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Polymer 48 (2007) 4907e4920

Feature Article
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Multiwall carbo aotube elastomeric composites! A review
"iliae #o$ob%a
"aboratoire PPM&' (.).P.*.+.' ,0 rue -au.ueli' 7/20, Paris *e1e2' Frace
3eceive1 ,7 February 20074 receive1 i revise1 5orm ,0 6ue 20074 accepte1 ,7 6ue 2007
Available olie 27 6ue 2007
Abstract
8aostructure1 materials 9aie1 9reat importace i t:e past 1eca1e o accout o5 t:eir wi1e ra9e o5 potetial applicatios i may areas.
A lar9e iterest is 1evote1 to carbo aotubes t:at e2:ibit e2ceptioal electrical a1 mec:aical properties a1 ca t:ere5ore be use1 5or t:e
1evelopmet o5 a ew 9eeratio o5 composite materials. 8evert:eless' poor 1ispersio a1 poor iter5acial bo1i9 limit t:e 5ull utili%atio o5
carbo aotubes 5or rei5orci9 polymeric me1ia.
+ t:is paper' recet a1vaces o carbo aotubes a1 t:eir composites will be presete1 t:rou9: results o5 t:e aut:or;s researc:' essetially
base1 o 5ille1 elastomeric etwor$s. <:e itrisic potetial o5 carbo aotubes as rei5orci9 5iller i elastomeric materials will be 1emo=
strate1. +t will be s:ow t:at' 1espite a poor 1ispersio' small 5iller loa1i9s improve substatially t:e mec:aical a1 electrical be:aviors o5 t:e
so5t matri2. >it: t:e a11itio o5 , p:r o5 multiwall carbo aotubes i a styreeebuta1iee copolymer' a 4/? icrease i mo1ulus a1 a 70?
icrease i t:e tesile le9t: are ac:ieve1. )traii9 e55ects ivesti9ate1 by atomic 5orce microscopy a1 i5rare1 a1 3ama spectroscopies'
provi1e iteresti9 results 5or t:e u1ersta1i9 o5 t:e mec:aical be:avior o5 t:ese aotube=base1 composites. All t:e e2perimetal 1ata lea1
to t:e belie5 t:at t:e orietatio o5 t:e aotubes plays a ma@or role i t:e mec:aical rei5orcemet. <:e stro9 restrictio i e.uilibrium swell=
i9 i toluee wit: t:e M>8< cotet is ot ascribe1 to 5illerematri2 iter5acial iteractios but to t:e occlusio o5 rubber ito t:e a99re9ates.
A t:e ot:er :a1' carbo aotubes impart co1uctivity to t:e isulator matri2. #etwee 2 a1 4 p:r' t:e co1uctivity icreases by 5ive or1ers
o5 ma9itu1e re5lecti9 t:e 5ormatio o5 a percolati9 etwor$. *:a9es i resistivity u1er uia2ial e2tesio complete1 by AFM observatios
o5 stretc:e1 composites bri9 ew isi9:ts ito t:e properties o5 t:ese composites by :i9:li9:ti9 t:e cotributio o5 orietatioal e55ects.
2007 Publis:e1 by (lsevier "t1.
Beywor1s! *arbo aotubes4 (lastomers4 3ei5orcemet
,. +tro1uctio
(lastomers are usually rei5orce1 wit: mieral 5illers i
or1er to 9et substatial improvemets i stre9t: a1 sti55ess.
<:e e2tet o5 property improvemet 1epe1s o several
parameters iclu1i9 t:e si%e o5 t:e particles' t:eir aspect
ratio' t:eir 1e9ree o5 1ispersio a1 orietatio i t:e matri2
a1 t:e 1e9ree o5 a1:esio wit: t:e polymer c:ais C,D.
<:e last 5ew years :ave see t:e e2tesive use o5 aopar=
ticles because o5 t:e small si%e o5 t:e 5iller a1 t:e correspo1=
i9 icrease i t:e sur5ace area allowi9 to ac:ieve t:e
re.uire1 mec:aical properties at low 5iller loa1i9s.
(=mail a11ress! "iliae. # o$ob%aEespci .5r
0002=087,/F = see 5rot matter 2007 Publis:e1 by (lsevier "t1.
1oi!,0.,0,7/@.polymer.2007.07.047
+ or1er to create ew material systems wit: superior prop=
erties' various aoparticle morp:olo9ies :ave bee use1 as
rei5orci9 5illers i elastomeric matrices. <:ese aometer=
scale rei5orci9 particles iclu1e sp:erical particles suc: as
silica or titaia C2e/D' platelets suc: as layere1 silicates C7e
,2D' carbo C,0D or clay 5ibers C,4D a1 multiwall or si9le=
wall carbo aotubes C,/e,7D.
)ole9el tec:i.ue 9eerati9 ao=si%e1 silica or titaia
particles wit:i a :ost matri2 :as prove1 to be a e2cellet ap=
proac: 5or t:e syt:esis o5 :ybri1 systems w:ere t:e or9aic
a1 ior9aic compoets are itimately mi2e1 ito a ew
material e2:ibiti9 9reatly improve1 mec:aical properties.
"ayere1 silicates :ave 9eerate1 si9i5icat iterest be=
cause t:ey ca 9ive rise to e25oliate1 systems i w:ic: t:e i=
1ivi1ual silicate aolayers are :omo9eeously a1 ui5ormly
1isperse1 t:rou9:out t:e polymer matri2. <:e e25oliate1
4908 ". #o$ob%a / Polymer 48 (2007) 4907e4920
aocomposites e2:ibit si9i5icatly e:ace1 mec:aical
a1 p:ysical properties w:e compare1 to u5ille1 polymers
or covetioal composites.
)ice t:eir 1iscovery i ,99, C,8D' carbo aotubes
(*8<s) :ave attracte1 eormous attetio 5or t:eir 5u1ame=
tal be:avior a1 5or t:eir use i a wi1e variety o5 applicatios
i aoelectroic 1evices C,9e2,D' probe tips 5or scai9
probe microscopes C22e27D or i t:e automotive a1 aero=
space i1ustries 5or t:e 1issipatio o5 electrostatic c:ar9es
C27'28D. Awi9 to t:eir structural c:aracteristics a1 t:eir
electrical a1 mec:aical properties' oe o5 t:e most im=
portat opportuities i t:e 5uture is t:e emer9ece o5 a ew
9eeratio o5 composite materials sice relatively low carbo
aotube loa1i9 (G,0 wt.?) wit:i polymeric matrices' are
re.uire1 5or various applicatios C29'00D.
2. *:aracteristics' syt:esis met:o1s a1 processi9
o5 carbo aotubes 5or composite materials
*arbo aotubes ca be visuali%e1 as 9rap:ee layers
rolle1 ito cyli1ers cosisti9 o5 a plaar :e2a9oal arra9e=
met o5 carboecarbo bo1s. <:eir outsta1i9 properties
are a cose.uece o5 t:is ui.ue bo1i9 arra9emet com=
bie1 wit: topolo9ical 1e5ects re.uire1 5or rolli9 up t:e
s:eets o5 9rap:ite ito cyli1ers. &uri9 9rowt:' 1epe1i9
o t:e syt:esis met:o1s' t:ey ca assemble eit:er as co=
cetric tubes (multiwall aotubes' M>8<s) or as i1ivi1ual
cyli1ers (si9le=wall aotubes' )>8<s). <:eir 1iameters
ra9e 5rom about a aometer to tes o5 aometers wit:
le9t:s ra9i9 5rom several micrometers to millimeters or
eve cetimeters.
*arbo aotubes ca be syt:esi%e1 by 1i55eret tec:=
i.ues iclu1i9 arc=1isc:ar9e C0,'02D' laser ablatio C00e
07D a1 various catalytic c:emical vapor 1epositio (**-&)
C07e40D.
+ t:e arc=1isc:ar9e tec:i.ue' a electric arc is 9eerate1
betwee two 9rap:ite electro1es u1er a :elium or ar9o at=
mosp:ere' w:ic: causes t:e 9rap:ite to vapori%e a1 co1ese
o t:e cat:o1e. <:e 1eposit cotais t:e aotubes a1 also
5ullerees' amorp:ous carbo materials a1 catalyst particles.
<:is tec:i.ue re.uires 5urt:er puri5icatio to separate t:e
*8<s 5rom t:e by=pro1ucts preset i t:e cru1e material.
<:e electro1es o5 9rap:ite are 1ope1 wit: catalytic metal
atoms (8i' *o) 5or t:e pro1uctio o5 )>8<s. A :i9:=
temperature pulse1 arc=1isc:ar9e tec:i.ue :as bee
1evelope1 5or t:e syt:esis o5 si9le= a1 1ouble=wall
(&>8<s) carbo ao= tubes wit: arrower tube 1iameters
t:a t:ose obtaie1 wit: t:e stea1y arc met:o1 C4,'42D.
+ laser ablatio' a laser ablates a 9rap:ite tar9et i 5lowi9
ar9o at temperatures ear ,200

*. <:e 9rap:ite tar9et
cotais a small amout o5 a metal catalyst suc: as ic$el'
cobalt' iro' platium' yttrium. +t :as bee s:ow t:at bimetal=
lic catalysts are more pro1uctive t:a si9le metals. -arious
co5i9uratios o5 laser ablatio e2perimets were 1evelope1
5or t:e pro1uctio o5 si9le=wall carbo aotubes. <:ey
ra9e 5rom a si9le or a 1ual pulse1 laser to a cotiuous laser.
<:e yiel1' mea 1iameter a1 1iameter 1istributio ca be
varie1 by varyi9 t:e 9rowt: temperature' 9as' pressure'
catalyst compositio' laser pulse' etc.
)mall amouts o5 *8<s ca be 5orme1 by arc=1isc:ar9e
a1 laser vapori%atio w:ic: is really a limitatio to scale
up pro1uctio to t:e i1ustrial level. "ar9er .uatities o5 ao=
tubes ca be obtaie1 by t:e pyrolysis o5 a carbo source suc:
as carbo moo2i1e' :y1rocarbo 9ases (acetylee' et:ylee'
met:ae) or li.ui1 alip:atic saturate1 :y1rocarbos' over
metal catalysts supporte1 o silica' alumia or %eolite at tem=
peratures betwee /00 a1 ,000

*. <:e catalyst cosists o5
ao=si%e1 particles o5 a si9le metal (Fe' *o or 8i) or a mi2=
ture o5 metals. **-& :as bee reporte1 to be a low cost
met:o1 i pro1uci9 multiwall carbo aotubes a1 ao=
tube bu1les. Aot:er iteresti9 aspect is t:e ability to i1uce
t:e tube 9rowt: i a 9ive 1irectio wit: a cotrol o5 t:e 1i=
mesios a55ecte1 by t:e e2perimetal co1itios (ature o5
t:e catalyst' type o5 support' carbo source' temperature).
*omposites obtaie1 by 1ispersi9 aotubes ito 1i55eret
polymeric matrices :ave attracte1 wi1e attetio i or1er to
1evelop ultra=li9:twei9:t a1 e2tremely stro9 materials. +
polymer composites' 5iller 1ispersio as well as iter5acial
iteractios :ave bee s:ow to be crucial parameters 5or e=
:ace1 mec:aical properties. + 5act' oe o5 t:e bi99est c:al=
le9es is to obtai a :omo9eeous 1ispersio o5 carbo
aotubes i a polymer matri2 because va 1er >aals iter=
actios betwee i1ivi1ual tubes o5te lea1 to si9i5icat
a99re9atio or a99lomeratio' t:us re1uci9 t:e e2pecte1
property improvemets o5 t:e resulti9 composite. #ut to
1ate' 1espite t:e 5act t:at muc: pro9ress :as bee ma1e i
t:e processi9 tec:i.ues' t:e mec:aical improvemet
brou9:t about by icorporatio o5 aotubes remais mior
wit: re9ar1 to t:e potetial base1 o t:e properties o5 t:e
aotube itsel5. A review o5 <:osteso et al. C40D a1 Mo=
iru%%aam a1 >iey C44D illustrates t:e si9i5icat c:alle9es
t:at must be overcome be5ore t:e potetial is reali%e1.
&i55eret tec:i.ues to attempt to optimi%e t:e aotube
1ispersio wit:i t:e polymeric me1ium :ave bee use1.
<:ey iclu1e solutio mi2i9 C4/D' soicatio C47'47D' coa9u=
latio C48D' melt compou1i9 C49e/,D' i situ miiemulsio
polymeri%atio C,/'/2'/0D' o2i1atio C/4D or c:emical 5uc=
tioali%atio o5 t:e tube sur5ace C//e/7D' use o5 sur5actats
C/8D. <:e ultimate 9oal o5 t:ese processi9 co1itios is to
separate t:e i1ivi1ual aotubes i or1er to 9et a :omo9e=
eous 1ispersio t:rou9:out t:e matri2 w:ile t:e c:emical
5uctioali%atio is ite1e1 to bri9 some a1:esio betwee
t:e aotubes a1 t:e polymer t:us eabli9 e55ective stress
tras5er at t:e polymere5iller iter5ace.
-arious strate9ies 5or c:emical 5uctioali%atio o5 carbo
aotubes :ave alrea1y bee reporte1. <:ey ivolve covalet
or ocovalet attac:mets o5 5uctioal 9roups i or1er to
improve solubility a1 processability o5 *8<s i or9aic me=
1ia. <:e use o5 ball milli9 i speci5ic atmosp:ere allowe1 t:e
itro1uctio o5 5uctioal 9roups suc: as t:iol' amie' ami1e'
c:lori1e' carboyl' t:iomet:o2y a1 acyl c:lori1e' oto
carbo aotubes C/9D. Fuctioali%atio o5 )>8<s via elec=
troc:emical re1uctio o5 a variety o5 aryl 1ia%oium salts was
1escribe1 C70D. Fuctioali%atio ca also be carrie1 out
". #o$ob%a / Polymer 48 (2007) 4907e4920
4909
t:rou9: o2i1atio o5 t:e aotubes to i1uce 5ormatio o5
carbo2ylic' carboyl or :y1ro2yl 9roups to aotube e1=
caps or si1ewalls. <:ese 5uctioalities serve as ac:ori9
sites a1 ope t:e way to 5urt:er 1erivati%atio reactios
t:at ma1e t:e aotubes soluble i or9aic solvets. For e2am=
ple' *8<s 5uctioali%e1 by o2i1i%i9 aci1 treatmet ca be
submitte1 to 5luoriatio a1 subse.uet 1erivati%atio or to
amie reactios wit: al$ylcarbo2yl 9roups attac:e1 to t:e
aotubes C7,e74D. <:ese types o5 approac:es were success=
5ully applie1 5or t:e syt:esis o5 epo2y matrices i w:ic: t:e
aotubes were ite9rate1 ito t:e structure o5 t:e epo2y sys=
tem t:rou9: t:e si1ewall amio 5uctioal 9roups C72'70D.
>ater=soluble )>8<s' iteresti9 5or c:emical a1 biome1i=
cal applicatios' were also obtaie1 by 9ra5ti9 9lucosamie
a5ter pro1uci9 acyl c:lori1e o aci1=treate1 aotubes C7/D.
Fuctioali%atio via vi9orous o2i1atio processes 5ol=
lowe1 by covalet bo1i9 :as bee s:ow to itro1uce 1e5ect
sites wit:i t:e aotube structure w:ere sp
2
:ybri1i%atio is
coverte1 to sp
0
:ybri1i%atio' w:ic: may a55ect t:e
properties o5 t:e aotube itsel5 C77D. (lectroc:emical
mo1i5icatio C77'78D' sur5ace=iitiate1 polymeri%atio i
w:ic: polymer c:ais are covaletly couple1 oto t:e *8<
sur5ace w:ic: bears polymeri%atio iitiators C79e7,D :ave
bee use1 to miimi%e 1ama9e o5 *8<s. A t:e ot:er
:a1' s:ortei9 a1 mec:aical 1ama9e suc: as buc$li9'
be1i9 a1 1islo= catios i t:e carbo structures were also
i1uce1 by t:e so= icatio tec:i.ue use1 to 1isperse t:e
*8<s C72'70D. ):ortei9 t:e aotubes coul1 be 1etrimetal
sice it re1uces t:e :i9: aspect ratio w:ic: is oe o5 t:e
potetial a1vata9es o5 t:e aotubes 5or t:eir use as
rei5orci9 5iber i polymer matrices.
0. *:aracteri%atio o5 carbo aotubes
<:e morp:olo9y a1 state o5 1ispersio o5 t:e carbo ao=
tubes i a polymer matri2 ca be ivesti9ate1 usi9 trasmis=
sio electro microscopy (<(M) a1 atomic 5orce microscopy
(AFM).
):ow i Fi9. , are typical <(M ima9es o5 a toluee sus=
pesio o5 multiwall carbo aotubes (M>8<s) previously
soicate1 be5ore bei9 put oto copper 9ri1s 5or observatio
(Fi9. ,Ae&). Fi9. ,A reveals a broa1 1istributio i le9t:s
a1 1iameters w:ic: are i t:e ra9e o5 0.,e/ mm a1 ,0e
/0 m' respectively' a1 Fi9. ,# s:ows t:e curle1 structure
o5 a i1ivi1ual tube. <:e aotubes ca be :i9:ly eta9le1
wit: oe aot:er a1 5orm a itercoecti9 structure
(Fi9. ,*). Fi9. ,& ma9i5ies t:e aostructure o5 a multiwall
carbo aotube wit: several layers o5 9rap:itic carbo a1
a :ollow core.
Fi9. ,(eH s:ows t:e <(M ima9es o5 composite base1 o
styreeebuta1iee rubber ()#3) 5ille1 wit: 4 p:r o5 M>8<s
(p:r I parts per :u1re1 parts o5 rubber). #u1le1 M>8<s
ca be clearly i1eti5ie1 i Fi9. ,(. +1ivi1ual aotubes are
visuali%e1 i Fi9. ,F a1 J a1 blac$ spots correspo1 to
a99re9ates. A ma9i5icatio o5 oe bu1le (Fi9. ,H) s:ows
a orietatio o5 aotubes occurri9 probably 1uri9 :ot
pressi9 o5 t:e 5ilm. <:is orietatio is e2pecte1 to play
a role i mec:aical rei5orcemet.
<(M ima9es were obtaie1 o a 6(A" ,00*K++. Pure car=
bo aotubes were soicate1 i toluee a1 1roplets o5 t:e
suspesio were put oto copper 9ri1s 5or observatio. Lltra=
t:i 5ilms (70 m t:ic$) o5 t:e composite samples were cut by
meas o5 a ultramicrotome "(+*A L"<3A*L< L*< coole1
at 80

* by li.ui1 itro9e a1 put oto copper 9ri1s.
A11itioal i5ormatio o :ow t:e aotubes are actually
bei9 1istribute1 wit:i t:e polymer matri2 ca be obtaie1
5rom atomic 5orce microscopy. AFM :as bee s:ow to be
particularly well suite1 5or t:e c:aracteri%atio o5 5ille1 elasto=
mers a1 more 9eerally o5 :etero9eeous systems wit: com=
poets o5 1i55eret sti55ess C74D.
AFM ima9es o5 )#3 5ille1 wit: ,0 p:r o5 M>8<s' s:ow
i Fi9. 2' 9ive some i1icatio o5 a lar9er scale 1ispersio t:a
t:at 9ive i Fi9. ,. <:e bri9:ter 1omais easily i1eti5ie1 a1
rat:er :omo9eeously 1istribute1 i t:e 5ilm' are ascribe1 to
5iller a99re9ates. +t :as to be recalle1 t:at topo9rap:y a1 error
si9al reveal sur5ace rou9:ess w:ile p:ase ima9i9' w:ic:
provi1es variatio o5 sur5ace sti55ess' is particularly use5ul
i elastomeric composites 5ille1 wit: carbo aotubes o
accout o5 :u9e 1i55ereces i mo1uli betwee t:e two
compoets.
AFM ivesti9atios were per5orme1 wit: a <:ermomicro=
scope *P 3esearc: )ystem' usi9 tappi9 mo1e a1 p:ase im=
a9i9. <opo9rap:y' error si9al a1 p:ase ima9es were
simultaeously recor1e1 i or1er to 9et a topo9rap:ic a1
compositioal mappi9 o5 t:e sur5ace.
4. Mec:aical properties o5 aotube=base1
elastomeric composites
*ovetioal 5illers suc: as carbo blac$ or silica' w:e
a11e1 to elastomeric systems usually cause a icrease i t:e
mo1ulus ivolvi9 a :y1ro1yamic e55ect arisi9 5rom t:e i=
clusio o5 ri9i1 particles a1 a icrease i t:e cross=li$i9
1esity create1 by polymere5iller iteractios C7/e8,D.
<:e aisometry o5 particle a99re9ates or a99lomerates is
also e2pecte1 to icrease t:e mo1ulus as well as t:e occlu1e1
rubber' cosi1ere1 as a typical mec:aical iteractio a1
cosisti9 o5 elastomer c:ais trappe1 isi1e t:e 5iller a99re=
9ates. <:is occlu1e1 rubber' w:ic: is assume1 to be partially
s:iel1e1 5rom 1e5ormatio' icreases t:e e55ective 5iller
cocetratio.
<:e e2tet o5 5iller a99lomeratio :as a mar$e1 i5luece
o t:e low strai 1yamic properties o5 5ille1 vulcai%ates.
>:ile u5ille1 elastomers 1isplay little c:a9es i 1yamic
properties upo icreasi9 strai amplitu1e' t:e stora9e mo1=
ulus o5 5ille1 systems 1ecreases si9i5icatly s:owi9 a typical
o=liear be:avior $ow as t:e Paye e55ect C82D. A lar9e
amout o5 wor$ :as bee reporte1 o t:is e55ect but t:e
most accepte1 iterpretatio is t:e 9ra1ual brea$1ow o5
t:e 5iller etwor$ or 5iller MMetwor$i9;; as 1eomiate1 by
>a9 C80D' wit: icreasi9 strai amplitu1e. + :is paper
reviewi9 t:e e55ect o5 5iller c:aracteristics o 1yamic prop=
erties i coectio wit: processi9 co1itios a1 a11itives'
49,0 ". #o$ob%a / Polymer 48 (2007) 4907e4920
Fi9. ,. <(M ima9es. Ae&! pure M>8<s4 (eH! )#3/4 p:r M>8< composite.
>a9 1emostrates t:at t:e 5ormatio o5 t:e 5iller etwor$ is
ot oly t:e result o5 5illere5iller iteractios but also o5 poly=
mere5iller a1 polymerepolymer iteractios. 8evert:eless
ay processi9 met:o1 improvi9 1ispersio a1 avoi1i9
t:e 5ormatio o5 1irect iter=particle cotacts or icreasi9
t:e polymere5iller iteractios will 1epress 5iller etwor$i9.

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". #o$ob%a / Polymer 48 (2007) 4907e4920
Fi9. 2. AFM ima9es o5 )#3 5ille1 wit: ,0 p:r o5 multiwall carbo aotubes (M>8<s).
49,,
Also relate1 to rei5orcemet is t:e stress=so5tei9 e55ect
calle1 t:e MMMullis e55ect;;' observe1 at :i9: e2tesios a1
c:aracteri%e1 by a proouce1 loweri9 i t:e stress w:e
t:e 5ille1 vulcai%ate is e2te1e1 a seco1 time C84D. <:is
process' w:ic: ca be cosi1ere1 as a :ysteretic mec:aism
relate1 to eer9y 1issipate1 by t:e material 1uri9 1e5orma=
tio' correspo1s to a 1ecrease i t:e umber o5 elastically
e55ective etwor$ c:ais. +t results 5rom c:ais t:at reac: t:eir
limit o5 e2tesibility by strai ampli5icatio e55ects cause1 by
t:e iclusio o5 u1e5ormable 5iller particles C8/'87D. )tress=
so5tei9 i 5ille1 rubbers :as bee associate1 wit: t:e rupture
properties a1 a .uatitative relatios:ip betwee total :yster=
esis (area betwee t:e 5irst e2tesio a1 t:e 5irst release
curves i t:e 5irst e2tesio cycle) a1 t:e eer9y re.uire1
5or rupture :as bee 1erive1 C87'88D.
A accout o5 t:eir e2tremely :i9: mo1uli' carbo ao=
tubes are e2pecte1 to provi1e muc: :i9:er rei5orcemet
e55ects t:a covetioal 5illers. #y usi9 a atomic 5orce mi=
croscope' )alvetat et al. C89D measure1 elastic mo1uli o5
)>8<s arou1 , <Pa a1 wit: a tec:i.ue base1 o electri=
cally i1uce1 mec:aical 1e5lectios o5 M>8<s i a trasmis=
sio electro microscope' istea1 o54 elastic be1i9 mo1ulus
was 5ou1 to 1ecrease s:arply (5rom about , to 0., <Pa) wit:
icreasi9 1iameter (5rom 8 to 40 m) C90D. A t:e ot:er :a1'
tesile stre9t:s o5 i1ivi1ual M>8<s were measure1 wit:
a MMaostressi9 sta9e;; locate1 wit:i a scai9 electro
microscope C9,D. +t was s:ow t:at t:e M>8<s bro$e i
t:e outermost layer a1 t:e tesile stre9t: o5 t:is layer ra9e1
5rom ,, to 70 JPa w:ile t:e Nou9;s mo1ulus varie1 5rom
270
)ome stu1ies also report t:e use o5 *8<s i elastomeric
matrices. )>8<s C,7D a1 M>8<s C97D were icorporate1
i atural rubber. + t:e 5irst paper' t:e rei5orci9 e55ect o5
t:e aotubes is reveale1 by a 1yamic mec:aical aalysis
s:owi9 a icrease i t:e stora9e mo1ulus. + t:e seco1 pa=
per' tesile stre9t:' tesile mo1ulus a1 tou9:ess are s:ow
to icrease wit: t:e 5iller loa1i9 w:ile t:e elo9atio at brea$
1ecreases. <esile tests per5orme1 o a silicoe rubber mi2e1
wit: )>8<s also 1isplay 1ramatic improvemet i t:e me=
c:aical properties as a 5uctio o5 5iller cotet C,7D. <:e
iitial mo1ulus icrease :as bee s:ow to be appro2imately
liear wit: wei9:t 5ractio' wit: a slope o5 200?/wt.?.
>e :ave ivesti9ate1 t:e e55ect o5 icorporatio o5 multi=
wall carbo aotubes (M>8<s) ito elastomeric matrices.
<:e level o5 rei5orcemet is assesse1 t:rou9: a mec:aical
c:aracteri%atio as a 5uctio o5 aotube loa1i9.
Fi9. 0 s:ows' as a typical e2ample' stressestrai curves 5or
a pure styreeebuta1iee rubber ()#3) a1 5or M>8<s/)#3
composites a1 t:e e2perimetal mec:aical properties are
liste1 i <able ,. <:e styreeebuta1iee rubber cotais
/
,0 p:r
7 p:r
4
/ p:r
0
to 9/0 JPa.
)i9i5icat improvemets i mec:aical properties o5 poly=
meric matrices by *8< a11itio :ave bee reporte1. Allaoui
2
et al. C92D 5ou1 t:at t:e icorporatio o5 , wt.? o5 M>8<s
ito a epo2y matri2 results i a icrease i t:e Nou9;s
mo1ulus a1 i t:e yiel1 stre9t: by' respectively' ,00 a1
,
200? compare1 to t:e pure matri2. 3ei5orcemet e55ects
were also observe1 by a11i9 M>8<s i p:eolic resis
C90'94D a1 i polystyree C9/D. 8evert:eless' i polyet:ylee
0
0 p:r
4 p:r
2 p:r
, p:r
composites' Mc8ally et al. C97D observe1 a 1ecrease i t:e
ultimate tesile stre9t: a1 elo9atio at brea$ wit: a11itio
o5 M>8<s su99esti9 poor iter5acial iteractios betwee
t:e M>8<s a1 t:e polymer matri2.
0 ,00 200 000 400 /00
strai ( )
Fi9. 0. )tressestrai curves 5or pure )#3 a1 M>8</)#3 composites. <:e
5iller cotet is e2presse1 i p:r (p:r I parts per :u1re1 parts o5 rubber).
49,2 ". #o$ob%a / Polymer 48 (2007) 4907e4920
<able ,
Mec:aical properties o5 )#3 a1 )#3 composites
Filler loa1i9
(p:r)
(
(MPa)
)tress at ,00?
(MPa)
)tress at 200?
(MPa)
)tress at 000?
(MPa)
)tress at brea$
(MPa)
)trai at brea$
(?)
O
rubber
0 0.24 0.49 0.7, 0.97 0.9/ 000 7./4
, 0.0/ 0.// 0.8/ ,.2, ,.74 090 /.99
2 0.40 0.70 ,.,0 ,.72 2.08 070 /./9
0 0./9 0.89 ,.47 2.,, 0.,0 420 4.92
4 0.7, 0.87 ,./, 2.02 2.8/ 070 4.80
/ 0.70 ,.,, ,.89 2.84 0.07 0/0 4.74
7 0.90 ,.48 2./4 0.77 4.,4 0/0 0.8,
,0 ,.40 2.44 0.9, e 4.92 270 0.,/
O
rubber
represets t:e e.uilibrium swelli9 ratio o5 t:e rubber p:ase i toluee.
2/ wt? o5 styree uits. <:e microstructure o5 t:e buta1iee
p:ase is t:e 5ollowi9! ,0? cis' ,7? tras' 70? ,'2.
<:e straiestress measuremets were carrie1 out at room
temperature o strips o5 /0 / 0.2 mm
0
betwee
two clamps by meas o5 a se.uece o5 icreasi9 wei9:ts
attac:e1 to t:e lower clamp. <:e 1istace betwee two
mar$s o t:e
superior e55iciecy as rei5orci9 5illers' it is iteresti9 to
compare t:e e2perimetal 1ata wit: t:eoretical mo1els i=
te1e1 to pre1ict t:e properties o5 composite materials. <:e
Jut: mo1el C,02D oly base1 o t:e aspect ratio' 5' a1 volume
5ractio' 5' o5 5iller' :as bee wi1ely use1 to accout 5or t:e
c:a9e i mo1ulus i 5ille1 elastomers!
sample was measure1 wit: a cat:etometer a5ter allowi9 su5=
5iciet time (,0 mi a5ter a11i9 a wei9:t) 5or e.uilibratio.
( I (
0

, P
0!775 5P ,!725
2
5
2
4 Q,R
*learly t:ere is rei5orcemet as evi1ece1 by cosi1erable
improvemets i sti55ess a1 tesile stre9t: o5 t:e compos=
ites wit: t:e 5iller loa1i9. >it: t:e a11itio o5 oly , p:r o5
M>8<s (p:r I parts per :u1re1 parts o5 rubber)' a 4/? i=
crease i elastic mo1ulus a1 a 70? icrease i t:e tesile
stre9t: are ac:ieve1. <:e sli9:t re1uctio i t:e ultimate
strai observe1 5or t:e sample 5ille1 wit: ,0 p:r o5 M>8<s
wit: re9ar1 to t:e pure polymer may result 5rom t:e presece
o5 a99re9ates icreasi9 wit: t:e 5iller cotet.
As t:ese systems are submitte1 to sul5ur vulcai%atio' )H=
5uctioali%e1 M>8<s were also use1 i or1er to 1etermie
w:et:er t:e 9ra5te1 9roups are ivolve1 i t:e vulcai%atio
process' t:us bri9i9 some a1:esio betwee t:e or9aic
a1 ior9aic p:ases. 8o 5urt:er improvemet i t:e mec:a=
ical properties is 9aie1 wit: re9ar1 to t:e results obtaie1
wit: utreate1 carbo aotubes w:ic: is probably 1ue to
t:e small 1e9ree o5 aotube 5uctioali%atio w:ic: is
arou1 ,?. + a recet paper o5 Milter et al. C98D 1eali9
wit: aocomposites base1 o et:yleeeviyl acetate copoly=
mer i combiatio wit: several types o5 or9aoclay or carbo
aotubes' c:emically 5uctioali%e1 carbo aotubes bear=
i9 acetate or :y1ro2y moieties at t:eir sur5ace are see to
1isplay less iteractios t:a clay=5ille1 systems at similar
loa1i9. <:e aut:ors also metio t:e limite1 1e9ree o5 sur=
5ace 5uctioali%atio.
<:e e2tet o5 rei5orcemet 1epe1s o several 5iller c:ar=
acteristics suc: as its mo1ulus' 9eometry a1 orietatio
wit:i t:e :ost matri2 C99',00D. <:e e2tremely :i9: mo1ulus
o5 carbo aotubes (t:e value o5 , <Pa is usually reporte1 i
t:e literature) may provi1e composites wit: mec:aical prop=
erties t:at e2cee1 t:ose o5 ay previously e2isti9 materials.
A t:e ot:er :a1' accor1i9 to t:eories a1 mo1els 1escrib=
i9 t:e tesile be:avior o5 5ille1 composites' 5ibers are t:e
most e55iciet at e:aci9 sti55ess C,0,D. + or1er to ta$e a1=
vata9e o5 t:e 5ull potetial o5 carbo aotubes 5or ay 9ive
applicatio i polymer aocomposites a1 to u1ersta1 t:eir
( a1 (
0
are t:e mo1uli o5 t:e composite a1 t:e u5ille1
elastomer' respectively.
<:e Halpie<sai mo1el C,00D also pre1icts t:e sti55ess o5
t:e composite as a 5uctio o5 t:e aspect ratio. <:e lo9itu1i=
al mo1ulus measure1 parallel to per5ectly oriete1 5ibers is
e2presse1 i t:e 9eeral 5orm!
( I (
0
Q, P 25 5:RSQ, 5:R Q2R
w:ere : is 9ive by
: I

(
5
S(
0
,

(
5
S(
0
P 25

Q0R
(
5
bei9 t:e mo1ulus o5 t:e 5iller.
+ elastomeric composites' (
5
C (
0
' so (.. (2) re1uces to
( I (
0
Q, P 25 5RSQ, 5R Q4R
+ Fi9. 4' t:e e2perimetal values o5 (/(
0
are
compare1 wit: t:e Jut: a1 Halpie<sai pre1ictios usi9
t:e respec= tive aspect ratios o5 40 a1 4/ to 5it t:e 1ata.
>:ile t:e Jut: mo1el 1eparts 5rom t:e e2perimetal results
at t:e :i9:= est 5iller loa1i9s' t:e Halpie<sai mo1el'
5or per5ectly ali9e1 5ibers' s:ows 9oo1 a9reemet wit:i t:e
volume 5rac= tio ra9e ivesti9ate1. +t is iteresti9 to
metio t:at bot: mo1els yiel1 almost similar aspect ratios.
<:e values re.uire1 to 5it t:e e2perimetal 1ata are lower t:a
t:at calculate1 5rom t:e avera9e 1imesios o5 t:e M>8<s.
+t is most probably 1ue to a99re9atio o5 t:e aotubes
w:ic: re1uces t:e aspect ratio o5 t:e rei5orcemet.
As alrea1y metioe1' aotube ali9met occurri9' par=
tially 1uri9 5ilm processi9 or' o5 course 1uri9 stretc:i9'
:as to be ta$e ito accout i t:e mec:aical be:avior o5
t:e composites. P:ase=cotrast tappi9=mo1e AFM ima9i9
o5 silica=5ille1 elastomers u1er uia2ial stretc:i9 :as 9reatly
improve1 our molecular u1ersta1i9 o5 rubber rei5orce=
met C,04D. AFM observatio o5 carbo aotube=5ille1 )#3
was also carrie1 out i or1er to :ave a loo$ at t:e be:avior
(
/
(
0
". #o$ob%a / Polymer 48 (2007) 4907e4920
49,0
8
(2perimetal poits
7
Jut: mo1el (5S40)
Halpi/<sai mo1el (5S4/)
7
/
4
0
2
,
0
0 0.0, 0.02 0.00 0.04 0.0/
volume 5ractio o5 5iller
Fi9. 4. (2perimetal mo1uli plotte1 versus volume 5ractios o5 M>8<s a1
compariso wit: t:eoretical pre1ictios.
Fi9. /. )tretc:i9 1evice 5or AFM e2perimets.
o5 5iller a99re9ates upo applicatio o5 a macroscopic strai
a1 also a5ter suppressio o5 t:e strai a1 seco1 stretc:i9.
<:e sample (arou1 200 mm t:ic$) was put o a small stretc:=
i9 1evice specially 5itte1 to t:e sample :ol1er o5 t:e multi=
mo1e AFM (Fi9. /). <:e 1e5ormatio is maitaie1' t:a$s
to t:e clamps screwe1 i t:e bo1y o5 t:e 1evice. <:e strai
ca be evaluate1 5rom t:e measuremet o5 t:e 1istace be=
twee t:e two i$ lies 1raw o t:e sur5ace o5 t:e 5ilm.
P:ase ima9es o5 5ilms stretc:e1 to e2tesio ratio (ratio o5
t:e le9t: o5 t:e sample i t:e 1irectio o5 strai to t:e iitial
le9t: be5ore 1e5ormatio) e.ual to ,.8 a1 t:e 2.8 are s:ow
i Fi9. 7 5or t:e ,0 p:r 5ille1 composite. Applyi9 a uia2ial
1e5ormatio to t:e sample results i orietatio o5 t:e 5iller a9=
9re9ates appeari9 as w:ite areas. At t:e :i9:est elo9atio'
t:e bu1les ca be see to be bro$e up ito lo9 strai9:t
structures. A .uite 1i55eret morp:olo9y is obtaie1 a5ter re=
la2atio o5 t:e sample to t:e ustresse1 state (Fi9. 7a) w:ic:
is i 5act more 1e5orme1 t:a t:e ori9ial material o accout
o5 t:e permaet 1e5ormatio e2:ibite1 by 5ille1 elastomers.
+ t:e rela2e1 sample' t:e 1ata su99est a rotatio o5 1omais
a1 a orietatio o5 t:e bu1les perpe1icular wit: t:e stress
1irectio. A seco1 stretc:i9 at a e2tesio ratio o5 2.0 :as
ot t:e same e55ect as t:at per5orme1 o t:e ori9ial material.
Aot:er i1irect evi1ece o5 c:ai orietatio i1uce1 by
tube ali9met :as bee obtaie1 by i5rare1 aalysis o5
stretc:e1 M>8<=5ille1 atural rubber. 8atural rubber is able
to crystalli%e u1er strai' a p:eomeo t:at ca be 5ollowe1
by i5rare1 spectroscopy w:ere it is see t:at t:e ba1 associ=
ate1 wit: t:e *eH out=o5=plae vibratio' locate1 at 807 cm
,
i t:e isotropic state s:i5ts to :i9:er waveumbers upo crys=
talli%atio (Fi9. 8a). <:e c:a9e i waveumber upo uia2ial
stretc:i9 is observe1 at a lower e2tesio ratio 5or t:e com=
posite t:us s:owi9 t:at t:e strai=i1uce1 crystalli%atio pro=
cess occurs at a lower 1e5ormatio i t:e presece o5 carbo
aotubes as a result o5 a stro9er orietatio o5 polymer
c:ais i1uce1 by ali9met o5 5iller bu1les (Fi9. 8b). <:is
Fi9. 7. <appi9=mo1e AFM p:ase=cotrast ima9es (/ mm / mm) 5or t:e ,0 p:r M>8<=5ille1 )#3 u1er two 1i55eret elo9atios.
>
a
v
e

u
m
b
e
r
s

(
c
m
=
,
)
49,4 ". #o$ob%a / Polymer 48 (2007) 4907e4920
Fi9. 7. AFM ima9es a5ter total release o5 t:e stress (a) a1 subse.uet stretc:i9 at a I 2.0 (b).
iterpretatio w:ic: is speculative ee1s to be co5irme1 by
5urt:er ivesti9atios o stretc:e1 systems.
/. (2perimetal evaluatio o5 t:e iteractios betwee
carbo aotubes a1 elastomers
Most o5 t:e t:eoretical mo1els pre1icti9 t:e elastic mo1=
ulus o5 5ille1 rubbers assume ui5orm 1ispersio a1 per5ect
a1:esio betwee t:e polymer a1 t:e matri2. <(M aalysis
o5 t:e composites :as reveale1 a poor 1ispersio. A t:e ot:er
:a1' t:e e2istece o5 iter5acial iteractios betwee t:e
aotubes a1 t:e matri2' w:ic: is critical i mec:aical rei=
5orcemet' is ot obvious. <:e stro9 restrictio i e.uilibrium
swelli9 i toluee wit: t:e M>8< cotet (<able ,) woul1
su99est t:at a certai polymere5iller bo1i9 or a state o5
a1:esio betwee t:e two p:ases is establis:e1. #ut a more
realistic iterpretatio o5 t:e swelli9 1e5icit i t:e presece
o5 carbo aotubes woul1 be t:e occlusio o5 rubber ito
t:e a99re9ates. &uri9 processi9' carbo aotubes are
well 1isperse1 i toluee solutio a1 t:e rea99lomerate a5ter
icorporatio o5 polymer t:us etrappi9 elastomer molecules
w:ic: be:ave li$e 5iller a1 1o ot swell C,0/D. A t:e ot:er
:a1' some :ysteresis (area betwee t:e 5irst stretc: a1 t:e
seco1 stretc:) :as bee observe1 at lar9e strais 5or t:e sam=
ples 5ille1 wit: M>8<s (Fi9. 9). A5ter stretc:i9 a1 release'
t:e sample e2:ibits a lar9e 1e9ree o5 permaet 1e5ormatio.
<:e :ysteresis' also calle1 MMstress=so5tei9 e55ect;; :as bee
s:ow to correspo1' i t:e case o5 covetioal composites'
to a loss o5 elastic c:ais ta$i9 place at t:e polymere5iller
iter5ace C87D. +t is very low i t:e case o5 poor polymere5iller
iteractios C,07D. + view o5 t:e AFM observatios' we are i
a positio to believe t:at i carbo aotube=5ille1 samples'
t:e stressestrai be:avior o5 t:e composites cotais a lar9e
cotributio arisi9 5rom orietatioal e55ects a1 t:at t:e
proouce1 loweri9 i t:e stress observe1 i t:e seco1
stretc:i9 correspo1s to a loss o5 orietatio oce t:e stress
is release1.
&yamic mec:aical aalysis measuremets were per=
5orme1 o pure atural rubber (83) a1 composites wit: up
to ,0 p:r o5 M>8<s. <:e temperature 1epe1ece o5 t:e
(a)
2.2
2
,.8
,.7
T S /./
T S 2
T S 4.2/
(b)
844
840
842
84,
83 U M>8< (2./ p:r)
83
,.4 840
,.2
809
,
808
0.8
807
0.7
880
870 840 820 800 780
807
, 2 0 4 / 7
>aveumbers (cm
=,
) e2tesio ratio T
Fi9. 8. ):i5t o5 t:e *eH out=o5=plae absorptio ba1 upo crystalli%atio o5 u5ille1 atural rubber (a) a1 1epe1ece o5 its waveumber o t:e e2tesio ratio
a (b).
t
a


1
e
l
t
a
)
t
o
r
a
9
e

m
o
1
u
l
u
s

J
V

(
P
a
)
8
o
m
i

a
l

s
t
r
e
s
s

(
M
P
a
)
". #o$ob%a / Polymer 48 (2007) 4907e4920
49,/
/
4
0
5irst a1 seco1 stretc:
2
,
0
0 /0 ,00 ,/0 200 2/0
)trai ( )
Fi9. 9. Mullis :ysteresis 5or t:e )#3/,0 p:r M>8< composite.
stora9e mo1ulus J
0
a1 o5 t:e loss 5actor ta 1 5or t:e u5ille1
a1 ,0 p:r M>8<=5ille1 83 are reporte1 i Fi9. ,0. Arou1
70

*' t:e stora9e mo1ulus J
0
1ecreases abruptly w:ile
ta 1 passes t:rou9: a ma2imum. <:is rela2atio process is
o5 course relate1 to a eer9y 1issipatio associate1 wit: t:e
9lass trasitio p:eomeo o5 t:e rubber p:ase. As see i
Fi9. ,0' t:e 9lass trasitio temperature ta$e at t:e ma2imum
o5 ta 1 1oes ot c:a9e si9i5icatly upo icorporatio o5
t:e aotubes i t:e matri2' sice t:e <
9
values
icreases 5rom 7,.0

* 5or pristie 83 to e/9.8

* 5or t:e
5ille1 sam= ple. <:is small e55ect o5 M>8<s o t:e 9lass
trasitio tem= perature o5 t:e rubber caot be a si9 o5 a
lac$ o5 a1:esio o5 t:e 5iller to t:e elastomer sice several
aut:ors :ave reporte1 little i5luece o5 t:e presece o5
carbo blac$s o <
9
eve at :i9: 5iller loa1i9 a1 wit:
rei5orci9 blac$s C82D.
+ covetioal composites' t:e a1sorptio o5 polymer
molecules 9ives rise to t:e 5ormatio o5 a a1sorptio layer'
evi1ece1 by 1ielectric or soli1 state 8M3 spectroscopies
C/',07D' w:ose t:ic$ess :as bee estimate1 arou1 2 or
0 m a1 w:ere motios o5 c:ai uits are more restricte1
t:a t:ose i t:e mobile p:ase. <:e loss i se9metal mobility
woul1 result i a icrease i <
9
a1 most probably i a
c:a9e o5 t:e t:ermal e2pasio o5 t:e 5ree volume.
)urprisi9ly' ivesti9atios carrie1 out o a
styreeebuta1iee copolymer
5ille1 wit: 1i55eret carbo blac$s' s:ow t:at <
9
is oly i=
crease1 by about ,

* by every /0 p:r o5 :i9:ly rei5orci9
5iller but remais ua55ecte1 by relatively iert carbo blac$
w:ile t:e coe55iciet o5 e2pasio o5 t:e polymer compoet
o5 t:e composite is substatially ua55ecte1 by all carbo
blac$s i t:e rubbery re9io C,08D.
For composites o5 poly(met:yl met:acrylate (PMMA) a1
umo1i5ie1 )>8<s ta 1 pea$ broa1es but t:e pea$ is at t:e
,0/

* value o5 bul$ polymer 5or t:e u5uctioali%e1 com=
posite w:ile t:e ami1e=5uctioali%e1 PMMA composite 1is=
plays a ta 1 pea$ s:i5te1 to a :i9:er temperature by 00

*
wit: re9ar1 to t:e pure polymer C/7D. <:e ami1e=5uctioal=
i%e1 PMMA composite 1isplays a ta 1 pea$ s:i5te1 to a
:i9:er temperature by 00

* wit: re9ar1 to t:e pure polymer.
<:e au= t:ors su99est t:e e2istece o5 1iscrete iterp:ase
re9ios wit: umo1i5ie1 )>8<s 1ue to clusteri9 o5 tubes
w:ile t:e 5uc= tioali%e1 composite system :as a stro9er
iter5acial bo1i9 via t:e covalet li$a9es betwee t:e
two p:ases lea1i9 to t:e 5ormatio o5 a e2tesive re9io
wit: altere1 properties. From )(M aalysis o5
M>8</polycarboate composites' PoW tsc:$e et al. C,09D a1
&i9 et al. C,,0D observe1 tube 1iam= eters lar9er t:a t:ose o5
t:e pristie M>8<s use1 i t:e sam= ple preparatio a1
su99est t:e e2istece o5 a a1sorbe1 layer o5 polymer o t:e
tubes; sur5ace but u5ortuately 1o ot me= tio i5 a s:i5t i
<
9
is associate1 wit: t:e tube coati9. A11i= tioally' a
1epe1ece o5 t:e aotube cotet o t:e 9lass trasitio
temperature was observe1 5or M>8</epo2y com= posites
wit: a stro9er icrease i <
9
5or samples cotaii9 amio=
5uctioali%e1 aotubes C//D. <:e aut:ors 1o ot e2= clu1e a
possible e55ect o5 t:e a11itioal 5uctioal 9roups o t:e
curi9 reactio o5 t:e epo2y matri2.
As see i Fi9. ,0' at :i9:er temperatures' t:e stora9e mo1=
ulus reac:es a plateau arou1 0.0 MPa at 20

* 5or t:e
u5ille1 83 a1 7.2 MPa 5or t:e composite. <:is lar9e
mo1ulus icrease i t:e rubbery plateau' w:ic: represets t:e
rei5orcemet pro= vi1e1 by t:e carbo aotubes' is muc:
:i9:er t:a t:at ob= taie1 i t:e tesile mec:aical
c:aracteri%atio because it iclu1es t:e cotributio arisi9
5rom 5illere5iller iteractios. <:is cotributio is usually
evi1ece1 t:rou9: t:e strai 1epe= 1ece o5 t:e stora9e
mo1ulus. 3ei5orce1 elastomers a1 more 9eerally systems
cotaii9 5iller 1ispersios are c:aracter=
i%e1 by a o=liear viscoelastic be:avior' $ow as t:e
MMPaye
,0
,0
,0
9
,0
8
,0
7
,0
7
,0
/
0 p:r
,0 p:r
,0 p:r
0 p:r
0
2./
2
,./
,
0./
0
e55ect;; C,,,',,2D. >it: re9ar1 to t:e u5ille1 rubber' t:e com=
posite cotaii9 ,0 p:r o5 M>8<s :as bee s:ow to 1isplay
a 9reater Paye e55ect probably associate1 wit: t:e brea$1ow
o5 lar9e a99lomerates o5 carbo aotubes (Fi9. ,,).
+teractios betwee t:e aotube bu1les a1 t:e matri2
are re.uire1 5or a e55iciet stress tras5er 5rom t:e matri2 to
t:e aotubes. 3ama spectroscopy :as prove1 to be very se=
sitive 5or a evaluatio o5 t:e stre9t: o5 t:e polymere5iller i=
ter5ace. + 5act' carbo aotubes e2:ibit well=1e5ie1 3ama
pea$s locate1 5or our M>8<s at ,04/' ,/9/ a1 2700 cm
,
'
respectively' assi9e1 to t:e 1isor1ere1 9rap:ite structure (&
=80 =70 =40 =20 0
<emperature (X*)
Fi9. ,0. <emperature 1epe1ece o5 t:e stora9e mo1ulus a1 o5 t:e loss 5actor
5or pure 83 a1 83/,0 p:r M>8< composite.
ba1)' ta9etial stretc:i9 mo1e o5 carboecarbo bo1s
(J ba1) a1 to t:e overtoe o5 t:e & ba1 (J
0
ba1)
(Fi9. ,2). *ooper et al. C,,0D :ave s:ow t:at t:e J
0
ba1
s:i5ts
to a lower waveumber upo applicatio o5 a tesile stress o
)
t
o
r
a
9
e

m
o
1
u
l
u
s

J
V

(
P
a
)
+

t
e

s
i
t
y
v
o
l
u
m
e

r
e
s
i
s
t
i
v
i
t
y

(
Y
.
c
m
)
v
o
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e

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49,7 ". #o$ob%a / Polymer 48 (2007) 4907e4920
0 ,0
7
2./ ,0
7
2 ,0
7
,./ ,0
7
, ,0
7
/ ,0
/
0
,0 p:r
0 p:r
< S 298B
composites base1 o epo2y resis a1 si9le or multiwall car=
bo aotubes. Accor1i9 to t:e aut:ors' t:is s:i5t i1icates
stress tras5er 5rom t:e matri2 to t:e aotubes a1 :ece re=
i5orcemet. 8evert:eless' t:e rates o5 ba1 s:i5t were 5ou1
to 1i55er 5or all t:e aotubes ivesti9ate1. Poorer 1ispersio'
worse a1:esio a1 lower aspect ratio were ivo$e1 to accout
5or smaller s:i5t rate. + our case' t:e 3ama pea$s were ot
5ou1 to s:i5t w:e t:e composite is sub@ecte1 to a e2te=
sioal strai' i1icati9 wea$ iter5acial iteractios.
7. (lectrical properties
+ a11itio to improvi9 t:e mec:aical properties' blac$
5illers (carbo blac$ or carbo aotubes) impart co1uctivity
to low resistivity elastomeric matrices. + may applicatios'
0., , ,0 ,00
)trai ( )
Fi9. ,,. )trai 1epe1ece o5 t:e stora9e mo1ulus 5or pure 83 a1 83/,0 p:r
M>8< composite.
&isor1ere1
ba1 (&)
Jrap:itic
ba1 (J)
Avertoe
o5 t:e & ba1
)#3 U M>8<s (,0 p:r)
M>8<s
,200 ,700 2000 2400 2800
3ama s:i5t cm
=,
Fi9. ,2. 3ama spectra o5 pure M>8<s a1 )#3/M>8< composite at
/,4 m e2citatio. +tesities o5 t:e spectra :ave bee a1@uste1 to
improve presetatio.
electrical co1uctivity is re.uire1 to 1issipate electrostatic
c:ar9e. <:e electrical properties are stro9ly a55ecte1 by t:e
5iller cocetratio' t:e 5iller morp:olo9y suc: as particle
si%e a1 structure as well as 5illere5iller a1 5illerematri2
iter= actios w:ic: 1etermie t:e state o5 1ispersio.
8aotube ori= etatio will also i5luece t:e electrical
co1uctivity. <:ere is a critical volume 5ractio $ow as t:e
percolatio t:res:ol1 at w:ic: t:e co1ucti9 iclusios 5orm
a itercoecti9 5iller etwor$ lea1i9 to a s:arp 1rop i
t:e electrical resistace.
Fi9. ,0 s:ows t:e e55ect o5 5iller loa1i9 o t:e volume re=
sistivity o5 carbo blac$ (8000 5rom *abot) (*#) a1 M>8<=
5ille1 composites base1 o isulati9 styreeebuta1iee
rubber. (lectrical resistivity measuremets were 1etermie1
o samples o5 ,0 20 0.2 mm
0
by measuri9 t:eir resis=
tace o a :i9: resistace meter (Beit:ley 7/,7A) betwee
two co1uctive rubber electro1es wit: a alterative volta9e
o5 , -. <:is alterative volta9e is ee1e1 to avoi1 a
bac$9rou1 curret e55ect. <:e measure1 resistaces 3
were t:e co= verte1 ito volume resistivity r usi9 t:e
5ollowi9 e.uatio!
r I
3)
Q/R
1
(a)
,0
,/
(b)
,0
,/
,0
,0
,0
,0
,0
,,
,0
,,
,0
9
,0
9
,0
7
,0
7
,0
/
,0
/
,000
,000
0 2 4 7 8 ,0 ,2 0 ,0 20 00 40 /0
5iller loa1i9 (p:r)
5iller loa1i9 (p:r)
Fi9. ,0. -olume resistivity a9aist 5iller loa1i9 5or )#3 composites 5ille1 wit: M>8<s (a) or *# (b).
v
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". #o$ob%a / Polymer 48 (2007) 4907e4920
49,7
w:ere ) is t:e cross=sectioal area perpe1icular to t:e curret
a1 1 is t:e t:ic$ess o5 t:e sample betwee t:e two
electro1es.
<:e cotiuous etwor$ is 5orme1 at a lower 5iller loa1i9
o5 t:e aotube bu1les wit: M>8<s t:a wit: *#. <:e
:i9:er aspect ratio o5 t:e aotube bu1les w:ic: icreases
t:e probability o5 particleeparticle cotacts e2plai t:e low
percolatio t:res:ol1. Aur results are i a9reemet wit: t:ose
o5 Fla1i et al. C,,4D a1 o5 <:o9rua9 et al. C,,/D w:o
s:owe1 t:at t:e percolatio=t:res:ol1 cocetratio i com=
posites is arou1 ,0e,/ wt.? 5or carbo 5iber a1 :i9: struc=
ture carbo blac$ a1 arou1 40e/0 wt.? 5or low structure
carbo blac$ a1 9rap:ite. <:e :i9: electrical co1uctivity
o5 carbo aotube=5ille1 composites obtaie1 at a relatively
low volume 5ractio is oe o5 t:e ma@or attributes o5 carbo
aotubes sice t:at allows to retai t:e 1esire1 mec:aical
properties. <:e :i9:er loa1i9s o5 carbo blac$' re.uire1 to
provi1e t:e same level o5 co1uctivity' o5te lea1 to a i=
crease i viscosity a1 cose.uetly to a re1uctio a1 pro=
cessi9 ease a1 ca be associate1 wit: a re1uctio i
mec:aical properties.
)ice t:e resistivity o5 t:e u5ille1 elastomer is several or=
1ers o5 ma9itu1e lar9er t:a t:at o5 t:e 5ille1 vulcai%ate' ay
rearra9emet o5 t:e 5iller particle 1istributio i1uce1' 5or e2=
ample' by applicatio o5 a 1e5ormatio' lea1s to a c:a9e i
t:e vulcai%ate co1uctivity. )i9i5icat c:a9es i electrical
resistivity a9aist 1e5ormatio i blac$=5ille1 composites
:ave alrea1y bee reporte1 i t:e literature C,,4',,7e,2,D.
At small 1e5ormatios' c:a9es i 1yamic mo1uli wit: strai
amplitu1e :ave bee 5ou1 to be very similar to c:a9es i
co1uctivity wit: strai amplitu1e C,,7e,,8D. <:e stora9e
mo1ulus' J
0
a1 t:e 1yamic co1uctivity :ave bee s:ow
to 1ecrease i a similar way as t:e amplitu1e o5 1yamic os=
cillatio was icrease1. <:e re1uctio o5 bot: co1uctivity
a1 mo1ulus :as bee associate1 wit: t:e brea$1ow o5 t:e
carbo etwor$.
Here' is cosi1ere1' t:e e55ect o5 a uia2ial 1e5ormatio o
t:e electrical properties o5 a material w:ose M>8< co=
cetratio is above t:e isulatoreco1uctor trasitio re9io.
<o measure c:a9es i resistivity' strips (si%e! /0 ,/
, mm
0
) were stretc:e1 wit: a maual stretc:i9 mac:ie i
Measuremets were ma1e at about / m a5ter eac: elo9atio
step. )tatic resistace' 3' o5 t:e vulcai%ate u1er uia2ial e2=
tesio was measure1 i t:e 1irectio o5 strai a1 t:e resis=
tivity' r' was calculate1 5rom t:e 5ollowi9 e2pressio!
r I
3)
I
3)
0
Q7R
" a
2
"
0
w:ere )
0
a1 "
0
are' respectively' t:e iitial cross=
sectioal area a1 le9t: betwee t:e two clamps be5ore
1e5ormatio a1 a is t:e e2tesio ratio. L1er uia2ial
e2tesio' t:e 1e= 5orme1 le9t:' "' becomes a"
0
w:ile ) is
e.ual to )
0
/a' i5 t:e volume remais costat 1uri9
1e5ormatio.
<:e c:a9e i resistivity 1uri9 uia2ial e2tesio 5or a
composite 5ille1 wit: ,0 p:r o5 M>8<s is s:ow i Fi9. ,/.
+t is observe1 t:at t:e resistivity o5 t:e sample icreases 9ra1=
ually wit: t:e applie1 strai. Aur results 1i55er 5rom t:ose
presete1 by Nama9uc:i et al. C,2,D 5or carbo blac$=5ille1
elastomers w:ere a icrease i resistivity at low strais is
observe1' 5ollowe1 by a subse.uet re1uctio at :i9:er e2te=
sios. <:e aut:ors e2plai t:e rise i t:e iitial resistivity by
a brea$1ow o5 carbo blac$ a99lomerates ito smaller a99re=
9ates a1 cose.uetly a re1uctio i t:e total umber o5 co=
1uctio pat:s. <:ey attribute t:e subse.uet re1uctio to t:e
orietatio o5 t:e carbo blac$ a99re9ates i t:e 1irectio o5
strai. &as et al. C,20D observe1' 5or carbo blac$ a1 s:ort
carbo 5iber 5ille1 rubber composites' t:at t:e resistivity
icreases rapi1ly wit: t:e 1e9ree o5 elo9atio strai a1
e2plai t:e icrease i resistivity by a brea$1ow o5 e2isti9
co1uctive etwor$s a1 5ormatio o5 ew co1uctive et=
wor$s by rearra9emets a1 orietatio o5 blac$ particle
a99re9ates or 5ibers. &oet a1 -oet C,,8D cosi1er t:at t:e
strai 1epe1ece o5 t:e electrical properties o5 carbo blac$=
loa1e1 vulcai%ates ca be iterprete1 at small e2tesios by
t:e reversible 5ormatio a1 1estructio o5 t:e trasiet carbo
etwor$' up to ,/0? e2tesio by a orietatio o5 carbo
,0
/
w:ic: two clamps coecte1 to t:e :i9: resistace meter'
were place1 alo9 t:e le9t: o5 t:e specime (Fi9. ,4).
,0
4
,000
,00
,0
seco1 stretc:
5irst stretc:
, ,./ 2 2./ 0 0./ 4
e2tesio ratio T
Fi9. ,4. )tretc:i9 mac:ie 5or electrical measuremets u1er
uia2ial e2tesio.
Fi9. ,/. &epe1ece o5 t:e electrical resistivity o t:e e2tesio ratio a 5or t:e
)#3/,0 p:r M>8< composite.
49,8 ". #o$ob%a / Polymer 48 (2007) 4907e4920
blac$ a99re9ates a1 to rupture o5 elastomerecarbo bo1s at
still :i9:er e2tesios.
Accor1i9 to our AFM e2perimets u1er strai' we as=
cribe t:e 9ra1ual icrease i resistivity wit: strai (Fi9. ,/)
to t:e orietatio o5 t:e aotube bu1les rat:er t:a to t:e
1estructio o5 lar9e 5iller structures. Aur iterpretatio is i
a9reemet wit: t:e results o5 &u et al. C48D w:o s:owe1
t:at ali9met o5 a aotubes worses t:e electrical co1uc=
tivity a1 also s:i5ts t:e percolatio t:res:ol1.
+ or1er to parallel t:e mec:aical measuremets' electrical
measuremets are also carrie1 out 1uri9 a seco1 stretc:i9
per5orme1 , : a5ter total uloa1i9 o5 t:e sample.
A5ter total uloa1i9 o5 t:e sample' as alrea1y reporte1 i
ot:er stu1ies C,20',2,D' t:e resistivity o5 t:e 5ully rela2e1
composite is si9i5icatly :i9:er t:a t:at measure1 i t:e
ustraie1 elastomer s:owi9 t:at t:e 5iller etwor$ is ot
re=5orme1 a5ter removal o5 t:e stress. &uri9 t:e seco1
stretc:i9 per5orme1 , : a5ter retractio' t:e resistivity sli9:tly
1ecreases o accout o5 a re5ormatio o5 ew co1uctive co=
tacts. >:e t:e strai reac:es t:e ma2imum value o5 t:e 5irst
stretc:i9' t:e two curves coici1e w:ic: meas t:at t:e
sample is i t:e same state as it was at t:e 5irst stretc:i9.
+ li9:t o5 t:e AFM e2perimetal observatios' we ca ascribe
t:e stro9 :ysteresis i t:e co1uctivityestrai curve to rear=
ra9emets a1 1isorietatio o5 t:e bu1les.
7. *oclusio
+ t:is review' results obtaie1 o carbo aotube rei=
5orce1 polymers are presete1. >:ile t:e polymeric me1ia
are 5ocuse1 o elastomeric matrices' results obtaie1 o ot:er
materials are also metioe1 w:e ee1e1 i t:e 1iscussio.
A5ter a brie5 presetatio o t:e syt:esis met:o1s a1
processi9 o5 aotube=base1 polymer composites' t:e 5actors
e2pecte1 to cotrol t:eir mec:aical properties are 1iscusse1
i relatio to w:at is alrea1y $ow o composites 5ille1
wit: covetioal 5illers suc: as carbo blac$ or silica.
)peci5ic 5eatures o5 carbo aotubes relate1 to t:eir mo1ulus'
9eometry a1 orietatio' are also ta$e ito accout. +
particular' atomic 5orce microscopy ima9i9 u1er uia2ial
e2tesio o5 t:e sample 9ives evi1ece o5 t:e cotributio o5
t:e orietatioal e55ects.
Poor 1ispersio a1 lac$ o5 iter5acial a1:esio betwee
t:e tubes a1 t:e polymer are limiti9 5actors 5or 5ull reali%a=
tio o5 5iller capability. Lp to ow' t:e improvemets i me=
c:aical properties o5 t:e eat polymer by carbo aotube
icorporatio remai mo1est wit: re9ar1 to w:at s:oul1 be
e2= pecte1 5rom a aometer=scale rei5orcemet. <:is
1emo= strates t:e ee1 5or optimi%i9 t:e processi9
co1itios to ac:ieve 9oo1 1ispersio a1 9oo1 iteractios
wit: t:e poly= mer c:ais. <:is coul1 be 1oe by a
appropriate 5uctioal= i%atio o5 t:e tube sur5ace or by
itro1uci9 i t:e me1ium a type o5 coupli9 a9et able to
react wit: bot: p:ases. A t:e ot:er :a1' a met:o1 o5
icorporati9 simultaeously car= bo aotubes a1 aot:er
type o5 5iller' amely carbo blac$ particles' coul1 be o5
iterest o accout o5 possible syer9is= tic e55ects t:at coul1
arise betwee t:e two 1i55eret 5illers.
<:rou9: a combiatio o5 bee5its o5 eac: type o5 5iller' t:ese
:ybri1 composites coul1 potetially e2:ibit improve1 c:ar=
acteristics wit: re9ar1 to si9le=5iller materials. + particular'
carbo blac$ particles may improve t:e 5ormatio o5 co=
ecte1 structures by bri19i9 ucotacte1 tubes.
<:e capability o5 carbo aotubes to impart co1uctivity
to isulati9 elastomeric matrices :as bee clearly s:ow.
(lectrical measuremets carrie1 out u1er uia2ial 1e5orma=
tio 1isplay a 9ra1ual icrease i resistivity as a result o5 a
brea$1ow a1 a orietatio o5 t:e 5iller particles.
+ coclusio' t:is prelimiary e2perimetal wor$ i car=
bo aotube=base1 elastomeric composites :as 1emostrate1
t:e potetial o5 t:is ew 5orm o5 carbo as a rei5orci9 5iller
o5 rubber materials. Most mar$e1ly' t:is wor$ :as illustrate1
t:e problems ecoutere1 wit: t:e 1ispersio a1 iteractio
i t:e :ost polymeric me1ium.
3e5ereces
C,D #o$ob%a ". Macromolecular Materials a1 (9ieeri9 20044289!707.
C2D Mc*art:y &>' Mar$ 6(' )c:a55er &>. 6oural o5 Polymer
)ciece'
Part #! Polymer P:ysics ,998407!,,77.
C0D Mc*art:y &>' Mar$ 6(' *larso )6' )c:a55er &>. 6oural o5 Polymer
)ciece' Part #! Polymer P:ysics ,998407!,,9,.
C4D Bo:@iya )' Mura$ami B' +io )' <aa:as:i <' +$e1a N. 3ubber
*:emistry a1 <ec:olo9y 200,474!,7.
C/D &ewimille "' #resso #' #o$ob%a ". Polymer 200/447!4,0/.
C7D Asma MA' Atalla: A' Muller M' )uter L>. Polymer 200,442!7/4/.
C7D 6oly )' Jarau1 J' Allitrault 3' #o$ob%a ". *:emistry o5
Materials
20024,4!4202.
C8D -ar9:ese )' Bar9er=Bocsis 6. Polymer
2000444!492,4 3ubber >orl1 20044200!02.
C9D Bim 6=t' A: <=s' "ee &=:. Polymer +teratioal 20044/0!407.
C,0D Arroyo M' "oZ pe%=Mac:a1o MA' Herrero #. Polymer 2000444!2447.
C,,D #ala P' )amataray #B' )rivastava )B' 8a1o J#. 6oural o5 Applie1
Polymer )ciece 2004492!0/80.
C,2D 6eo H)' 3ames:waram 6B' Bim J. 6oural o5 Polymer )ciece' Part
#! Polymer P:ysics 2004442!,000.
C,0D Jaut:ier *' *:a%eau "' Prasse <' *availleZ 6N. *omposites )ciece
a1
<ec:olo9y 200/47/!00/.
C,4D #o$ob%a "' *:auvi 6=P. Polymer 200/447!4,44.
C,/D #arra%a H6' Pompeo F' A;rear (A' 3esasco &(. 8ao "etters 200242!
797.
C,7D Fro9ley M&' 3avic: &' >a9er H&. *omposites )ciece a1 <ec:ol=
o9y 2000470!,747.
C,7D "oZ pe%=Mac:a1o MA' #ia9iotti 6' -aletii "' Bey 6M. 6oural
o5
Applie1 Polymer )ciece 2004492!0094.
C,8D +i@ima ). 8ature ,99,40/4!/7.
C,9D #ac:tol1 A' Ha1ley P' 8a$ais:i <' &e$$er *. )ciece 200,4294!,0,7.
C20D &eryc$e -' Martel 3' Appe%eller 6' Avouris P:. 8ao "etters 200,4,!
4/0.
C2,D 3ot$i )-' [:arov +. +teratioal 6oural o5 8aosciece 20024,!047.
C22D A$ita )' 8is:i@ima H' 8a$ayama N' <o$umasu F' <a$eyasu B.
6oural
o5 P:ysics &! Applie1 P:ysics ,999402!,044.
C20D *:eu9 *"' Ha5er 6H' A1om <>' Bim B' "ieber *M. Applie1 P:ys=
ics "etters 2000477!0,07.
C24D >ilso 83' *ob1e &H' Macp:erso 6-. 6oural o5 P:ysical *:emis=
try # 20024,07!,0,02.
C2/D Neilme% (' >a9 O' 3obert 36' >a9 &' &ai H. Applie1 P:ysics
"etters 2002480!222/.
C27D Ne O' *assell AM' "iu H' *:ao B=6' Ha 6' Meyyappat M.
8ao
"etters 200444!,00,.
C27D #reuer A' )u1arara@ L. Polymer *omposites 200442/!700.
". #o$ob%a / Polymer 48 (2007) 4907e4920
49,9
C28D >ise B(' Par$ *' )ioc:i (6' Harriso 6). *:emical P:ysics
"etters
2004409,!207.
C29D A@aya PM' ):a1ler ")' Jiaaris *' 3ubio A. A1vace1
Materials
20004,2!7/0.
C00D ):a55er M' Biloc: +A. *omposites )ciece a1 <ec:olo9y 2004474!
228,.
C0,D Hutc:iso 6"' Biselev 8A' Briic:aya (P' Brestii A-' "ou5ty
3A' Moraws$y AP' et al. *arbo 200,409!77,.
C02D )aito N' 8a$a:ira <' Lemura ). 6oural o5 P:ysical *:emistry # 20004
,07!90,.
C00D [:a9 N' +i@ima ). Applie1 P:ysics "etters ,99947/!0087.
C04D )cott *&' Arepalli )' 8i$olaev P' )malley 3(. Applie1 P:ysics A
200,4
72!/70.
C0/D Arepalli ). 6oural o5 8aosciece a1 8aotec:olo9y 200444!0,7.
C07D 6ia9 >' Molia P' Fer$el H. 6oural o5 Mau5acturi9 )ciece
a1
(9ieeri9 200/4,27!700.
C07D Hirao$a <' Bawa$ubo <' Bimura 6' <ai9uc:i 3' A$amuto
A' A$a%a$i <' et al. *:emical P:ysics "etters 20004082!779.
C08D &arabot Al' 8emes=+c%e P' BerteZs% B' <apas%oZ "' BooZ s
AA'
AsvaZt: [' et al. 6oural o5 Aptoelectroics a1 A1vace1
Materials
200/47!70,.
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"iliae #o$ob%a 9ra1uate1 i P:ysics a1
*:emistry 5rom t:e Liversity o5 Paris.
):e eare1 :er P:.&. at t:e Liversity o5
Paris i -ibratioal )pectroscopy. ):e
is curretly Pro5essor o5 )pectroscopy
at (cole )upeZrieure 1e P:ysi.ue et 1e
*:imie +1ustrielles 1e la -ille 1e Paris
(()P*+). ):e was promote1 *:evalier o5
t:e "e9io o5 Hoour i ,999' 9ot t:e
Jeor9e )ta55or1 >:itby Awar1 5rom t:e
3ubber &ivisio o5 t:e America
*:emical )ociety i
2002 a1 t:e 6ea "a9lois Awar1 5or
:er researc: activities i Paris (ovember'
2002).
"iliae #o$ob%a :as bee ivolve1 i
may areas o5 researc: i polymer sciece
iclu1i9 ivesti9atio o5 local 1yamics
o5 macromolecular c:ais i bul$ elastomeric systems by t:e e2cimer 5luores=
cece tec:i.ue' aalysis o5 molecular orietatio i elastomeric etwor$s by
i5rare1 1ic:roism' rei5orcemet o5 elastomers by mieral 5illers' a1 ew
1evelopmets i vibratioal spectroscopy. "iliae #o$ob%a;s wor$ :as bee
i over ,20 publicatios' several boo$ c:apters a1 s:e is 5re.uetly ivite1
to 9ive lectures i :er areas o5 e2pertise.

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