8

Impact of Nanowires on the Properties

of Magnetorheological Fluids
and Elastomer Composites
R. C. eII
1
, D. T. Zinneinan
1
, and N. M. WeieIey
2

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7
0'-+$1(-/) 48 9,1)*,':


0.3
1. Introduction
MagneloiheoIogicaI (MR) fIuids aie a lype of snail naleiiaI vhose effeclive viscosily nay le
iapidIy changed (~fev ns) in a neaiIy ieveisilIe nannei ly lhe appIicalion and ienovaI of an
exleinaIIy-appIied nagnelic fieId. ConvenlionaI MR fIuids aie conposed of nicion-scaIe,
feiionagnelic spheiicaI pailicIes (lypicaIIy 3O lo 4O voIune peicenl) suspended in a
hydiocailon, siIicone, oi aqueous caiiiei fIuid (KIingenleig, 2OO1). The viscosily and appaienl
sheai slienglh of lhese suspensions can le conlioIIed ly vaiying lhe slienglh of an appIied
nagnelic fieId. Wilhoul an appIied nagnelic fieId (off-slale), MR fIuids aie a viscous
Iiquid/pailicIe suspension vilh a viscosily in lhe iange of O.1 - 3 Ia s. Upon appIicalion of a
nagnelic fieId (on-slale), lhe pailicIes acquiie a nagnelic poIaiizalion and alliacl one anolhei
foining chain-Iike sliucluies lhal join lo foin coIunnai sliucluies paiaIIeI lo lhe appIied fieId
(schenalic, Iig. 1). The nevIy foined coIunns span lhe suifaces of lhe device paiaIIeI lo lhe
fieId Iines iesuIling in a naleiiaI lhal lehaves as a inghan pIaslic fIuid, vilh incieased
viscosily and appaienl yieId sliess undei sheai. The viscosily and yieId sliess of lhe fIuid is
scaIalIe vilh lhe nagnilude of lhe appIied nagnelic fieId unliI nagnelic saluialion of lhe
pailicIes is ieached (}ones & Saha, 199O). Al high fieIds, lhe fIuid is conveiled lo a seni-soIid
vilh a five lo six oideis-of-nagnilude change in appaienl viscosily (Cen & IhuIe, 2OO2). As
lhe pailicIe Ioading appioaches 4O voI. , lhe fieId-induced yieId sliess can ieach 1OO kIa.
Lxceeding lhe yieId sliess of lhe fIuid causes lhe filiiI chains and coIunnai sliucluies lo
conlinuousIy lieak and ie-foin, iesuIling in a posl-yieId viscosily.


Iig. 1. Schenalic iepiesenlalion of lhe nagneloiheoIogicaI effecl vilh spheiicaI pailicIes.
!
"
Ieiionagnelic
pailicIes
Caiiiei
fIuid
"
!
"
!
"
!
"
!
"
!
"
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Electrodeposited Nanowires and Their Applications

190
The iheoIogicaI piopeilies of MR fIuids depend nol onIy on lhe slienglh of lhe appIied
nagnelic fieId, lul aIso on lhe Ioading (voI. oi vl. ), size, conposilion, nagnelic
piopeilies, and noiphoIogy of lhe pailicIes, as veII as on lhe concenlialion and lype of
addilives vilhin lhe suspension. As lhe appIied nagnelic fieId is incieased, lhe sheai
slienglh of lhe fIuid evenluaIIy ieaches a naxinun as lhe nagnelizalion saluialion of lhe
pailicIes is ieached. IailicIe Ioading is lhe nosl inpoilanl facloi affecling lhe achievalIe
yieId slienglh of MR fIuids. WhiIe incieasing lhe voIune fiaclion of pailicIes in lhe
suspension iesuIls in an inciease in lhe yieId slienglh of lhe naleiiaI, il aIso iesuIls in an
inciease in lhe off-slale viscosily. The sheai slienglh of lhe suspensions incieases vilh an
inciease in size of lhe pailicIes (Cen & IhuIe, 2OO2), hovevei, spheiicaI pailicIes Iaigei lhan
aloul 1O !n lend lo sellIe iapidIy, even vilh lhe addilion of speciaI addilives. Suspensions
conposed of nanonelei-sized pailicIes lend lo sellIe noie sIovIy, if al aII, due lo iovnian
nolion. Hovevei, lhe effecliveness of iovnian nolion conlined vilh a snaIIei nagnelic
nonenl, aIso hindeis lhe foinalion of lhe chain-Iike sliucluies in lhese eneigized fIuids,
giealIy ieducing lhe yieId sliess of lhe naleiiaI (RosenfeId el aI., 2OO2, Ioddai el aI., 2OO4,
Chaudhuii el aI., 2OO5). Civen lhese conpeling faclois, lhe ideaI dianelei of pailicIes is in
lhe iange of 1 lo 1O !n. In lhis size iange, sedinenlalion sliII occuis due lo lhe inheienl
densily diffeience lelveen lhe pailicIes and lhe caiiiei fIuid. Upon sellIing, lhe pailicIes
lend lo foin lighlIy packed sedinenls iesuIling fion iennanl nagnelizalion vilhin lhe
pailicIes and aie nol easiIy ie-dispeised (IhuIe & Cindei, 1998). Since lhe yieId sliess of MR
fIuids is diieclIy ieIaled lo lhe voIune fiaclion of pailicIes in lhe suspension, lhe lehavioi of
lhe fIuid is Iess piediclalIe duiing lhis ienixing peiiod. The sellIing iale can le ieduced
sIighlIy and Iess dense sedinenls foined, ly lhe addilion of speciaI addilives such as
suifaclanls, nanopailicIes, and olhei non-spheiicaI pailicIes (Ioddai el aI., 2OO4, Chaudhuii
el aI., 2OO5, Chin el aI., 2OO1, Weiss el aI., 1997, WeieIey el aI., 2OO6).


Theie aie a gioving nunlei of appIicalions lhal expIoil lhe MR fIuids conlinuousIy
conlioIIalIe, fieId-dependenl yieId sliess incIuding vaiialIe danpeis, liakes, cIulches, and
oplicaI poIishing nachines (Kanalh el aI., 1999, Zipsei el aI., 2OO1, RanaIIo el aI., 2OO2,
HaiIand el aI., 2OO1, Koidonski el aI., 2OO6). ConvenlionaI MR fIuids have had sone
difficuIly finding videspiead conneiciaI use, oving lo ieIaliveIy high nanufacluiing cosls,
as veII as a Iinilalion on lhe voIune Ioading necessaiy lo nainlain lheii Iov off-slale
viscosily. The use of MR fIuids in noie diveise appIicalions have leen Iiniled, due lo lhe
sellIing of lhe pailicIes in lhe alsence of conlinuaI nixing (Chen & Chen, 2OO3) and pailicIe
veai (CaiIson, 2OO3) lhal lends lo ieduce lhe efficacy of lhe fIuid ovei line and evenluaIIy
Iead lo device faiIuie.
olh lhe yieId sliess and sellIing piopeilies of nagneloiheoIogicaI fIuids have leen shovn
lo depend on pailicIe noiphoIogy, hovevei, fev sludies have expIoied lhe pailicIe shape-
dependence in eilhei MR fIuids (Chin el aI., 2OO1, Nishiyana el aI., 2OO5, Kuzhii el aI., 2OO9,
Lpez-Lpez el aI., 2OO9) oi eIeclioiheoIogicaI (LR) fIuids (Kanu & Shav, 1998, LengIov el
aI., 2OO3, Sanchis el aI., 2OO4, Yin & Zhao, 2OO6). Sludies invoIving eIeclioiheoIogicaI fIuids
uliIizing eIongaled lilanale (TiO
2
) vhiskeis denonslialed giealIy ieduced sedinenlalion.
Moieovei, vilh a 1O voI. Ioading, lhese fIuids dispIayed an inciease in yieId sliess fion 8O
lo 11OO Ia vhen ~8O nn dianelei pailicIes veie exchanged vilh TiO
2
vhiskeis (vilh 1O nn
dianeleis ly seveiaI hundieds oi lhousands nanoneleis) (Yin & Zhao, 2OO6). Hovevei, il is
uncIeai vhelhei lhe inciease in yieId sliess vas due lo lhe diffeiences in pailicIe
noiphoIogy oi due lo lhe Iaige nass diffeiences lelveen lhe pailicIes. Sludies on MR fIuids
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

191
vilh up lo 7 voI. 6O !n Iong, 4.8 !n dianelei colaIl niciofileis dispIayed sulslanliaI
niligalion of sedinenlalion and an inciease in yieId sliess as conpaied lo suspensions
conlaining 1.34 !n dianelei colaIl spheies (Lpez-Lpez el aI., 2OO9). Il vas suggesled lhal
lhe enhancenenl of lhe yieId sliess vas due lo inlei-filei soIid fiiclion. Yel, lhe fileis used
in lhese sludies had non-unifoin dinensions, iough suifaces, and lhe diffeience in lhe size
of lhe pailicIes nade a diiecl conpaiison lelveen lhe piopeilies of lhe lvo lypes of
suspensions difficuIl lo inleipiel. AII of lhese sludies suffeied fion lioad size disliilulion,
inconsislency in pailicIe shape, suiface ioughness, and pailicIe fiagiIily, naking il difficuIl
lo foin concIusions oi infei lhe undeiIying physics. Thus, vhiIe MR/LR fIuids enpIoying
eIongaled pailicIes denonslialed ieduced sedinenlalion piopeilies, lhe effecl on yieId
sliess ienained uncIeai.
Moie iecenl sludies uliIizing nanoviies have shovn pionising iesuIls foi nol onIy ieducing
oi pievenling sellIing, lul have aIso incieased lhe appaienl yieId sliess of lhe naleiiaIs (eII el
aI., 2OO7, eII el aI., 2OO8, Ngalu el aI., 2OO8, Zinneinan el aI., 2OO9). UnIike lhe feiionagnelic
oxide pailicIes used in pievious sludies (Chin el aI., 2OO1) and lhose foined fion spheiicaI
pailicIes adjoined in lhe piesence of a nagnelic fieId (Lpez-Lpez el aI., 2OO9), nanoviies
have veII defined sliucluie and conlioIIalIe Ienglh disliilulions. This faciIilales syslenalic
expeiinenlaI and lheoielicaI sludies and viII Iead lo incieased undeislanding and design
conlioI. Nanoviie-lased MR fIuids have lvo dislincl advanlages ovei suspensions lhal
conlain onIy spheiicaI pailicIes (eII el aI., 2OO7, eII el aI., 2OO8, Ngalu el aI., 2OO8). Iiisl, lhe
naxinun achievalIe yieId sliess can le lvice lhal of convenlionaI fIuids (oi giealei, even al
lhe sane nelaI Ioading) and nanoviie-lased fIuids aIso piovide noie sensilive conlioI ovei
lhe yieId sliess al fieId slienglhs leIov nagnelic saluialion of lhe suspension. Second,
sedinenlalion is giealIy ieduced, if nol eIininaled. Hovevei, one diavlack lo puie nanoviie
fIuids is lhe Iinil on pailicIe Ioading lo 1O voI. , iesuIling in fIuids vilh a naxinun yieId
sliess nuch Iovei lhan nosl convenlionaI MR fIuids. The viies occupy a nuch Iaigei
effeclive voIune conpaied lo spheies, due lo lhe excIuded voIune concepl. Lven so, fIuids
using onIy nanoviies dispIay sone veiy inleiesling and usefuI piopeilies. Ioi appIicalions
lhal iequiie lhe highesl yieId sliess (and lhus naxinun pailicIe Ioading of 35-4O voI. ), a
dinoiphic fIuid vas geneialed lhal conlains lolh spheiicaI and nanoviie pailicIes. These
fIuids nol onIy dispIay ieduced sedinenlalion, lul sone foinuIalions aIso dispIay an inciease
in yieId sliess ovei convenlionaI fIuids.
2. Synthesis of magnetorheological fluids
Tvo lypes of feiionagnelic pailicIes veie used in lhis sludy. To iepIicale convenlionaI MR
fIuids, ve used spheiicaI iion pailicIes having dianeleis of 1 - 3 !n oi 6 - 1O !n (AIfa
Aesai), colaIl pailicIes vilh noninaI dianeleis of 1.6 !n (AIfa Aesai), and nickeI pailicIes
vilh dianeleis in lhe iange of 1 lo 1O !n (Novanel). Nanoviie-lased fIuids veie
synlhesized using viies geneialed via lenpIale-lased eIecliodeposilion lechniques.
2.1 Nanowire generation and characterization
The nanoviies veie geneialed via lenpIale-lased eIecliodeposilion using conneiciaIIy
avaiIalIe, anodized aIunina nenlianes (Whalnan) as lenpIales and vaiious eIeclioIylic
soIulions depending on nanoviie conposilion. The eIeclioIyle soIulion foi nickeI nanoviies
consisled of 1.1 9 NiSO
4
, O.19 9 NiCI
2
, and O.6 9 H
3
O
3
, vilh lhe pH of lhe soIulion
Electrodeposited Nanowires and Their Applications

192
adjusled lo 3.5 using H
2
SO
4
. A 99.5 nickeI foiI vas used as lhe voiking eIecliode. Iion
nanoviies veie faliicaled using an eIeclioIylic soIulion consisling of O.9 9 IeSO
4
, O.O3 9
IeCI
2
, O.1O 9 NH
4
CI, O.O1 9 C
6
H
8
O
6
, and O.5 9 H
3
O
3
al a pH of 3 using H
2
SO
4
. A 99.99
iion foiI vas used as lhe voiking eIecliode. ColaIl nanoviies veie geneialed fion a
soIulion conlaining O.2 9 CoSO
4
, O.O2 9 CoCI
2
, and O.3 9 H
3
O
3
adjusled lo a pH of 3.5
using H
2
SO
4
. A 99.97 colaIl foiI vas used as lhe voiking eIecliode. The voiking
eIecliodes veie suspended appioxinaleIy 2 cn fion lhe aIunina lenpIale in lhe
eIeclioIylic soIulions. Wiies veie eIecliodeposiled using a cuiienl densily ianging fion 4.8-
5.5 nA cn
-2
undei anlienl condilions vilhoul agilalion. The dianelei of lhe viies vas
fixed ly lhe dianelei of lhe channeIs vilhin lhe nenliane and lhe Ienglhs of lhe viies
veie conlioIIed ly lhe cuiienl and deposilion line. The nanoviies veie iecoveied ly
dissoIving lhe viie-fiIIed lenpIales in a 1 9 NaOH soIulion.
IailicIe dinensions and size-disliilulion infoinalion foi lolh lhe spheiicaI pailicIes and
nanoviies veie ollained using Hilachi S57O and Hilachi S8OO scanning eIeclion
nicioscopes (SLM). Hundieds of inages veie exanined lo deleinine an aveiage and
slandaid devialion foi lhe dianelei and Ienglh. The size disliilulion of lhe viies can le
seen in lhe SLM niciogiaphs in Iig. 2.
Using induclion-coupIed pIasna speclioneliy (ICI), lhe sloichioneliic puiily of aII viie
conposilions vas deleinined lo le giealei lhan 99.4. In pailicuIai, lhe ICI dala indicales
lhal lhe viies do nol conlain significanl anounls of gaIIiun, indiun, coppei, aIuninun, oi
olhei eIenenls lhal cone in conlacl vilh lhe viies duiing faliicalion.
The coeicivily, ienanence, and nagnelic saluialion aII infIuence lhe nagneloiheoIogicaI
piopeilies of lhe fIuids and depend on lhe conposilion and aspecl ialio of lhe pailicIes. The
nagnelic piopeilies of lhe pailicIes and MR fIuids veie deleinined al ioon lenpeialuie
using a Lakeshoie 74OO seiies vilialing sanpIe nagnelonelei (VSM). Iiguie 3 shovs
hysleiesis cuives exhililed in iion nanoviies aIigned paiaIIeI lo one anolhei vilhin an
aIunina lenpIale, vheie lhe easy axis is paiaIIeI lo lhe fieId fIux and lhe haid axis is
peipendicuIai lo lhe fIux. This ieveaIs a shape-anisoliopy in lhe viies due lo lheii aspecl


Iig. 2. SLM niciogiaphs of 6.8 1.7 !n Iong colaIl nanoviies vilh dianeleis of 296 39
nn.
1 1O O ! !n n
5 5O OO O n nn n
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

193
-1
-O.8
-O.6
-O.4
-O.2
O
O.2
O.4
O.6
O.8
1
-1O -5 O 5 1O
#
$
#
!
% '()*+

Iig. 3. VSM neasuienenls foi 7.89 n iion nanoviies sliII conlained vilhin lhe aIunina
lenpIale and lheiefoie aIigned paiaIIeI lo one anolhei. Wiies aIigned paiaIIeI lo lhe fieId aie
iepiesenled ly lhe ied cuive and viies aIigned peipendicuIai lo lhe fieId aie iepiesenled ly
lhe lIue cuive.
ialio. This anisoliopy causes lhe suspended viies vilhin an MR fIuid lo expeiience a loique
vhen exposed lo lhe sIighlIy non-unifoin nagnelic fieId, iesuIling in lhe seIf-aIigning
lehavioi of lhe nanoviies discussed in ($;/-4' <=7. Since lhe saluialion nagnelizalion (9
.
) is
ollained vhen aII nagnelic nonenls in lhe naleiiaI aie aIigned in lhe sane diieclion, il is
an inliinsic naleiiaI piopeily vhich is unieIaled lo sanpIe noiphoIogy. Theiefoie, ve
vouId expecl lolh lhe spheies and nanoviies lo have a vaIue lhal is ieIaliveIy siniIai lo lhe
luIk naleiiaI of lhe sane conposilion. The nagnelic saluialion of lhe iion spheies and
nanoviies is 2OO.8 enu cn
-3
and 174.1 enu cn
-3
, iespecliveIy. When lolh aie assuned lo
have a luIk densily, lhe nagnelic saluialion foi colaIl spheies is 126.3 enu g
-1
and foi lhe
nanoviies, il diops lo 111.6 enu g
-1
. This devialion fion lhe luIk vaIue is nol suipiising
due lo lhe oxide Iayei lhal is piesenl. Il is nol unexpecled lhal lhe nanoviies vouId dispIay
a Iovei vaIue due lo incieased suiface aiea and lhe conconilanl inciease in oxide. As
expecled, spheiicaI iion pailicIes exhilil a neai zeio coeicivily.


Iig. 4. XRD of 8.7 2.7 !n Iong ly 318 51 nn dianelei iion viies. The Iallice pIanes foi iion
aie indicaled in ( ) liackels and lhose iesuIling fion lhe oxide Iayei aie indicaled in | j liackels.
-1O
4O
9O
14O
19O
24O
29O
34O
5 15 25 35 45 55 65
,
-
.
*
-
/
0
.
1

'
2
3
4
-
.
/
+
5!'6*7+
|311j
(2OO)
(11O)
Electrodeposited Nanowires and Their Applications

194
To deleinine lhe luIk ciyslaI sliucluie and appioxinale giain size of lhe ciyslaIIiles
foining lhe spheies and nanoviies, x-iay diffiaclion (XRD) palleins aie acquiied using a
Scinlag X2 aulonaled diffiaclonelei equipped vilh a IeIliei soIid-slale delecloi. XRD of lhe
fiee viies indicales lhal iion viies giov in a lcc poIyciyslaIIine sliucluie and lhal colaIl
viies giov in a hexagonaI poIyciyslaIIine sliucluie. Using Scheiieis foinuIa, lhe
appioxinale ciyslaIIile size foi as-deposiled viies vas deleinined lo le 23.8 nn, 14.8 nn,
and 42.2 nn foi lhe nickeI, iion, and colaIl, iespecliveIy. The XRD ieveaIed lhe
suscepliliIily of lhe iion nanoviies lo oxidalion (sone sanpIes dispIay a conposilion as
high as 28 iion oxide) vhiIe lhose of nickeI and colaIl dispIayed onIy ninoi peaks (oi
none al aII) foi lheii coiiesponding oxides. We olseived ninoi nelaI oxide peaks foi lhe
iion spheiicaI pailicIe disliilulions, lul none foi lhose of nickeI oi colaIl.
2.2 Magnetorheological fluid composition
The MR fIuids veie piepaied ly lhoioughIy nixing lhe feiionagnelic pailicIes in siIicone
oiI. Lecilhin vas added lo lhe oiI piioi lo lhe addilion of pailicIes as a suifaclanl foi
pioducing good dispeisions vilh 2 vl. lolaI pailicIe nass. Ioi lhe nickeI-lased MR fIuids,
lhe pailicIes veie suspended in O.2 Ia s siIicone oiI (AIfa Aesai). MagneloiheoIogicaI fIuids
used foi lhe peicoIalion sludies (.$;/-4' >) veie piepaied using a O.45 Ia s viscosily siIicone
oiI. A noie viscous fIuid vas used foi lhese Iov voI. suspensions lo avoid sedinenlalion
and lo pievenl lhe oiI fion leing expeIIed fion lhe iheonelei. AII olhei MR fIuids veie
piepaied using a O.18 Ia s viscosily siIicone oiI (CL SI96-2OO).
2.3 Rheological fluid testing
To deleinine lhe fIov cuives (sheai sliess vs. sheai iale), neasuienenls veie caiiied oul on
an Anlon-Iaai Ihysica MCR3OO paiaIIeI pIale iheonelei equipped vilh a MRD18O
nagnelic ceII. A slandaid gap of 1 nn vas nainlained lelveen lhe pIales and a noninaI
O.3 nL sanpIe of fIuid vas pIaced lelveen lhen. A HaII piole (I.W. eII IH3O1) vas
pIaced vilhin lhe gap lo caIiliale lhe eIeclionagnel cuiienl of lhe iheonelei in leins of lhe
nagnelic fIux densily vilhin lhe fIuid-conlaining gap. Ioi lhe peicoIalion sludies, a gap of
O.5 nn vas nainlained lelveen lhe pIales and a noninaI O.15 nL sanpIe of fIuid vas
used. A nagnelic fIux densily fion O lo 1.O T vas used foi lhe vaiious sludies and lhe
lenpeialuie of aII sanpIes vas nainlained al 25C vilh a cIosed-cycIe cooIing syslen. To
avoid sedinenlalion, lhe lesls veie slailed as soon as lhe lhoioughIy-nixed fIuid vas
injecled lelveen lhe disks.
Ioi lhe pieIininaiy sludies of lhe nickeI nanoviie-lased MR fIuids, a cuslon luiIl
iheonelei vas consliucled. This device consisled of a C-shaped eIeclionagnel capalIe of
geneialing fieIds up lo O.6 T as neasuied ly a HaII piole lelveen lhe poIes of lhe nagnel.
The sanpIe vas lhen pIaced lighlIy lelveen lhe poIes. To neasuie effeclive viscosily, a lhin
aIuninun pIale vas sulneised 1.3 cn inlo lhe fIuid vilh 1 nn of lhe MR fIuid on eilhei
side of lhe pIale. Wilh lhe nagnelic fieId appIied, a foice liansducei (iange of O.O2 - 45 N)
neasuied lhe foice iequiied lo puII lhe pIale oul of lhe fIuid al a iale of 1.O6 nn/s.
Hovevei, due lo lhe pooi iesoIulion of lhis foice liansducei, lhe naxinun fieId of O.6 T
vas necessaiy lo neasuie lhe yieId sliess vilhin a ieasonalIe unceilainly. Thus, aII fuluie
sludies veie conducled on lhe afoienenlioned Anlon-Iaai iheonelei.
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

195
2.4 Sedimentation testing
The sedinenlalion veIocily of pailicIes vilhin lhe suspensions vas deleinined ly
expIoiling lhe nagnelic piopeilies of MR fIuid pailicIes. As seen in Iig. 5, lhe inheienl
densily diffeience lelveen lhe caiiiei fIuid and nagnelic pailicIes iesuIls in sedinenlalion
of lhe pailicIes, Ieaving a voIune of supeinalanl fIuid (lhe cIaiified fIuid alove lhe sedinenl
nudIine). To quanlify and conpaie lhe sedinenlalion veIocily of convenlionaI spheie-
lased MR fIuids vilh lhose conlaining nanoviies, an induclance-lased soIenoid sensoi vas
consliucled lo liack lhe nudIine Iocalion of lhe sellIing fIuid (Ngalu & WeieIey, 2OO7). The
sedinenlalion veIocily is defined as lhe iale al vhich lhe nudIine descends due lo pailicIe
sellIing, unliI lhe pailicIes pack lighlIy al lhe lollon of lhe viaI vilhoul fuilhei
sedinenlalion. The nagnelic peinealiIily of lhe MR fIuid is highIy dependenl on lhe
voIune fiaclion of fIuid. Theiefoie, lhe induclive sensoi soIenoid is nainlained vilhin lhis
iegion. The peinealiIily of lhe MR fIuid vilhin lhe sensoi iegion is ieIaled lo lhe sensoi
induclance ? as

2
0
!
! "
r
N A
L
l
(1)
vheie @ is lhe nunlei of luins of lhe soIenoid, 3 is cioss-seclionaI aiea of lhe coiI, * is
soIenoid Ienglh, !
O
is lhe vacuun peinealiIily, and !
1
is ieIalive peinealiIily of lhe MR
fIuid. Thus, lhe iale of change of lhe nudIine can le deleinined as il liaveises lhiough lhe
sensoi ly neasuiing lhe iale of change of nagnelic induclance vilhin lhe sensoi.
Anolhei nelhod lo quanlify lhe sedinenlalion piopeilies of fIuids is lhe peicenlage of
sedinenlalion, ", given ly
100 #
$ %
" &
' (
) *
voIune of supeinalanl fIuid

lolaI voIune of fIuid
(2)
The peicenlage of sedinenlalion is an indicalion of hov lighlIy-packed lhe pailicIes lecone
once sellIed and is diieclIy ieIaled lo lhe ease vilh vhich lhe suspensions can le ie-dispeised.


Iig. 5. Sedinenlalion lesling appaialus foi deleinining sellIing veIocily of MR fIuids. The
induclance neasuiing insliunenl is conpiised of lhe sensoi assenlIy, an induclance nelei,
and a sland lo nounl lhe appaialus and sanpIe.
MR IIuid SanpIe
SoIenoid
x - MudIine
l - SoIenoid Lenglh
Induclance Melei
x
l
Sensoi AssenlIy
IIux ieluin
MudIine
Supeinalanl fIuid
Electrodeposited Nanowires and Their Applications

196
3. Nanowire-based magnetorheological fluids
3.1 Nickel-based MR fluids
To invesligale lhe feasilIe peifoinance of lhe nev nanoviie-lased MR fIuids, ve
conducled a pieIininaiy invesligalion of lhe iheoIogicaI piopeilies and sellIing
chaiacleiislics of fIuids conlaining nickeI nanoviies vilh an aveiage Ienglh of 5 - 25 !n and
dianeleis of 3OO 3O nn (eII el aI., 2OO7). Using lhe cuslon-designed iheonelei desciiled
in seclion 2.3, lhe iheoIogicaI piopeilies of lhese fIuids veie conpaied lo convenlionaI
fIuids conlaining nickeI-cailonyI spheies (iange of 1-1O !n dia.) having lhe sane voIune
peicenl of suspended pailicIes. The iheoIogicaI and sellIing piopeilies of lhe MR fIuids
consisling of 7.6 voI. nickeI nanoviies veie conpaied lo fIuids conlaining 7.6, 17.5, and
4O.O voI. nickeI spheies. These iniliaI sludies indicaled lhal lheie vas no diffeience in lhe
naxinun yieId sliess of lhe suspensions. Hovevei, lhe sellIing piopeilies of lhe fIuids
veie significanlIy diffeienl. The nanoviie-lased fIuids dispIayed no sellIing aflei seveiaI
nonlhs (discussed fuilhei leIov). Hovevei, lhese sludies suffeied fion seveiaI
shoilconings. The cuslon-luiIl iheonelei Iacked lhe sensilivily lo exanine fIuids leIov
nagnelic saluialion and couId nol neasuie lhe iheoIogicaI piopeilies al high sheai iales. In
addilion, lhe viies veie nol veII-chaiacleiized and an aveiage viie Ienglh couId nol le
deleinined fion lhe Iiniled SLM inages acquiied foi lhis sludy. Hovevei, lhe sellIing
iesuIls veie so pionising lhal lhese iniliaI sludies paved lhe vay foi noie caiefuIIy
consliucled fIuids using insliunenlalion capalIe of exanining lhe iheoIogicaI and
sedinenlalion piopeilies vilh giealei sensilivily.
3.2 Iron-based MR fluids
We lhen focused oui allenlion on iion nanoviie-lased MR fIuids vilh lvo dislincl Ienglh
disliilulions: 5.4 5.2 !n and 7.6 5.1 !n vilh dianeleis of 26O 3O nn. These veie
conpaied vilh convenlionaI spheie-lased MR fIuids (eII el aI., 2OO8). These sludies
iIIuslialed lhe dislincl diffeiences lelveen convenlionaI MR fIuids enpIoying spheiicaI
pailicIes lo nanoviie-lased fIuids vilh lhe sane feiionagnelic naleiiaI and pailicIe Ioading.
The iheoIogicaI piopeilies of lhe fIuids veie deleinined using lhe paiaIIeI pIale iheonelei
nodified vilh an eIeclionagnel lo aIIov appIicalion of a vaiialIe nagnelic fieId acioss lhe
sanpIe. We pIolled sleady-slale fIov cuives of sheai sliess (#) veisus sheai iale ( +! ) as seen
in Iig. 6. A inghan-pIaslic (I) conslilulive nodeI (}oIIy el aI., 1999) vas used lo fil lhe
fIov cuive lo deleinine lhe appaienl yieId sliess (#
)
) and lhe posl-yieId viscosily, $. The I
nodeI foi lhe viscopIaslic fIov vilh yieId sliess is given ly
0 ( )
y
, , -+ + " . / ! ! (3)
The vaIues of #
)
and $ veie deleinined ly filling vilh a veighled Ieasl-squaies-eiioi
nininizalion foi each fIuid lesled al aII vaIues of lhe appIied fieId. y using lhe neasuied
sheai iales as lhe veighling facloi, lhe nodeI piovided a lellei fil lo lhe high sheai iale dala.
As shovn in Iig. 7, lhe dynanic yieId-sliess dispIays a dependence on lhe appIied fieId foi
aII lhe fIuids sludied. Al a saluialed nagnelic fIux densily, il appioaches a naxinun vaIue
of 4.72 kIa foi fIuids conlaining 6 voI. iion spheies. Ioi fIuids conlaining lhe 5.4 !n iion
nanoviies in siIicone oiI, ve olseived naxinun yieId sliesses of O.65, 2.23, and 4.76 kIa foi
lhe 2, 4, and 6 voI. fIuids, iespecliveIy. The yieId sliess incieased lo 8.23 kIa foi lhe 6 voI.
fIuid vhen lhe aveiage Ienglh of lhe viies incieased lo 7.6 !n.
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

197

Iig. 6. LxpeiinenlaI fIov cuives foi fIuids conlaining 6 voI. 7.6 !n Ie nanoviies. The
appIied nagnelic fieId vas vaiied fion O.O T (lollon) lo O.72 T (lop).

1O
8
6
4
2
O
8
0
*
9
6

/
.
:
*
/
/
;

!
!

'
(
<
=
+
O.7O O.6O O.5O O.4O O.3O O.2O O.1O O.OO
#=7-*.02 >94? 6*-/0.1 '@+
5.4 n viies
7.6 n viies
1-3 n spheies

Iig. 7. YieId sliess veisus nagnelic fIux densily foi MR fIuids conlaining 5.4 !n and 7.6 !n
iion nanoviies and foi lhose fIuids vilh 1 - 3 !n iion spheies. AII fIuids have a 6 voI.
pailicIe Ioading. The dolled cuives aie incIuded sinpIy as a visuaI aid.
As seen in Iig. 7, lhe nanoviie-lased fIuids exhilil a noie sensilive iesponse dispIaying a
highei yieId sliess al Iov fieId as conpaied lo lhe spheie-lased fIuids. This enhancenenl in
lhe iesponse is IikeIy alliiluled lo nagnelic shape-anisoliopy of lhe viies. The nanoviies
expeiience a loique vilhin lhe appIied nagnelic fieId foicing lhen lo aIign vilh lheii Iong
axis paiaIIeI lo fieId (Qi el aI., 2OO3) and lhey expeiience a giealei nagnelizalion due lo lhe
shape anisoliopy (Sun el aI., 2OO5).

O.OO
2.OO
4.OO
6.OO
8.OO
1O.OO
12.OO
O.OO 2OO.OO 4OO.OO 6OO.OO 8OO.OO 1OOO.OO
!
A
*
=
:

/
.
:
*
/
/

'
(
<
=
!
/
+
!A*=: :=.* '/
BC
+
Electrodeposited Nanowires and Their Applications

198
ModeIs of lhe yieId sliess (#
)
) foi spheie-lased fIuids piedicl a chaiacleiislic iesponse al
inleinediale fieIds leIov saluialion as given ly

1 2 3 2
0
/ /
y S
M H , 0! 1 (4)
vheie A
O
is lhe peinealiIily of fiee space, 0 is lhe voIune fiaclion, 9
.
is lhe nagnelic
saluialion of lhe naleiiaI, and B is lhe slienglh of lhe appIied nagnelic fieId. The spheie-
lased suspensions used in lhis sludy dispIayed siniIai lehavioi. Hovevei, foi lhe
nanoviie-lased suspensions, lhe liend in lhe yieId sliess is found lo le piopoilionaI lo lhe
squaie iool of lhe appIied fieId,

1 2
0
/
y
H , 0! 1 (5)
Hov lhe nagnelic saluialion and shape anisoliopy of lhe pailicIes quanlilaliveIy affecls lhe
yieId sliess of lhe nanoviie-lased suspensions is sliII nol veII undeislood. The nagnelic
saluialion of lhe nanoviies is a funclion of lheii Ienglh and dianelei, vilh Iongei viies
(vilh fixed dianelei) having a highei nagnelic saluialion (Han el aI., 2OO2). Yel lhe
diffeience in lhe nagnelic saluialion of lhe pailicIes cannol accounl foi lhe sulslanliaI
diffeience in lhe yieId sliesses of lhe fIuids conlaining lhe lvo viie Ienglhs olseived in oui
sludies. Theiefoie, olhei faclois such as nagneloslalic coupIing lelveen neighloiing viies
(lhis lends lo cieale a nagnelic easy axis peipendicuIai lo lhe viie axis), inlei-filei fiiclion,
and sliucluiaI diffeiences of lhe lvo lypes of suspensions in an appIied nagnelic fieId nusl
aIso le consideied. Sone sliucluiaI diffeiences lelveen spheie-lased fIuids and nanoviie-
lased fIuids aie appaienl in lhe SLM niciogiaphs of Iig. 8.
Knoving lhe sliucluie of lhe suspension lolh in lhe piesence (on-slale sliucluie) and
alsence (off-slale sliucluie) of a nagnelic fieId is essenliaI lo undeislanding lhe piopeilies
of lhese fIuids. To geneiale lhese inages, lhe viies veie suspended in a diop of valei and a
unifoin nagnelic fieId vas appIied acioss lhe diopIel. The diopIel vas lhen aIIoved lo


Iig. 8. SLM niciogiaph shoving lhe coIunnai sliucluies of (a) spheiicaI 1 - 3 !n dianelei
iion pailicIes and (l) 1O.6 !n Iong iion nanoviies vilh 26O nn dianeleis foined in lhe
piesence of a nagnelic fieId.
7 75 5 ! !n n
a
8 8. .6 6 ! !n n
b
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

199
evapoiale vhiIe lhe fieId vas nainlained. The spheies Iine up lo foin inleiconnecled
coIunns as depicled in Iig. 1. In addilion lo foining coIunnai sliucluies, lhe nanoviies of
lhe viie-lased fIuids aIso lend lo inleiIock vilh one anolhei due lo lheii eIongaled shapes.
Theie aie a nunlei of faclois lhal nusl le consideied lo undeisland lhe inciease in lhe
yieId sliess of lhe nanoviie-lased fIuids as conpaied lo lhe spheie-lased fIuids. As noled
pieviousIy, foi spheie-lased fIuids, yieId sliess scaIes vilh pailicIe size. If lhe inciease in
yieId sliess depended on lhe voIune of lhe individuaI pailicIes aIone, ve vouId expecl lhe
fIuids conlaining lhe 1 - 3 !n spheies lo exhilil nuch highei yieId sliesses lhan lhe viie-
lased fIuids. (The voIune of a 2 !n dianelei spheie is 4.19 !n
3
and lhe voIunes of 5.4 and
7.6 !n Iong viies vilh 26O nn dianeleis aie O.29 and O.4O !n
3
, iespecliveIy.) Al fieIds
leIov nagnelic saluialion, lhe viies have a snaIIei denagnelizalion facloi and lhus il is
easy lo undeisland lheii noie sensilive iesponse al Iovei nagnelic fieIds. ul alove
saluialion, diffeiences in nagnelic saluialion no Iongei appIy.
Civen lhal lhe suspensions conlain lhe sane nass of iion pailicIes (and lheiefoie, lhe sane
voIune), lhe nagnelic peinealiIily of lhe lvo lypes of suspensions is expecled le veiy
siniIai. Hovevei, lhe IocaI packing densily of lhe nanoviies nay le sIighlIy highei lhan
lhal of lhe puie spheies (eII el aI., 2OO8), vhich vouId iesuIl in a highei IocaI peinealiIily
and lhus sliongei coIunnai sliucluies vilhin lhe suspension. The packing densily of lhe
lvo nanoviie disliilulions shouId le siniIai and ve vouId expecl lhe yieId sliess of lhese
lvo fIuids lo le siniIai. Hovevei, il is appaienl fion Iig. 7 lhal lhe Iongei nanoviies
dispIay a nuch giealei yieId sliess lhan lhe shoilei viies al lhe sane Ioading. This suggesls
lhal lhe packing efficiency of lhe fIuids nay onIy pIay a ninoi ioIe in lhe oveiaII yieId sliess
of lhe fIuid.
The off-slale viscosily of lhe fIuids is aIso an inpoilanl facloi lhal nusl le accounled foi
vhen deveIoping nev lypes of MR fIuids, lhe Iovei lhe off-slale viscosily, lhe Iaigei lhe
iange of achievalIe viscosilies. The puie siIicone oiI used in lhese sludies had a viscosily of
O.41 Ia s and lhe off-slale viscosily foi lhe 6 voI. fIuids conlaining spheies vas O.66 Ia s.
The nanoviie-lased fIuids denonsliale a siniIai off-slale viscosily of O.68 Ia s foi lhe 6
voI. fIuids, vhich diops lo O.5O Ia s foi lhe 2 voI. fIuids. Hovevei, as ve nov discuss,
lhe nanoviie-lased fIuids dispIay a nuch highei degiee of viscoeIaslicily.
Nanoviie-lased fIuids dispIay no disceinalIe sellIing al voIune fiaclions giealei lhan ~4
voI. of ~11 !n Iong viies aflei 2 nonlhs of silling undisluiled. The exacl voI. iequiied
lo effecliveIy slop sedinenlalion (undei vilialion fiee condilions) depends on lhe Ienglh of
lhe viies: shoilei viies iequiie highei voIune peicenlages lhan Iongei ones. A
disadvanlage of lhe nanoviie-lased suspensions is lhal lhe naxinun voIune fiaclion of
nanoviies (< 1O voI. ) is nuch Iess lhan lhe desiied 3O - 4O voI. , achievalIe vilh
spheiicaI pailicIes, vhich is necessaiy foi high yieId-sliess appIicalions. Ioi lhese ieasons,
suspensions lhal conlain sliiclIy nanoviies vouId le noie usefuI in appIicalions vheie
sedinenlalion vouId le exlieneIy deliinenlaI oi vheie Iov yieId-sliess is sufficienl.
On lhe olhei hand, fIuids enpIoying 6 voI. spheies dispIayed 79 sellIing in jusl 48 houis.
The diffeience in lhe sedinenlalion (and lhe viscoeIaslic piopeilies) of lhe lvo fIuid lypes is
IikeIy a iesuIl of seveiaI faclois, incIuding nanoviie enlangIenenl, incieased suiface aiea
conpaied lo spheies, and hydioslalic and nagnelic inleiaclions lelveen nanoviies,
pailicuIaiIy lhose due lo iennanl nagnelizalion. Conpaiing lhe lolaI suiface aiea of lhe
pailicIes in fIuids vilh lhe sane voIune fiaclion of pailicIes, fIuids conlaining 5.4 !n Iong
nanoviies vilh 26O nn dianeleis have noie lhan 5 lines lhe lolaI suiface aiea pei voIune
lhan fIuids vilh 2 !n dianelei spheies (lhis diffeience vaiies IillIe vilh viie Ienglh).
Electrodeposited Nanowires and Their Applications

200
Hovevei, enlangIenenl of lhe nanoviies is IikeIy lhe piinaiy facloi iesponsilIe foi lhe
diffeiences lelveen lhe sedinenlalion and viscoeIaslic piopeilies of lhe lvo lypes of fIuids.
LnlangIenenl occuis vhen lhe voIune fiaclion of viies is high enough so lhal neighloiing
viies iesliicl lhe end-ovei-end iolalionaI and liansIalionaI nolion of lhe viies
peipendicuIai lo lhe Iong axis (Doi & Ldvaids, 1978). Hovevei, lhis does nol giealIy affecl
lhe off-slale viscosily of lhe nanoviie-lased suspensions undei sheai lecause lhe viies lend
lo Iine up and sIide pasl one anolhei easiIy, iesuIling in a viscosily lhal is siniIai lo lhal of
lhe caiiiei fIuid al Iov pailicIe concenlialions (eicea & Navaid, 2OOO).
4. Percolation phenomena in MR fluids
The aliIily lo piedicl lhe effeclive physicaI piopeilies of MR-fIuid conposiles fion lhe
knovn piopeilies of lhe consliluenls vouId have a lienendous inpacl foi nuneious
indusliiaI piocesses. Hovevei, foinuIaling an effeclive-nediun nodeI is conpIicaled
vhen lhe physicaI piopeilies of lhe consliluenls vaiy giealIy. In such cases, lhe conposile
naleiiaI lypicaIIy exhilils a phase liansilion al a ciilicaI voIune fiaclion of lhe conponenl
of inleiesl. The piololypicaI exanpIe is lhal of a nelaI-insuIaloi conposile vilh eIecliicaI
conduclivily lhal can change ly 16-2O oideis of nagnilude as a ciilicaI voIune of lhe
conducling conponenl is ieached. Such a phase change in lhe physicaI piopeilies of
naleiiaIs is knovn as a peicoIalion liansilion. Nuneious sludies ovei lhe pasl fev decades
have focused piinaiiIy on eIeclionic and lheinodynanic lianspoil and lo sone exlenl on
lhe eIaslic and nechanicaI piopeilies of naleiiaIs neai lhe ciilicaI poinl.

Vaiious peicoIalion nodeIs invoIving slalic naliices have leen deveIoped using lolh
disciele-Iallice nelvoiks and conlinuun nelvoiks (Slauffei & Ahaiony, 1994, and
iefeiences lheiein). Lach of lhese nodeIs allenpls lo deleinine lhe scaIing lehavioi of lhe
syslen using diffeienl ciilicaI exponenls (( and /, in lhe case of conduclivily nelvoiks) lo
desciile lhe naluie of lhe liansilion as lhe ciilicaI voIune fiaclion (0
;
) is appioached. In so-
caIIed eIaslic peicoIalion nelvoiks (LINs), a lvo-conponenl nixluie consisls of londs vilh
finile eIaslic noduIus logelhei vilh conpIeleIy non-iigid londs. As 0
;
is appioached fion
alove, lhe geneiaI eIaslic noduIus (C) of an LIN is lhoughl lo vanish as (Ieng el aI., 1987,
Depluck el aI., 1985, Sahini, 1996),

f
c
G 0 0 2 ~ ( )

(6)

In conliasl, a supeieIaslic peicoIalion nelvoik (SLIN) consisls of a nixluie of peifeclIy iigid
londs and londs vilh finile eIaslic conslanls. eIov lhe ciilicaI poinl, lhe eIaslic noduIi
diveige as (eignan, 1986),

c
c
G 0 0
2
2 ~ ( )

(7)

Sone sludies indicale lhal foi 0 > 0
;
, lhe eIaslic exponenl is equaI lo lhe conduclivily
exponenl, 8 = / (Tokila & Hikichi, 1987, Ciaciun el aI., 1998). Olhei sludies on lhe iheoIogy
of nagnelic suspensions exhililing eIaslic lehavioi suggesl lhal 8 depends on concenlialion,
vaiying fion 1.O lo 2.26 (Kanai el aI., 1992). Hovevei, nosl expeiinenlaI neasuienenls
and lheoielicaI nodeIs indicale lhal 8 > /, vilh lypicaI 8-vaIues in lhe iange of 3.5 - 4.O (Ieng
el aI., 1987, Depluck el aI., 1985, Sahini, 1996), vhich aie alliiluled lo lhe highei lensoiiaI
oidei of LINs. Sludies of SLIN lehavioi in lvo dinensions indicale lhal lhe ciilicaI
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

201
exponenl ; shouId scaIe as lhe supeiconduclivily exponenl ( (eignan, 1986), vhiIe
nuneiicaI sinuIalions have shovn ; lo le sIighlIy snaIIei lhan ( (Ieng, 1987).
To invesligale fuilhei lhe iheoIogicaI lehavioi of nanoviie-lased MR fIuids, ve have
syslenalicaIIy vaiied 0 in colaIl-nanoviie MR fIuids and neasuied lhe dynanic yieId sliess
foi vaiying appIied nagnelic fieId slienglhs (Zinneinan el aI., 2OO9). In doing so, ve
olseive a peicoIalion liansilion in lhe yieId sliess and find lhe lehavioi neai lhe ciilicaI
poinl lo depend on lhe nagnilude of lhe appIied fieId.
We vaiied lhe appIied nagnelic fieId incienenlaIIy ovei lhe iange of O - 1.O T foi sanpIes
having colaIl-nanoviie voIune fiaclions in lhe iange 0 = O - O.O6 (nole lhal ve aie using
voIune fiaclion ialhei lhan voI. ). Iiguie 9 shovs a seiies of #
)
veisus 0 cuives lhal ieveaI
lhe dependence of lhe ciilicaI voIune fiaclion and lhe liansilion onsel on lhe appIied fieId.
To chaiacleiize lhe dala ve enpIoyed a noinaIized, lvo-paianelei fil lased on Lq. 8 and 9
using vaIues of lhe yieId sliess exliapoIaled lo 0 = O (#
*4D
~ 5 - 12 Ia) and fai leyond 0
;
(#
#-6#

~ 1O
5
Ia).
,
0 0
, , 0 0
0
2
$ % 2
" 3
' (
) *
c
c
y low c
c
(8)

1
,
0 0
, , 0 0
0
$ % 2
" /
' (
2
) *
f
c
y high c
(9)
The dala exhilil seveiaI liends: ; decieases vilh incieasing fieId, vhiIe 0
;
incieases, and 8
appeais lo le ieIaliveIy conslanl, independenl of lhe appIied fieId. The exliacled vaIues of 8
foi aII fieId-slienglhs iange fion 1.O lo 1.2. These aie inliiguingIy ieniniscenl of lhe


Iig. 9. The appaienl yieId sliess (#
)
) of on-slale, colaIl-nanoviie MR fIuids as a funclion of
nanoviie voIune fiaclion (0) foi vaiying appIied nagnelic fieIds. The soIid cuives iepiesenl
lhe lesl fil lo expecled povei-Iav dependence given in Lq. 8 and 9. Dala up lo 0 = O.O6 vas
used in lhe anaIysis, lul nol shovn foi lhe sake of cIaiily neai lhe ciilicaI poinl.
Electrodeposited Nanowires and Their Applications

202
conduclivily exponenl in lvo-dinensionaI slalic naliices (/ ~ 1.3) and lhe vaIues of lhe
eIaslic exponenl (8 ~ 1.3) found in lvo-dinensionaI, slalic-naliix nuneiicaI sludies (IIischke
& }os, 1998, Iaiago & Kanloi, 2OOO). This suggesls lhal an MR fIuid syslen suljecled lo a
ieIaliveIy unifoin nagnelic fieId lehaves lvo-dinensionaIIy, possilIy lecause lhe appIied
fieId defines a piefeiied spaliaI diieclion foi chain foinalion. The vaiialion in ; and 0
;
aie
difficuIl lo expIain in Iighl of knovn scaIing nodeIs. In conduclivily nelvoiks, lhe ciilicaI
voIune fiaclion is expecled lo deciease as lhe nelaI/insuIaloi pailicIe-size ialio decieases
(Kusy, 1978), and al lhe sane line, inciease vilh aspecl ialio due lo lhe effecl of excIuded
voIune (aIleig el aI., 1984). Yel, neilhei of lhese is a vaiialIe in lhe MR fIuid syslen undei
sludy. The ciilicaI exponenl, ;, piesunalIy ieIaled lo lhe giovlh of eIaslic cIusleis leIov lhe
liansilion (feiionagnelic chains in lhis case), vaiies consideialIy vilh lhe nagnelic fieId.
The vaiialion in ; nay le desciiling lhe changes in lhe iandon ieinfoicenenl of lhe MR
fIuid ly chain giovlh leIov lhe ciilicaI voIune fiaclion lhal does nol span lhe sanpIe. In
aII IikeIihood, lhe fIuid-chain noiphoIogy of lhe on-slale MR fIuids and lhe dynanic naluie
of lhe iheoIogicaI neasuienenls nay aIso pIay a significanl ioIe in lhe chaiaclei of lhe
peicoIalion liansilion. The inpoilance of lhis issue cannol le undeieslinaled in Iighl of lhe
nuneious appIicalions lhal expIoil lhe MR effecl.
WhiIe lhe vaIues of lhe ciilicaI voIune fiaclion aie ieasonalIe foi nanoviies having a high
aspecl ialio (~3O), lhe dependence of ciilicaI voIune fiaclion on lhe appIied fieId is
unexpecled and IikeIy alliiluled lo lhe dynanic naluie of lhe neasuienenl lechnique and
lhe inhonogeneilies of lhe iheonelei nagnelic fieId. UnIike lhe piesenl sludy, invoIving a
dynanic-naliix fIuidic syslen vilh lolh shoil-iange conlacl and Iong-iange nagnelic
inleiaclions, lhe vasl najoiily of olhei sludies have consideied slalic syslens vilh shoil-
iange inleiaclions oi lhose invoIving diiecl pailicIe-pailicIe conlacls. In fuluie sludies, ve
viII vaiy lhe nanoviie aspecl-ialio, use olhei feiionagnelic naleiiaIs (e.g., iion and nickeI),
and enpIoy quasislalic, ialhei lhan dynanic neasuienenls, lo heIp sepaiale lhese issues
fion lhe undeiIying physicaI nechanisns.
5. Dimorphic magnetorheological fluids
Dinoiphic MR fIuids veie conceived as a vay lo ieaIize lhe lenefils of lolh nanoviie-
lased and convenlionaI MR fIuids (Ngalu el aI., 2OO8). In pailicuIai, ve vanled lo
synlhesize an MR fIuid having Iov sedinenlalion piopeilies yel having sufficienlIy high
pailicIe-Ioading lo achieve high yieId sliess. We invesligaled lhe iheoIogy and
sedinenlalion slaliIily of lhese dinoiphic fIuids, vhich sulslilule a given peicenlage of
spheies vilhin a convenlionaI MR fIuid foi nanoviies. Ioi lhese sludies, ve used iion
spheies of dianelei 8 2 n and iion nanoviies vilh dianeleis of 23O nn and Ienglhs
ianging 7.6 5.1n suspended in a O.18 Ia s siIicone oiI. SanpIes veie geneialed foi lolaI
pailicIe Ioadings of 5O, 6O, and 8O vl. conlined vilh nanoviie Ioading fion O lo 8 vl.
in 2 vl. incienenls. This iesuIled in off-slale viscosilies foi fIuids vilh a lolaI Ioading of
8O vl. ianging fion 1.3 Ia s foi lhe puie spheie fIuids lo 4.4 Ia s foi lhe 8 vl.
nanoviie-sulsliluled dinoiphic fIuids.
Dinoiphic MR fIuids vilh nodeiale pailicIe Ioading of 5O and 6O vl. dispIayed yieId-
sliess lehavioi veiy siniIai lo convenlionaI fIuids as seen in Iig. 1O. Hovevei, ve olseive
sIighl diffeiences in lhe yieId-sliess of dinoiphic MR fIuids al 8O vl. . Al Iov fieId
slienglhs, a sIighl inciease in yieId sliess vilh incieasing viie sulslilulion vas olseived,
consislenl vilh lhe enhanced iesponse olseived in puie nanoviie MR fIuids al Iovei fieId
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

203
slienglhs. Al nodeiale fieId slienglhs lheie veie no diffeiences in peifoinance. Al high
fieIds appioaching lhe nagnelic saluialion of lhe pailicIes, lheie vas an inciease in yieId-
sliess of 1O foi 2 vl. sulsliluled dinoiphic fIuids. Yel, vilh a fuilhei inciease in
nanoviie sulslilulion ve olseive a ~5 :$;1$,($ foi 8 vl. sulsliluled dinoiphic fIuids.
This vas hypolhelicaIIy expIained ly consideiing lhe chain sliucluies foined in
convenlionaI fIuids conpaied lo lhose foined ly dinoiphic fIuids. Al highei Ioadings, SLM
niciogiaphs shoved lhal lhe viies legan lo inleifeie vilh lhe coIunnai sliucluie of lhe on-
slale fIuids.
Sedinenlalion slaliIily anaIysis of dinoiphic fIuids shoved diaslic inpiovenenls acioss aII
ianges of pailicIe Ioading. Tine consliainls veie a facloi in lhis sludy since onIy one sanpIe
couId le lesled al a line and each lesl iequiied a nininun of one nonlh. Thus, nol aII
sanpIes undeivenl lolh iheoIogicaI and sedinenlalion lesls. Ioi fIuids in lhe nodeiale
pailicIe Ioading ianges of 5O and 6O vl. , onIy one convenlionaI and one dinoiphic sanpIe
veie lesled so lhal lhe noie highIy-Ioaded fIuid sanpIes of 8O lolaI vl. , vhich aie noie
connonIy enpIoyed lhioughoul indusliy, couId undeigo noie exlensive lesling.
Sedinenlalion lesls of lhe nodeialeIy Ioaded fIuids shoved a decieased (oidei of
nagnilude Iovei) sedinenlalion veIocily vhen conpaiing 5O vl. convenlionaI fIuids lo
dinoiphic fIuids vilh 6 vl. sulslilulion, as veII as 6O vl. convenlionaI fIuids lo 8 vl.
sulsliluled dinoiphic fIuids. Dinoiphic fIuids vilh a lolaI Ioading of 8O vl. aIso shoved

O.O
1O.O
2O.O
3O.O
4O.O
5O.O
6O.O
7O.O
8O.O
9O.O
O O.5 1 1.5 2 2.5 3 3.5
8
0
*
9
6

/
.
:
*
/
/

'
(
<
=
+
#=7-*.02 >94? 6*-/0.1 '@+
8O vl Spheies
78/2 vl (spheies/viies)
76/4 vl (spheies/viies)
74/6 vl (spheies/viies)
72/8 vl (spheies/viies)
6Ovl Spheies
52/8 vl (spheies/viies)
5Ovl Spheies
44/6 vl (spheies/viies)

Iig. 1O. YieId sliess veisus nagnelic fieId foi convenlionaI spheie-lased fIuids and foi
dinoiphic fIuids of lhe sane lolaI pailicIe Ioading.
Electrodeposited Nanowires and Their Applications

204
a significanl sedinenlalion iale deciease. The iale of 2 vl. sulsliluled fIuids deciease ly a
facloi of lvo, vhiIe lhe iale of 4 vl. sulsliluled dinoiphic fIuids dispIayed an oidei of
nagnilude deciease. SiniIaiIy, lhe diffeience in lhe degiee of sedinenlalion lelveen
convenlionaI and dinoiphic fIuids foi lhe sane sanpIes shoved a lolaI sedinenlalion
deciease of 5O in 5O vl. Ioaded fIuids and an 8O deciease in 6O vl. Ioaded fIuids.
The 8O vl. fIuids shoved a deciease in lolaI sedinenlalion of 4O in 2 vl. sulsliluled
fIuids and 6O in 4 vl. sulsliluled fIuids. ResuIls of lhe sedinenlalion lesls aie
sunnaiized in TalIe 1.

Conposilion
Sedinenlalion
VeIocily |!n/sj
Sedinenlalion
Ieicenlage ()
5O vl. spheies 1.9 72.9
44 vl. spheies + 6 vl. viies O.O36 23.4
6O vl spheies O.86 66.7
52 vl spheies + 8 vl viies O.O17 14.O
8O vl spheies O.O254 14.8
78 vl spheies + 2 vl viies O.O122 8.8
76 vl spheies + 4 vl viies O.OO21 5.7
TalIe 1. The sedinenlalion veIocily and peicenlage sedinenlalion of iion-lased dinoiphic
fIuids conlaining vaiious vl. sulslilulions of spheies ly nanoviies.
In sunnaiy, lhe lenefils of using dinoiphic MR fIuids ovei convenlionaI MR fIuids aie
effecled ly lhe heleiogeneous chain sliucluies foined in dinoiphic fIuids - lhe nanoviies
appeai lo sliucluiaIIy suppoil lhe chains lhal aie piinaiiIy foined ly spheies (Ngalu el aI.,
2OO8). Hovevei, as viie sulslilulion is incieased, lheie appeais lo le a lhieshoId ieached
vheie lhe viies legin lo inleifeie vilh lhe coIunnai sliucluies foined ly lhe spheies
iesuIling in a Iovei yieId sliess al highei viie sulslilulion.
6. Magnetorheological elastomers
LIasloneis (i.e., siIicone, poIyuielhane, naluiaI iullei, elc.) have leen connonIy used foi
passive shock and vilialion allenualion, yel passive danping peifoinance is Iiniled due
lo lhe fixed viscoeIaslic piopeilies of lhese naleiiaIs. To oveicone lhese peifoinance
Iinilalions, nagneloiheoIogicaI eIasloneis (MRLs) have leen iecenlIy inlioduced and aie
leing acliveIy sludied. MRLs aie nuIlifunclionaI naleiiaIs as lhey can aIso le used as
sensois oi aclualois siniIai lo olhei conlioIIalIe, aclive-danping naleiiaIs such as
piezoeIecliics, nagnelosliiclives, eIeclioaclive poIyneiics, and so on. Hovevei, in conliasl
lo olhei aclive-danping naleiiaIs, MRLs can opeiale in a passive node as veII. MRLs
opeiale in lhe aclive node ly appIicalion of a vaiialIe appIied nagnelic fieId lhal changes
lhe fiequency-dependenl eIaslic noduIus.
We exanined lolh lhe slalic and dynanic chaiaclei of nanoviie-lased MRL conposiles
(Song el aI., 2OO9a, Song el aI., 2OO9l). These MRLs veie synlhesized using a siIicone iullei
enledded vilh feiionagnelic pailicIes of iion and colaIl of vaiying veighl fiaclion (1O, 3O,
and 5O vl. ). To assess lhe effecl of pailicIe noiphoIogy, ve conpaied nanoviie-lased
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

205
MRL conposiles lo lhose nade vilh spheiicaI pailicIes. y neans of a nodified naleiiaI
lesling nachine using lolh slalic and sinusoidaIIy-osciIIaling conpiessive Ioads, ve
neasuied such fieId-dependenl piopeilies as slalic and dynanic sliffness, eIaslic noduIus,
yieId sliess, and equivaIenl danping. To invesligale nagnelic anisoliopy effecls in
nanoviie-lased MRL conposiles, sanpIes veie cuied lolh in lhe piesence and alsence of a
nagnelic fieId lo yieId sanpIes vilh nanoviies lolh aIigned and iandonIy oiienled vilh
iespecl lo lhe fieId, iespecliveIy.
The slalic sliffness of lolh niciospheie- and nanoviie-lased MRL conposiles incieased
IineaiIy as lhe pailicIe veighl fiaclion incieased as shovn in Iig. 11. Iion nanoviie-lased
MRL conposiles dispIayed a giealei sensilivily lo lhe veighl fiaclion lhan lhal of iion
niciospheie-lased MRL conposiles. The inciease in sliffness of lhe nanoviie-lased MRLs
is piinaiiIy due lo lhe incieased suiface aiea of nanoviies conpaied lo lhal of spheies. This
diffeience in slalic sliffness is lhus alliiluled lo lhe incieased conlacl suiface aiea in
nanoviies conlined vilh lhe giealei conpiessive slienglh of lhe nanoviies conpaied lo
lhe niciospheies.
The piedicled eIaslic noduIus of lhe nanoviie-lased MRL conposile vas deleinined ly
lhe nodified HaIpin-Tsai equalion (HaIpin & Kaidos, 1976) and conpaied vilh lhe
expeiinenlaI iesuIls. Il vas shovn lhal lhe lheoielicaI nodeI can adequaleIy piedicl lhe
eIaslic piopeilies of lhe conposiles (Song el aI., 2OO9l).

The nanoviie-lased MRL conposiles exhililed Iaigei specific noduIi (defined as lhe eIaslic
noduIus ovei lhe densily) lhan lhe niciospheie-lased sanpIes, inpIying lhal lhe
nanoviie-lased MRL conposiles viII dispIay enhanced peifoinance ovei lheii heaviei
counleipails (i.e., Iovei vl. nanoviie MRLs can le used in pIace of lhe heaviei, highei
vl. niciospheie conposiles). Conpaied lo lhe iion nanoviie-lased MRL conposile, lhe
colaIl nanoviie-lased MRL conposile dispIayed an even highei specific noduIus.
Using lhe inghan nodeI, lhe lolaI foice of an MRL conposile can le nodeIed in leins of
lhe eIaslic and MR effecl as foIIovs:
( ) ( ) ( ) ( ) " . . !
total e e MRE
F t k x t c x t F t (1O)

O
1O
2O
3O
4O
5O
6O
O 1O 2O 3O 4O 5O 6O
!
.
=
.
0
2

/
.
0
>
>
-
*
/
/

'
(
"
$
D
+
E*07A. >:=2.03- 'F.G H+
Ie nanoviies
Ie spheies
Co nanoviies
Co spheies

Iig. 11. Measuied slalic sliffness of lhe nanoviie-lased MRL conposiles veisus lhe veighl
fiaclion of pailicIes in lhe alsence of nagnelic fieId.
Electrodeposited Nanowires and Their Applications

206
-O.O1
O
O.O1
O.O2
O.O3
O.O4
O.O5
O.O6
O.O7
O.O8
O.O9
O.1
O O.O5 O.1 O.15 O.2 O.25
8
0
*
9
6

/
.
:
*
/
/

'
#
<
=
+
#=7-*.02 >94? 6*-/0.1 '@+
Ie nanoviies
Ie spheies
Co nanoviies
Co spheies

Iig. 12. The yieId sliess of iion and colaIl nanoviie-lased MRL conposiles veisus nagnelic
fIux densily. The cuives aie sinpIy a guide foi lhe eye.
vilh

4 5
4 5
3
O
( )
4
( ) sgn ( )
3 ( )
)
9EF
1 G
H / I /
I I /
6 ,
"
.
! (11)
Heie, J
$
and ;
$
aie lhe sliffness and danping coefficienls of lhe MRL conposile, iespecliveIy.
H
9EF
(/) is lhe conlioIIalIe danping foice al a given nagnelic fIux densily, 1 is lhe iadius of
MRL conposile, and I
K
and I(/) aie lhe iniliaI posilion and excilalion dispIacenenl,
iespecliveIy. In addilion, lhe yieId sliess can le iepiesenled ly
( ) (in MIa)
y
B B
7
, 8 " (12)
vheie % and & aie an enpiiicaIIy-deleinined coefficienl and exponenl, and G is lhe nagnelic
fIux densily (G) in TesIa. The yieId sliess of lhe nanoviie-lased MRL conposiles veisus lhe
nagnelic fIux densily is shovn in Iig. 12. In lhis figuie, lhe yieId sliess vas caIcuIaled fion
lhe incienenl of foice (i.e., lhe diffeience in yieId sliess lelveen O.2 T and zeio fieId) ly
using Lqs. 1O-12. SiniIai lo lhe yieId sliess lehavioi of MR fIuids, lhe yieId sliess of lhe
MRL conposiles can le nodeIed as a povei-Iav funclion of G.
The dynanic iange of lhe nanoviie-lased MRL conposiles vas evaIualed ly neasuiing
fieId-dependenl dynanic sliffness and equivaIenl danping. The nanoviie-lased MRL
conposiles had neaiIy lhe sane dynanic sliffness, hovevei, lhese conposiles dispIay
giealei equivaIenl danping ianges lhan lhe niciospheie-lased MRL conposiles (Iig. 13).
In addilion, lhe 1O vl. colaIl nanoviie-lased MRL conposile had an incieased danping
capacily ovei lhal of lhe 1O vl. iion nanoviie-lased sanpIe.
The effecl of aIigned vs. nonaIigned pailicIes in lhe sanpIes vas olseived in 1O vl. colaIl
nanoviie-lased MRLs: aIigned nanoviie-lased MRL conposile dispIayed a nuch giealei
danping capacily lhan lhal of lhe nonaIigned sanpIes (Iig. 14).
The slalic sliffness of lolh spheiicaI niciopailicIe- and nanoviie-lased MRL conposiles
incieases nonolonicaIIy as lhe pailicIe-veighl-fiaclion is incieased. The nanoviie-lased
MRL conposiles dispIay a giealei sensilivily lo lhe veighl fiaclion lhan lhal of spheiicaI
Impact of Nanowires on the Properties of Magnetorheological Fluids and Elastomer Composites

207

Iig. 13. LquivaIenl danping foi 1O vl nanoviie MRL conposiles in lhe fiequency donain.


0
0.5
1
1.5
2
2.5
3
0 5 10 15 20 25
E
q
u
i
v
a
l
e
n
t

d
a
m
p
i
n
g

(
k
N

s
/
m
)
Frequency (Hz)
Aligned (0.0 T)
Aligned (0.2 T)
Non-aligned (0.0 T)
Non-aligned (0.2 T)

Iig. 14. LquivaIenl danping of lhe Co nanoviie-lased MRL conposile: AIigned vs.
nonaIigned pailicIes.
niciopailicIe-lased MRL conposiles, a iesuIl of lhe incieased suiface aiea of lhe nanoviies.
The nanoviie-lased MRL conposiles exhililed Iaigei specific noduIi lhan lhe
niciopailicIe-lased sanpIes, inpIying lhal lhe nanoviie-lased MRL conposiles having
high specific noduIi lhal can yieId enhanced peifoinance ovei lheii heaviei counleipails.
The nanoviie-lased MRL conposiles geneialed giealei dynanic sliffness and equivaIenl
danping ianges lhan lhe spheiicaI niciopailicIe-lased MRL conposiles. In addilion, lhe 1O
Electrodeposited Nanowires and Their Applications

208
vl Co nanoviie-lased MRL conposile had incieased danping capacily ovei lhe 1O vl
iion nanoviie-lased sanpIe.
7. Conclusions
Nanoviies aie veII suiled as nodeI pailicIes foi lhe expIoialion of lhe shape- and
conposilion-dependenl piopeilies of lhe suspended pailicIes in nagneloiheoIogicaI fIuid
and eIaslonei conposiles. Tvo najoi advanlages can le seen foi lhe nanoviie-lased MR
suspensions as conpaied lo lhose lhal conlain sliiclIy spheiicaI pailicIes. The nanoviie-
lased suspensions nake foi a noie efficienl MR fIuid (highei yieId sliesses) al Iov
nagnelic fieIds aIIoving foi noie sensilive conlioI of lhe fIuid piopeilies. The
sedinenlalion veIocily and lhe peicenlage of sedinenlalion aie lolh giealIy ieduced
conpaied lo convenlionaI MR fIuids. A disadvanlage of lhe suspensions is lhal lhe
naxinun voIune fiaclion of nanoviies is nuch Iess lhan lhe desiied 3O-4O voI.
achievalIe vilh spheiicaI pailicIes. Ioi lhese ieasons, suspensions lhal conlain sliiclIy
nanoviies vouId le noie usefuI in appIicalions vheie sedinenlalion vouId le exlieneIy
deliinenlaI and Iov yieId sliesses aie sufficienl. Dinoiphic MR fIuids exhilil veiy
alliaclive nagneloiheoIogicaI and sedinenlalion piopeilies lhal nake lhen feasilIe foi an
expanded sel of device appIicalions, since lhe highei nass Ioadings of convenlionaI MR
fIuids can le allained. WhiIe lhe diffeiences in lhe iheoIogicaI piopeilies of lhe fIuids
conlaining lhe spheiicaI and nanoviie pailicIes nusl iesuIl fion a conlinalion of nagnelic
and nechanicaI piopeilies, sepaialing lhe delaiIs of lhese effecls viII iequiie noie in-deplh
expeiinenlaI and lheoielicaI sludies. Iuilhei voik on lhis nev lype of MR fIuid viII consisl
of exanining suspensions vilh naiiov nanoviie Ienglh disliilulions and vaiying lhe
dianeleis lo fuilhei undeisland lhe dependency of nagneloiheoIogicaI and sedinenlalion
piopeilies on aspecl ialio. In lhe case of nanoviie-lased MRLs, lhe slalic sliffness vas
highei lhan lhal of spheiicaI pailicIe-lased eIasloneis in lhe alsence of a nagnelic fieId al
lhe sane veighl fiaclion due lo lhe incieased suiface aiea of lhe nanoviies as conpaied lo
lhe spheiicaI pailicIes. Wilh nanoviie-lased MRL sanpIes, lhe equivaIenl danping vas
significanlIy giealei in lhe piesence of a nagnelic fieId. Iuluie sludies viII incIude lhe
consideialion of aspecl ialio dependence, as veII as an expIoialion of lhe peicoIalion
liansilion vilhin lhese unique conposile naleiiaIs.
8. Acknowledgements
The aulhois acknovIedge funding suppoil fion lhe NalionaI Science Ioundalion (NSI-CLT-
O755696), The IennsyIvania Slale Univeisily, and AIloona CoIIege. AddilionaI suppoil
piovided ly a DARIA SIR Ihase 2 Conliacl No. W31I4Q-O6-C-O4OO (N. M. WeieIey). This
pulIicalion vas suppoiled ly lhe IennsyIvania Slale Univeisily MaleiiaIs Reseaich Inslilule
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O335765, NalionaI NanolechnoIogy Infiasliucluie Nelvoik, vilh CoineII Univeisily.
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