu ny ph thuc v nhiu yu t, c th k ra nh cu trc v hnh thi ca vt liu carbon s dng trn in cc. Nhiu th nghim ch ra rng tc electron vn chuyn trong CNTs l nhanh nht khi so snh vi nhng in cc carbon thong thng.Vi in cc nanotube c xy dng bng vic s dng cht kt dnh v p dng thnh cng trong nhiu phn ng in ha.Hiu qu hot ng ca chng c nhn nh l tuyt vi khi so snh vi in cc carbon khc khi xt trn kha cnh vn tc phn ng v kh nng o ngc phn ng. Vt liu nanotube a lp tinh tinh khit v vt liu nanotube a lp kt hp vi xc tc kim loi (Pd, Pt, g) c s dng xc tc cho phn ng kh oxy mt yu t quan trng trong pin nhin liu. C th thy rng trong nhiu nghin cu, NTs c th thay th mt cch xut sc cho in cc da trn carbon thong thng.Tng t, chn lc ca xc tc da trn NTs cng c ci tin. NTs c s h tr ca Ru c pht hin c kh nng vt tri so vi than ch vi cng kim loi v trn nhng vt liu carbon khc trong phn ng hydro ha pha lng cinnamaldehyde. ng dng np in cho pin in ha C s vi lithium

Nguyn tc c bn ca pin i sc c l vic np v phng i gia 2 in cc hot ng. Minh ha cho ng dng ny l pin lithim s dng kim loi chuyn tip, ixCoO2 hay ixMn2O4 lm cathodes v vt liu carbon, than ch hay v nh hnh lm anodes. Mc ch ca nghin cu ny l lm ra pin i vi kh nng tch tr nng lng cao, thi gian sc nhanh v chu k s dng di. h nng d tr nng lng ph thuc vo nng bo ha ca ithium trong nguyn liu lm in cc. i vi than ch, nng bo ha cn bng nhit ng l iC6, tng ng vi 372m h/g. Nng i cao hn c ghi nhn khi s dng carbon khng trt t, carbon cng mm v vt liu na bn to nn di p sut cao. Hnh 8 thng k li s liu qu trnh np phng in s dng pin in ha vi lp CNT v l lithium nh l 2 cc. in dung 100-640 m h/g c ghi nhn.

nh

Trn, Qu trnh np ithium vo NTs a lp, s liu c ghi nhn vi

cng 50 m h/h, s dng cht in ly l iClO4 trong ethylene carbonate/dimethyl carbonate. i Qu trnh np v phng in ca NTs n lp, in dung thun nghch l 1000 m h/g 3. ng dng trong vt liu composites C tnh ca CNTs l mt vn th v v CNTs c xem nh l si carbon siu vit.i vi si carbon thong thng, c bn ring ( bn/khi lng ring) hn thp khong 50 ln v c s dng rt tt trong vt liu composite. Do , CNTs c xem nh l ng c vin l tng cho nhng ng dng v cu trc. Si carbon c dng nh l vt liu tang cng cho nhiu loi composite bn cao, kh nng lm vic cao v khi lng nh. Ngi ta c th tm thy nhng ng dng rng ri ca cng ngh ny, t cy vt tennis n thn my bay v tu

khng gian. NASA gn y nghin cu quy m ln vic pht trin vt liu composite da trn CNTs dng trong vic thm him sao Ha trong tng lai. Nhng l thuyt trc y v nhng nghin cu gn y v mt s loi CNTs (ch yu l a lp) xc nhn NTs l mt trong nhng cu trc bn b nht t trc ti nay.V lien kt cng ha tr C C l mt trong nhng lin kt mnh nht trong t nhin. Do mt cu trc da trn vic sp xp li nhng lin kt ny theo trc ca CNTs s to ra mt loi vt liu vi vi c tnh tng vt. i vi NTs a lp, bn trong nhng tnh hung thc tin c th b nh hng bng vic trt nhng lp graphite hnh tr ln nhau. ng dng trong cc d nano v u d Vi kch thc rt nh, ng u cao, kh nng dn in cao, bn c hc cao nhng li do, NTs hon ton c th ng dng trong vic ch to cc d nano. Cc d c th dng trong nhiu lnh vc khc nhau, chng hn vic to phn nh phn gii cao, in cc nano, h thng dn truyn thuc, u d, b phn pht x h nng ca thit b pht x da trn NTs c bn trong phn trn. u im ca NT l kch thc cc mng v kh nng phn nh c trng (chng hn mt vt nt cc nh v su trn b mt vt th - iu gn nh khng th vi nhng cc d ln hn lm bng Si hay Fe).Nhng phn t sinh vt nh DN cng c th c to lp hnh nh vi phn gii cao khi s dng cc d nanotube, v d in hnh l vic to lp hnh nh ca amyloid-b-protofibrils lin quan n bnh lzheimer, vi phn gii cao nht tng thy. Ngoi ra, nh vo do cao, cc d NTs khng b gy khi chm vo b mt vt th nhng va chm c th lm cong hnh dng ca NT, nhng sau s d dng tr li hnh dng ban u. Hnh 3 bn di minh ha 1 u d FM c lm t NT a lp.

4.

nh

ng dng NT a lp lm u d FM. tm ca si carbon VGCF l NT a lp.

Ngoi vic s dng cc d NTs to lp hnh nh phn gii cao, n cn c th c dng nh cng c cho nhng thao tc b mt, chng hn 1 cp NTs c th c iu khin nh 1 ci nhp gp th nhng cu trc nano trn b mt. N cng c th c dng trong k thut in litho: Mt on thng di 10 nanometer c th c ghi li trn 1 tm nn silicon bng vic s dng u NTs tc cao 1 k thut ch c th c thc hin vi nhng ng c kch thc nh NTs. 5. ng dng lm hu n Nh vo li thng v hp trong lng ca NTs, n c th c lm y bng nhng vt liu khc to thnh dy nano 1 chiu. Nhng tnh ton trc y l xc nh bn ca nhng mao qun trong lng NTs cha lu cht kh v lu cht bn trong n. Minh chng u tin cho iu ny l 1 th nghim nm

1993, qua vic lm y mch mao qun bn trong NT a lpbng ch nng chy. Dy c ng knh 1.2 nm c to nn bng phng php ny. Nhiu th nghim mi y ang nghin cu kh nng lm y mao qun ca NTs bng vt liu kim loi v ceramic. h nng ny dn n 1 ng dng khc ca NTs c dng nh l khun to nn dy nano vi nhiu thnh phn v cu to khc nhau, da trn tnh cht ca nhng cht c nhi vo bn trong NTs. Hnh 4 bn di minh ha ng dng ny ca NTs

nh

ng dng lm khun ca NTs. nh b n tri l s m t vic lm y

mao qun 1 chiu ca NTs. (a) nh TEM ca 1 ng nano b oxi ha. (b) nh TEM ca 1 NTs a lp b oxi ha hon ton. (c) nh TEM ca 1 NTs vi mao qun c lm y bng ch oxide thng qua phng php mao dn.