Effect of Carbon Bl ack and Si l i ca Fi l l ers i n El astomer Bl ends

Yimin Zhang,

S. Ge,

B. Tang,

T. Koga,

M. H. Rafailovich,*
,
J . C. Sokolov,

D. G. Peiffer,

Z. Li,

A. J . Dias,

K. O. McElrath,

M. Y. Lin,

S. K. Satija,

S. G. Urquhart,
#,&
H. Ade,
#
and D. Nguyen
$
Department of Materials Scienceand Engineering, StateUniversity of New York at Stony Brook,
Stony Brook, New York 11794-2275; ExxonMobil Research and Engineering Company,
Annandale, New J ersey 08801; ExxonMobil Chemical Company, Polymer Scienceand Butyl
Technology Divisions, Baytown, Texas 77520; Center for Neutron Research, National I nstituteof
Standards and Technology, Gaithersburg, Maryland 20899; Department of Physics,
North Carolina StateUniversity, Raleigh, North Carolina 27695; and Brookhaven National
Laboratory, Upton, New York 11973
Received J anuary 30, 2001
ABSTRACT: The effects of carbon bl ack and pyrogeneous si l i ca fi l l ers on the i nterfaci al properti es of a
homopol ymer [pol ybutadi ene, (PB)] and a terpol ymer [bromi nated pol y(i sobutyl ene-co-p-methyl styrene),
(BI MS)] are reported. Neutron refl ecti vi ty (NR) was used to study the i nterfaci al structure. The resul ts
are compl emented by scanni ng transmi ssi on X-ray mi croscopy (STXM) and l ateral force mi croscopy (LFM),
whi ch were used to probe the morphol ogy and surface l ateral force. Smal l -angl e neutron scatteri ng (SANS)
was used to characteri ze the si ze and surface properti es of the fi l l er aggregates i n el astomers. Our resul ts
show that the i nterfaci al behavi or of PB/BI MS i s more sensi ti ve to carbon bl ack than to si l i ca. The
i nterfaci al broadeni ng i s si gni fi cantl y sl owed down wi th addi ti on of merel y
CB ) 0.01 (vol ume fracti on)
carbon bl ack fi l l ers. Thi s vol ume l evel i s much l ower than that used i n bul k rubbers (CB g 0.1).
Pyrogeneous si l i ca has a l ess pronounced effect on the i nterfaci al characteri sti cs. When both carbon and
si l i ca are i ncorporated i nto the PB l ayer, the effect of carbon bl ack i s offset by si l i ca fi l l ers.
Introduction
Fi l l ers exi st i n a vari ety of systems such as organi c,
bi ol ogi cal , bi omi meti c, and pol ymeri c materi al s.
1
I n the
l atter i nstance, the fi l l ers are i ntenti onal l y added. I n
pol ymer systems, fi l l ers not onl y reduce the cost of the
materi al but al so i mprove the mechani cal and dynami c
properti es of the compounds. Carbon bl ack and si l i ca
are the most wi del y used fi l l ers i n rubber i ndustry. For
exampl e, carbon bl ack i mparts strength and toughness
to el astomers, i mproves the rubbers resi stance to tear-
i ng, abrasi on, and fl ex fati gue, and al so i ncreases
tracti on and durabi l i ty.
2
Si l i ca and other types of fi l l ers
have a weaker pol ymer-fi l l er i nteracti on and are
extensi vel y used where a hi gh degree of rei nforcement
i s not essenti al .
3
Recentl y, si l i ca was found to i mprove
the processabi l i ty of rubbers and was used as parti al
or even compl ete repl acement for carbon bl ack fi l l ers.
4
Consequentl y, a si gni fi cant research effort was dedi -
cated to expl ai n the compl ex rei nforci ng effects of fi l l ers
i n rubber matri ces. Al though there are di sagreements
i n certai n areas, i t i s wel l accepted that the rei nforce-
ment effects are due to mol ecul ar i nteracti ons of the
rubber and fi l l er parti cl es.
5
Previ ous studi es of fi l l er-
el astomer systems have mostl y been conducted on bul k
rubber wi th a l arge vol ume fracti on ( g 0.1) of fi l l er
parti cl es. For exampl e, rheol ogi cal data on fi l l ed com-
pounds of varyi ng fi l l er vol ume fracti on, such as Mooney
vi scosi ty, mi ni mum torque of curometer measurement,
and modul us, i ndi cate that the rei nforci ng effect i s not
apparent unl ess the carbon bl ack fi l l er vol ume fracti on
i s more than 0.05.
I n many appl i cati ons, di fferent types of unfi l l ed and
fi l l ed rubber compounds are bl ended. The ul ti mate
properti es of these bl ends are di rectl y rel ated to the
i nterfaci al structure and properti es. Control of the
i nterfaci al properti es, such as adhesi on, can have a
dramati c i mpact on the performance of the bl end.
However, quanti fi cati on of surface and i nterface proper-
ti es i s l ess expl ored due to the compl exi ty of the
pol ymer-fi l l er matri x. Previ ousl y, several groups have
shown that the dynami cs of pol ymers near an attracti ve
i nterface can be drasti cal l y reduced.
6-9
I n a fi l l er-
pol ymer composi te, especi al l y i n pol ymer nanocompos-
i tes, there i s a l arge excess of i nterfaci al area created.
Hence, i t i s i mportant to determi ne how the i nterfaci al
i nteracti ons between the fi l l er and pol ymers affect the
dynami cs of i nterface formati on and rheol ogi cal proper-
ti es.
The two el astomers studi ed i n thi s work are pol y-
butadi ene (PB) and bromi nated pol y(i sobutyl ene-co-p-
methyl styrene) (BI MS), a syntheti c terpol ymer of i so-
butyl ene (I B), p-methyl styrene (PMS), and p-bromo-
methyl styrene (BrPMS). The mol ecul ar structures of
BI MS and i ts unbromi nated anal ogue copol ymer pol y-
(i sobutyl ene-co-p-methyl styrene) (I MS) are shown i n
Fi gure 1. I sobutyl ene-based el astomers are wi del y used
i n the automoti ve i ndustry because these materi al s
possess l ow permeabi l i ty to gases, and one can control
the mechani cal properti es by varyi ng the l evel of I B and
PMS as wel l as fi l l er content and cross-l i nk densi ty.
10
Consequentl y, i n standard rubber ti res, both the hard
si dewal l and the softer i nner l i ner can be made of
carbon-rei nforced BI MS bl ended wi th butyl and natural
rubber.
11

State Uni versi ty of New York at Stony Brook.

ExxonMobi l Research and Engi neeri ng Company.

ExxonMobi l Chemi cal Company.

Nati onal I nsti tute of Standards and Technol ogy.

#
North Carol i na State Uni versi ty.
$
Brookhaven Nati onal Laboratory.
&
Current address: Department of Chemi stry, Uni versi ty of
Saskatchewan, Saskatoon, SK S7N 5C9, Canada.
* To whom correspondence shoul d be addressed.
7056 Macromolecules 2001, 34, 7056-7065
10.1021/ma010183p CCC: $20.00 2001 Ameri can Chemi cal Soci ety
Publ i shed on Web 08/31/2001
I n thi s paper we descri be neutron refl ecti vi ty (NR)
measurements to determi ne the effects of l ow carbon
bl ack and si l i ca fi l l er fracti on on the i nterface formati on
between BI MS and PB. Smal l -angl e neutron scatteri ng
(SANS) i s used to characteri ze the domai n si ze of fi l l er
aggregates i n el astomer-fi l l er matri xes. Lateral force
mi croscopy (LFM) and scanni ng transmi ssi on X-ray
mi croscopy (STXM) are used to determi ne the surface
rheol ogi cal properti es i n the presence of fi l l ers.
Experimental Section
Materials. The characteri sti c data of several grades of
BI MS terpol ymer and the unbromi nated anal ogue copol ymer
(I MS), provi ded by ExxonMobi l Chemi cal Corp. (Baytown, TX),
are l i sted i n Tabl e 1. Both pol ymers are el astomeri c i n nature
wi th a l ow T
g (-50 C).
10
The pol ydi spersi ty of these com-
merci al pol ymers i s i n the range 2.5-2.8. Monodi sperse dPB
(Mn ) 223 000, Mw/Mn < 1.03) was purchased from Pol ymer
Source I nc., Montreal , Canada. Three types of carbon bl ack,
N330, N351, and N660, were suppl i ed by Carbot Corp.,
Bi l l eri ca, MA, wi th pri mary parti cl e si zes of 290, 290, and 500
, respecti vel y. Si l i ca parti cl es were pyrogenous si l i ca Aerosi l
300, wi th pri mary parti cl e si ze of 90 and speci fi c surface
area of 295 m
2
/g. The densi ty of carbon bl ack and si l i ca are
1.85 and 2.2 g/cm
3
, whi ch was used for conversi on from wei ght
fracti on to vol ume fracti on (). Detai l ed characteri sti cs of these
fi l l ers can be found el sewhere.
12,13
Hereafter, we use CB and
SF to descri be the vol ume fracti on of carbon bl ack and si l i ca
fi l l ers, respecti vel y.
Small-Angle Neuron Scattering (SANS). Prescri bed
amounts of carbon bl ack and pol ymer, as l i sted i n Tabl e 2,
were wei ghted and mi xed i n a Brabender at 100 rpm and 150
C for 10 mi n. Approxi matel y 0.5 g of the mi xture was pl aced
i n a sampl e hol der. The fi nal shape of the sampl e i s ci rcul ar
wi th a thi ckness of 1 mm wi th the fl at faces perpendi cul ar to
the neutron beam. Thi s path l ength was chosen to ensure the
best bal ance between the scatteri ng i ntensi ty and attenuati on.
Otherwi se, the sampl es are consi dered i sotropi c wi th no
preferred ori entati on.
To probe an extended range of the momentum transfer, or
scatteri ng wavevector, q, a combi nati on of conventi onal SANS
and ul trasmal l -angl e neutron scatteri ng (USANS) measure-
ments were performed. The conventi onal SANS was performed
at the Center for Neutron Research (NCNR), the Nati onal
I nsti tute of Standards and Technol ogy (NI ST), i n Gai thers-
burg, MD. A neutron wavel ength of 6 was used, wi th two
col l i mati on confi gurati ons. One has a sampl e-detector di s-
tance of 2.9 m, measuri ng the hi gh q range of 0.03-0.2
-1
.
The other has the sampl e-detector di stance set at 15.2 m,
measuri ng a medi um qrange from 0.003 to 0.04
-1
. Standard
sampl es were used to cal i brate the i nstrument so al l i ntensi ty
measured was of the absol ute scal e of scatteri ng cross secti on
per uni t vol ume (uni t of cm
-1
). The USANS experi ments were
performed at Oak Ri dge Nati onal Laboratory, i n Oak Ri dge,
TN. A Bonse-Hart setup wi th two tri pl e bounce Si crystal s was
used as monochromator and anal yzer for the ul trahi gh angul ar
resol uti on obtai ned.
14
Wi th the neutron wavel ength set at 2.59
, the i nstrument produces ul tral ow q range data of 0.0001-
0.002
-1
. Because USANS data were taken wi th sl i t geometry
and conventi onal SANS has pi nhol e geometry, a deconvol uti on
was done for the USANS data before al l three sets of the data
from the same sampl e were merged, produci ng a wi de qrange
from 0.0001 to 0.2
-1
.
Neutron Reflectometry (NR). A detai l ed procedure of
sampl e preparati on was descri bed i n a previ ous arti cl e.
15
Here
we onl y bri efl y descri be thi s procedure. The NR sampl es
consi st of two pol ymer l ayers. The fi rst l ayer of dPB was spi n-
coated on si l i con substrates from a tol uene sol uti on at 2500
rpm. To prepare anal ogue dPB l ayers wi th carbon bl ack or
hydrophobi c si l i ca fi l l ers, the fi l l er was wei ghted and di ssol ved
i n a smal l amount of tol uene by soni cati on, and then the fi l l er-
contai ni ng sol uti on was thoroughl y mi xed wi th a prescri bed
amount of the dPB sol uti on before spi n-coati ng. The si l i con
wafer substrate was 1 cm thi ck and 7.6 cm i n di ameter and
was etched by HF to ensure a hydrophobi c surface before
i ntroduci ng the fi rst l ayer of dPB. Thi s l ayer was then
preanneal ed at 120 C for 1 h i n a vacuum of 10
-3
Torr to rel ax
any strai ns and remove the sol vent i ntroduced from the
spi nni ng process. The second l ayer was prepared by mol di ng
5 g of BI MS (or carbon-fi l l ed el astomer of prescri bed composi -
ti on) i nto a di sk-shaped pi ece, whi ch has a thi ckness of 1 mm
and a di ameter of 7.6 cm. The two l ayers were sandwi ched
just pri or to the NR experi ment. To measure the i nterdi ffusi on
between the two pol ymer l ayers, the bi l ayer sampl e, confi ned
i n a speci al press, was pl aced i n an oven and anneal ed i n a
vacuum of 10
-3
Torr at 150 C for prescri bed ti mes. After
anneal i ng, the sampl es were qui ckl y quenched i n ai r to room
temperature wi thi n 5 mi n.
The sandwi ched wafers were then mounted on the hori zon-
tal sampl e tabl e at the NI STneutron refl ecti on spectrometer.
The NR geometry i s shown i n Fi gure 2. The neutron beam
enters through the 1 cm thi ck si l i con wafer i n the Q
i n di recti on,
and then i t i s refl ected from the BI MS/dPB and si l i con
i nterfaces and i s detected agai n i n the Qout di recti on. The
techni que of NR and i ts data anal ysi s were previ ousl y di s-
cussed i n a revi ew by Russel l .
16
I n thi s work, there are seven
Figure1. Mol ecul ar structures of the BI MS terpol ymers and
I MS copol ymer.
Table 1. Isobutylene, p-Methylstyrene,
p-Bromomethylstyrene, Number-Averaged Molecular
Weight (Mn), and Neutron Scattering Length Density
(SLD) of BIMS and IMS Polymers Used in This Study
pol ymer
PI B
(mol %)
PMS
(mol %)
BrPMS
(mol %)
Mn
(kg/mol )
SLD
(10
-6

-2
)
BI MS-1 93 6.2 0.75 189 -0.21
BI MS-2 94 5.2 0.85 200 -0.23
BI MS-3 96 2.5 1.2 200 -0.27
I MS 94 6.1 0 200 -0.23
Table 2. Composition and Aggregate Size of SANS
Samples
pol ymer vol fracti on () of fi l l er Rg of aggregates ()
I MS CB ) 0.025 1200
I MS CB ) 0.005 1200
BI MS-2 CB ) 0.025 1100
BI MS-2 CB ) 0.005 1100
BI MS-3 SF ) 0.025 >10000
Macromolecules, Vol. 34, No. 20, 2001 Fi l l ers i n El astomer Bands 7057
bi l ayer sampl es, the composi ti ons of whi ch are l i sted i n Tabl e
3. We wi l l hereafter menti on these bi l ayers as sampl es A-G.
ScanningTransmissionX-rayMicroscopy(STXM). The
STXM sampl es were prepared by spi n-coati ng fi l ms of ap-
proxi matel y 1200 thi ck on Si
3N4 membranes. The Si 3N4
membrane provi des an X-ray transparent substrate to support
the thi n pol ymer l ayers for X-ray mi croscopy i nvesti gati on. The
resul tant two fi l ms (50/50 bl end of dPB/BI MS-1 and 50/50
bl end of PB/BI MS-1 wi th fi l l ers CB ) 0.025) were anneal ed
i n a vacuum oven for 18 h at 150 C. The STXM experi ment
was performed on beaml i ne X1A at the Nati onal Synchrotron
Li ght Source (NSLS) at Brookhaven Nati onal Laboratory
(BNL). The STXM mi croscope uses di ffracti ve focusi ng opti cs
(a Fresnel zone pl ate) to produce a mi croprobe wi th a 35-50
nm di ameter. An i mage i s formed by measuri ng the transmi t-
ted X-ray si gnal as a thi n sampl e secti on (typi cal l y 100 nm
thi ck) i s raster scanned through the focus of the zone pl ate.
The X-ray energy used for i magi ng can be chosen to correspond
to di screte el ectroni c transi ti ons i n the materi al , such as the
C 1s f *
CdC transi ti on associ ated wi th CdC doubl e bonds,
whi ch occurs at 285 eV i n most materi al s. Thi s X-ray
absorpti on can be used to form a chemi cal i mage contrast. Thi s
mi croscope has been descri bed by Jacobsen et al .,
17
and the
appl i cati ons to pol ymers were recentl y revi ewed.
18
Lateral ForceMicroscopy(LFM). Si l i con wafers (300 m
thi ck, ori entati on 100, Wafer Worl d I nc., West Pal m Beach,
FL) were cut i nto 2 cm 2 cm pi eces and cl eaned by CrO3/
H2SO4 sol uti on fol l owed by di l ute HF to remove any organi c
and the oxi de l ayer. The i ni ti al l y stati onary wafer was fl ooded
wi th tol uene contai ni ng 14 mg/mL dPB and carbon bl ack N330
of CB ) 0-0.15 and then qui ckl y (wi thi n 2 s) accel erated to
2500 rpm for 30 s. The resul tant fi l ms, wi th thi ckness
approxi matel y 690 , were measured wi th a Rudol ph AutoEL
el l i psometer. The reference pol ystyrene (PS, Mn ) 280K,
Pol ymer Source I nc.) l ayers were fi rst spi n-coated onto gl ass
substrates. After bei ng fl oated off the gl ass substrates and onto
the surface of a di sti l l ed water bath, the PS fi l ms were pi cked
up by the si l i con wafers precoated wi th carbon-bl ack-fi l l ed dPB
l ayers. The PS fi l m i s 230 thi ck and onl y parti al l y covers
the precoated dPB surface. Subsequentl y, the doubl e-l ayer
sampl es were dri ed i n ai r for 24 h. The thi n fi l ms wi th si l i ca
fi l l ers were prepared by a si mi l ar procedure.
The topography and l ateral force of these dPB l ayers
contai ni ng di fferent
CB and SF were i maged wi th a DI 3000
AFM (Nanoscope I I I a, Di gi tal I nstruments, Co., Ltd., Santa
Barbara, CA). The AFM was operated i n the contact mode, at
room temperature, i n a seal ed gl ovebox purged wi th dry
ni trogen gas, usi ng a si l i con ni tri de ti p on a canti l ever wi th a
bendi ng spri ng constant of 0.02-0.1 N/m. The i mage force was
repul si ve, approxi matel y 25 nN. LFM i mages the l ateral
defl ecti ons of the canti l ever from forces on the canti l ever
paral l el to the pl ane of the sampl e surface. To obtai n the
maxi mum LFM si gnal , the canti l ever was scanned al ong the
di recti on perpendi cul ar to i ts axi s. The l ateral force measure-
ment i nvesti gates the fri cti on vari ati on of the el astomer
surfaces. Si nce the true val ue of canti l ever spri ng constant i s
unknown, the rel ati ve l ateral force was esti mated by usi ng a
reference PS l ayer covered on the sampl e surface.
Results and Discussion
Small-AngleNeutronScattering. SANS measures
the mi cromorphol ogy of a bul k sampl e. We combi ne
conventi onal SANS and USANS to probe l ength scal es
from 10 to mi crons. Therefore, the purpose of SANS
experi ments was to observe whether the fi l l er parti cl es
are wel l di spersed i n the el astomer matri x and to
characteri ze the si ze of fi l l er parti cl es or aggregates. I n
addi ti on, i nterfaci al properti es between the parti cl es
and thei r surroundi ng pol ymer chai ns can al so be
probed wi th SANS.
The resul t of two sl i ghtl y di fferent systems, N330/
BI MS-2 and N660/I MS, i s shown i n Fi gure 3 and Fi gure
4. I n the fi gures we pl ot the scatteri ng i ntensi ty I as a
functi on of q. The two curves i n each fi gure represent
two di fferent carbon/el astomer vol ume fracti ons (upper
curves,
CB
) 0.025; l ower curves,
CB
) 0.005) to test
concentrati on effects, i f any. The i ntensi ty for both
sampl es scal es wi th
CB
(actual scal i ng not shown),
Figure 2. Typi cal geometry of specul ar neutron refl ecti vi ty
setup. A thi n dPB fi l m i s spun-cast onto a 1 cm thi ck Si wafer.
A 1 mm thi ck di sk of BI MS i s pl aced on top of the dPB l ayer.
The neutron beam enters through the Si wafer i n the Qi n
di recti on. The beam i s refl ected from the dPB/BI MS i nterface
and i s detected i n the Qout di recti on.
Table 3. Structure and Composition of Seven Bilayer
Samples for NR Experiment
l ower dPB l ayer
top el astomer Layer
sampl e
desi gnati on
thi ckness
() fi l l er vol el astomer fi l l er vol
A 500 0 BI MS-1 0
B 450 CB ) 0.003 BI MS-1 0
C 380 CB ) 0.005 BI MS-1 0
D 380 CB ) 0.025 BI MS-1 0
E 580 0 I MS CB ) 0.025
F 600 SF ) 0.005 BI MS-1 0
G 600 0 BI MS-2 CB ) SF ) 0.01
Figure 3. A l og-l og pl ot of scatteri ng i ntensi ty (I ) as a
functi on of qfor I MS bl ended wi th carbon N330 of CB ) 0.025
(upper curve) and CB ) 0.005 (l ower curve).
Figure4. A l og-l og pl ot of scatteri ng i ntensi ty as a functi on
of q for BI MS-2 bl ended wi th carbon N660 of CB ) 0.025
(upper curve) and CB ) 0.005 (l ower curve).
7058 Zhang et al . Macromolecules, Vol. 34, No. 20, 2001
i ndi cati ng l i ttl e concentrati on effects. The combi nati on
of SANS and USANS data from q ) 0.0003 to 0.2
-1
cover a very broad q range for the carbon bl ack ag-
gregates. A rol l -over toward the l ow q end can be seen
from the curves, al l owi ng Gui ni er fi ts of the data to
obtai n the radi us of gyrati on of the i ndi vi dual ag-
gregates. Gui ni ers equati on i s as fol l ows:
19
where I i s the scattered i ntensi ty, I
0
i s a q-i ndependent
quanti ty, and R
g
i s the average radi us of gyrati on.
Therefore, i f l n(I ) i s pl otted vs q
2
i n the ul tral ow qrange
(q < 0.001
-1
), the sl ope of the l i near fi t equal s -
1
/
3
R
g
2
. I t shoul d be noted that thi s argument i s val i d onl y
i f there i s a l i near fi t between the two quanti ti es, and
qR
g
i s smal l er than or cl ose to 1. Usi ng thi s method, we
obtai ned the R
g
val ues of the two sl i ghtl y di fferent
carbon/el astomer systems (1100 and 1200 ), whi ch
were al so l i sted i n Tabl e 2. On the basi s of the pri mary
parti cl e si ze of 290 and 500 , we esti mate that
approxi matel y 10-50 pri mary parti cl es form an average
aggregate i n these systems.
Al so for the carbon bl ack sampl es, a power l aw
behavi or can be seen at hi gh q range. Fi ts to the Porod
form
20
reveal that the exponent for the power l aw i s R ) 4.03
(0.05, suggesti ng rather sharp surfaces of the parti cl es.
I n contrast, the l ow-q data for si l i ca/BI MS-3 system
(Fi gure 5) do not show a rol l -over shape i n the Gui ni er
regi on, even at the USANS range approachi ng q
mi n
)
0.0001
-1
or a l ength scal e of 1/q ) 1 m. Therefore,
the si ze of the aggregates or aggl omerates i s l i kel y
l arger than several mi crons. Thi s i s i n agreement wi th
the l i terature that si l i ca fi l l ers have much stronger
i nterparti cl e i nteracti ons.
21
The broad shoul der peak
whi ch corresponds to the form factor of the pri mary
parti cl es appeared around q ) 0.01
-1
. On the basi s
of the spheri cal model that takes the pol ydi spersi ty of
the parti cl es i nto account, the si ze of the pri mary
parti cl e was esti mated to be 90 wi th pol ydi spersi ty
of 30%, whi ch i s i n good agreement wi th the manu-
facturers speci fi cati on. I n addi ti on, the reasonabl e
strai ght-l i ne shape of the curve at l ow q suggests a
fractal structure wi thi n the aggregates or aggl omerates,
wi th a fractal di mensi on of d
f
) 2.41. From the fi tti ng
at l arger q, the curve bend to another power l aw, where
the same Porod exponent i s measured, R ) 4.05 ( 0.02.
As expected, both types of the fi l l er parti cl es do not fuse
wi th the surroundi ng el astomers.
Neutron Reflectivity. Al l of the refl ecti vi ty profi l es
were pl otted as l og R vs Qz, where Qz ) (4/) si n ,
and Qz, , and are the i nci dent neutron wave vector,
neutron wavel ength, and i nci dent angl e, respecti vel y.
For each sampl e, the refl ecti vi ty curves for di fferent
anneal i ng ti mes were verti cal l y shi fted i n the same
fi gure for cl ari ty and compari son purposes.
Fi gure 6 shows the refl ecti vi ty profi l es (R) obtai ned
for sampl e A after anneal i ng at 150 C for 0 (i .e., no
anneal i ng), 30, 60, and 150 mi n. From the refl ecti vi ty
curve for the unanneal ed sampl e we can see wel l -
defi ned Ki essi g osci l l ati ons, whi ch i ndi cate that the
i nterface between the dPB l ayer and the BI MS-1 i s
sharp. The curve for the unanneal ed sampl e i s fi t by a
si ngl e-l ayer model of dPB wi th an error functi on i nter-
face wi th the BI MS-1, whi ch i s assumed to be an i nfi ni te
medi um. The dPB l ayer i s wel l fi tted wi th a thi ckness
of 494 and a dPB/BI MS i nterfaci al wi dth w ) 30 ,
as shown i n the i nset. After anneal i ng for 30 mi n, the
ampl i tude of the osci l l ati ons decreases, i ndi cati ng that
the i nterface i s becomi ng more di ffuse. The concentra-
ti on profi l e of di ffused dPB l ayer can be fi tted by an
asymmetri c model descri bed el sewhere.
15
The dPB/
BI MS i nterface after 30 mi n of anneal i ng was found to
be 260 . Further anneal i ng for a total of 150 mi n
yi el ded a profi l e wi th an i nterfaci al wi dth of 340 ,
whi ch i s i n agreement wi th the equi l i bri um val ue
measured previ ousl y.
15
The remai ni ng l ow-frequency
osci l l ati on i s due to a monol ayer of dPB adsorbed to the
hydrophobi c si l i con surface, whi ch i s di scussed el se-
where.
15
Fi gure 7 shows the refl ecti vi ty profi l es for a sampl e
where carbon bl ack of
CB
) 0.003 was i ncorporated i n
the l ower dPB l ayer (sampl e B). From the fi gure we can
see that the i nterdi ffusi on has al ready begun to sl ow
even though the carbon bl ack concentrati on i s very
smal l .
22
The best fi ts to the data are shown i n the i nset
where we can see that the i nterface gradual l y broadens
Figure5. A l og-l og pl ot of scatteri ng i ntensi ty as a functi on
of q for BI MS-3 bl ended wi th hydrophi l i c si l i ca SF ) 0.005.
At l ow q regi on rol l over was not found. Dotted l i ne i s the
best fi t of spheri cal model to scatteri ng profi l es. The di ameter,
R, and pol ydi spersi ty, (R)/ R, of the parti cl es are 90 and
0.3, respecti vel y.
I ) I
0
e
-(1/3)q
2
R
g
2
(i f qR
g
e 1)
I ) Aq
-R
(i f qR
g
. 1)
Figure 6. Neutron refl ecti vi ty data for di fferent anneal i ng
ti mes of the bi l ayer sampl e wi th a l ower l ayer (dPB) 500
thi ck and an overl ayer (BI MS-1) 1 mm thi ck. The sol i d l i nes
represent the best fi ts to the experi mental data. The data sets
are offset for cl ari ty. The i nset shows best-fi t profi l es of dPB
vol ume fracti on as a functi on of di stance from the si l i con
surface.
Macromolecules, Vol. 34, No. 20, 2001 Fi l l ers i n El astomer Bands 7059
from 50 for the unanneal ed sampl e to a maxi mum of
228 after anneal i ng for 150 mi n. From Fi gure 8 we
can see that when
CB
i s i ncreased to 0.005 i n the dPB
l ayer (sampl e C), the i nterdi ffusi on i s drasti cal l y sl owed.
The Ki essi g osci l l ati ons i n the specul ar refl ecti vi ty are
hardl y damped even after anneal i ng at 150 bcC for 150
mi n. The vol ume profi l e that best fi ts the data i s shown
i n the i nset where we see that the i nterface broadens
onl y from 30 to 50 after 150 mi n of anneal i ng. When

CB
i s i ncreased to 0.025 (sampl e D), i nterdi ffusi on was
not observed at al l . From the refl ecti vi ty data shown i n
Fi gure 9 we can see that the Ki essi g osci l l ati ons are i n
fact sl i ghtl y sharper i n the anneal ed sampl e. The
profi l es used to fi t the data are shown i n the i nset where
we can see that the i nterface sharpens from 30 to 20
after anneal i ng for 150 mi n. To rul e out confi nement
effects i n the thi n dPB fi l m or other i nterference from
the proxi mi ty of the si l i con i nterface, we al so mi xed
carbon bl ack parti cl es i nto an I MS (i .e., the unbromi -
nated anal ogue of BI MS) matri x usi ng a Brabender
mi xer. I n Fi gure 10 we show the refl ecti vi ty data for
sampl e E whi ch corresponds to an unfi l l ed l ower l ayer
of dPB wi th a thi ckness of 580 sandwi ched wi th a 1
mm thi ck sl ab of I MS wi th
CB
) 0.025. From the fi gure
we can see that the Ki essi g fri nges persi st after anneal -
i ng for 150 mi n i n thi s sampl e as wel l . From the profi l es
that are used to fi t the data (shown i n the i nset) we
can see that onl y a smal l amount of i nterdi ffusi on
occurs. The i nterface shows a gradual broadeni ng from
22 to 95 . Most of the broadeni ng i s due to a l ong tai l
i n the fi tted vol ume fracti on profi l es, probabl y i nduced
by di ffusi on of the l ow mol ecul ar wei ght chai ns, as I MS
and BI MS both have a rel ati vel y l arge pol ydi spersi ty
of 2.5-2.7. Hence, the addi ti on of carbon bl ack drasti -
cal l y sl ows down the i nterdi ffusi on regardl ess of the
pol ymer matri x i n whi ch i t i s added. The quanti ti es
added are rel ati vel y smal l compared to the vol umes
usual l y added for commerci al appl i cati ons, such as
Figure 7. Neutron refl ecti vi ty data for di fferent anneal i ng
ti mes of the bi l ayer sampl e wi th a l ower l ayer (dPB fi l l ed wi th
carbon bl ack N351 of CB )0.003) 450 thi ck and an overl ayer
(BI MS-1) 1 mm thi ck. The sol i d l i nes represent the best fi ts
to the experi mental data. The data sets are offset for cl ari ty.
The i nset shows best-fi t profi l es of dPB vol ume fracti on as a
functi on of di stance from the si l i con surface.
Figure 8. Neutron refl ecti vi ty data for di fferent anneal i ng
ti mes of the bi l ayer sampl e wi th a l ower l ayer (dPB fi l l ed wi th
carbon bl ack N351 of CB )0.005) 380 thi ck and an overl ayer
(BI MS-1) 1 mm thi ck. The sol i d l i nes represent the best fi ts
to the experi mental data. The data sets are offset for cl ari ty.
The i nset shows best-fi t profi l es of dPB vol ume fracti on as a
functi on of di stance from the si l i con surface.
Figure 9. Neutron refl ecti vi ty data for di fferent anneal i ng
ti mes of the bi l ayer sampl e wi th a l ower l ayer (dPB fi l l ed wi th
carbon bl ack N351 of CB )0.025) 380 thi ck and an overl ayer
(BI MS-1) 1 mm thi ck. The sol i d l i nes represent the best fi ts
to the experi mental data. The data sets are offset for cl ari ty.
The i nset shows best-fi t profi l es of dPB vol ume fracti on as a
functi on of di stance from the si l i con surface.
Figure10. Neutron refl ecti vi ty data for di fferent anneal i ng
ti mes of the bi l ayer sampl e wi th a l ower l ayer (dPB) 580
thi ck and an overl ayer (I MS bl ended wi th carbon bl ack N660
of CB ) 0.025) 1 mm thi ck. The sol i d l i nes represent the best
fi ts to the experi mental data. The data sets are offset for
cl ari ty. The i nset shows best-fi t profi l es of dPB vol ume fracti on
as a functi on of di stance from the si l i con surface.
7060 Zhang et al . Macromolecules, Vol. 34, No. 20, 2001
rubber ti res and ti re-formi ng bl adders where the fi l l er
(
CB
) 0.10-0.15) i s added for enhanced mechani cal
properti es. To compare the effect of carbon bl ack wi th
si l i ca fi l l ers, hydrophi l i c si l i ca of
SF
) 0.005 was
i ncorporated i nto the dPB l ayer (sampl e F). The neutron
refl ecti vi ty data are shown i n Fi gure 11 where we see
that the Ki essi g osci l l ati ons are al most compl etel y
damped out after 60 mi n of anneal i ng. Further anneal -
i ng for a total of 120 mi n had onl y a modest effect on
the i nterface dynami cs. The i nset shows that the
i nterfaci al wi dth reached an equi l i bri um val ue of 350
, whi ch i s cl ose to that of the unfi l l ed sampl e (A).
I n many appl i cati ons di fferent fi l l ers are bl ended
together. An i mprovement i n properti es i s found vi a thi s
approach due to the possi bl e i nteracti ons between the
fi l l er types. We therefore mi xed two of the most common
fi l l ers, carbon bl ack and si l i ca of approxi matel y )0.01
each, i n the BI MS-2 l ayer, and sandwi ched thi s l ayer
wi th a 600 dPB l ayer (sampl e G). The neutron
refl ecti vi ty data are shown i n Fi gure 12. Despi te the
presence of the carbon bl ack, the i nterface qui ckl y
reaches equi l i bri um, wi th w approxi matel y 380 , as
shown i n the i nset of Fi gure 12. Hence, the i nterfaci al
behavi or of the mi xed fi l l er l ayer i s characteri sti c of the
si l i ca fi l l er rather than the carbon bl ack fi l l er.
Scanning Transmission X-ray Microscopy
(STXM). To exami ne the effects of carbon bl ack on the
equi l i bri um phase morphol ogy, symmetri c bl ends of
BI MS-1 and dPB wi thout and wi th
CB
) 0.025 were
spun-cast onto a Si
3
N
4
membrane and anneal ed for 18
h at 150 C. The STXM scans of the fi l l ed and unfi l l ed
sampl es are shown i n parts a and b of Fi gure 13,
respecti vel y. The dark areas i n the fi gure correspond
to the i ntensi ty of the 285 eV *(CdC) absorpti on i n
dPB,
17
si nce the dPB phase contai ns a hi gher concen-
trati on of doubl e bonds than the BI MS phase. From the
fi gures we can see that dPB forms the conti nuous phase,
whi l e BI MS i s the mostl y di sconti nuous phase. Carbon
bl ack has a broad absorpti on band starti ng at 284 eV;
hence, these fi l l ers can be i maged usi ng an X-ray energy
bel ow the onset of the dPB absorpti on. However, onl y
l arge aggregates of carbon bl ack coul d be seen si nce the
resol uti on of STXM mi croscopy was comparabl e to the
si ze of the average carbon cl usters as determi ned by
USANS. Compari ng the two fi gures, we see that the
BI MS domai ns are tal l er and more di sconti nuous i n the
fi l l ed bl end (Fi gure 13a) than i n the unfi l l ed bl end
(Fi gure 13b). Fi gure 14 i s a scanni ng force mi croscopy
i mage of the fi l l ed and unfi l l ed bl ends of the same
composi ti on, anneal ed at 150 C for 18 h. Compari ng
Fi gure 14 wi th the STXM i mage (Fi gure 13), we can
see that the BI MS domai ns dewet the dPB surface i n
both bl ends. From the cross secti on anal ysi s we obtai n
a contact angl e of 10 and 6 between the BI MS-1 and
dPB i n the fi l l ed and unfi l l ed bl ends, respecti vel y. From
these val ues we can esti mate the equi l i bri um i nterfaci al
wi dth to be 80 and 240 for the fi l l ed and unfi l l ed
systems.
23
These val ues are i n very good agreement wi th
the i nterfaci al wi dth obtai ned from the refl ecti vi ty data.
Hence, the addi ti on of smal l quanti ti es of carbon bl ack
appears to i nhi bi t i nterfaci al mobi l i ty. The quanti ti es
of carbon bl ack added shoul d not al ter the chemi cal
nature of BI MS or dPB, and the quanti ti es added are
too smal l to cause an i ncrease i n the Fl ory-Huggi ns
parameter. Hence, the observed effect i s probabl y due
to decreased dynami cs wi thi n the pol ymer matri x
caused by strong i nteracti ons between the pol ymer and
the fi l l er. These i nteracti ons are weakl y present wi th
si l i ca fi l l ers, and hence si l i ca fi l l ers do not perturb the
Figure11. Neutron refl ecti vi ty data for di fferent anneal i ng
ti mes of the bi l ayer sampl e wi th a l ower l ayer (dPB fi l l ed wi th
si l i ca of SF ) 0.005) 600 thi ck and an overl ayer (BI MS-1) 1
mm thi ck. The sol i d l i nes represent the best fi ts to the
experi mental data. The data sets are offset for cl ari ty. The
i nset shows best-fi t profi l es of dPB vol ume fracti on as a
functi on of di stance from the si l i con surface.
Figure12. Neutron refl ecti vi ty data for di fferent anneal i ng
ti mes of the bi l ayer sampl e wi th a l ower l ayer (dPB) 600
thi ck and an overl ayer (BI MS-2 bl ended wi th CB )SF )0.01)
1 mm thi ck. The sol i d l i nes represent the best fi ts to the
experi mental data. The data sets are offset for cl ari ty. The
i nset shows best-fi t profi l es of dPB vol ume fracti on as a
functi on of di stance from the si l i con surface.
Figure 13. STXM scan (285 eV) of (a) 49/49/2 dPB/BI MS-1/
carbon bl end and (b) 50/50 dPB/BI MS-1 bl end on Si 3N4
membranes. Both fi l ms were anneal ed i n a vacuum oven for
18 h at 150 C. The dark areas correspond to the dPB phase.
Macromolecules, Vol. 34, No. 20, 2001 Fi l l ers i n El astomer Bands 7061
i nternal dynami cs. Unfortunatel y, i t was not possi bl e
to conti nue anneal i ng the NR sampl es i n order to
determi ne the ul ti mate i nterface si nce prol onged an-
neal i ng of the bul k bi l ayer sampl es i s not practi cal as
degradati on of the pol ymer may resul t, and the materi al
begi ns to creep out of the sampl e hol ders.
Lateral Force Microscopy (LFM). A decrease i n
chai n mobi l i ty i nduced by fi l l ers shoul d al so refl ect i tsel f
i n the rheol ogi cal properti es of the fi l l ed homopol ymers.
Fi gure 15a-c shows the SFM and LFM i mages (l eft) of
dPB fi l ms, approxi matel y 690 thi ck, fi l l ed wi th
i ncreasi ng amounts of carbon bl ack. The topmost fi gure
corresponds to the unfi l l ed dPB fi l m. The l ateral force
l oop correspondi ng to the defl ecti on vol tage i n the
canti l ever trace and retrace si gnal s of these i mages i s
shown on the ri ght. From the l ateral force l oop of the
unfi l l ed sampl e we can see that the PS l oop i s much
smal l er than the dPB l oop. The sampl es were scanned
at room temperature, where the PS i s gl assy and hi gh
modul us (T
g
) 100 C), and hence the ti p sl i ps across
the PS surface, produci ng a smal l er fri cti onal drag. The
dPB l ayer, on the other hand, i s an el astomer and
rel ati vel y soft at room temperature (T
g
) -20 C), and
hence the vi scous drag on the ti p i s much l arger. The
magni tude of the l ateral force i s di rectl y proporti onal
to the defl ecti on vol tages where the proporti onal i ty
constant i s the spri ng constant of the canti l ever. Si nce
thi s val ue i s not wel l characteri zed, we use the PS l ayer
as a reference surface. I f we assume the l ateral force of
PS (denoted as V
PS
) to be a constant under the same
experi mental condi ti on, the rel ati ve normal i zed force
val ue (F
dPB
, i n arbi trary uni ts) of the dPB surface equal s
the rati o of the two potenti al s, i .e., V
dPB
/V
PS
, where V
dPB
and V
dPB
are the defl ecti on vol tages of the canti l ever i n
the dPB l oop and PS l oop, respecti vel y. From Fi gure 15a
we can see that F
dPB
i s typi cal l y much greater than 1
i n the absence of fi l l er. Fi gure 15b shows a dPB l ayer
wi th
CB
) 0.005. The l ateral force l oop on the ri ght
shows that F
dPB
has begun to decrease. A few l arge
aggregates have begun to appear on the surface, though
most of the carbon i s bel i eved to be present as 100 nm
parti cl es, whi ch are not vi si bl e wi th the AFM. Cl oser
exami nati on of Fi gure 15b shows that the aggregates
appear much broader i n the LFM than i n topography
i mages. The aggregates appear hi gher i n the area
covered by PS whi l e thei r fri cti on contrast i s very l ow
i n the covered regi on. On the other hand, i n the PB
regi on we can see that the center of each aggregate i s a
l ow fri cti on hard core surrounded by a l arge corona
where the fri cti on i s hi gher than the surroundi ng
background. Thi s area extends over di stances much
l arger than the topographi cal di sturbance, i ndi cati ng
that the perturbati on on the dynami cs due to the
parti cl es can be l ong-ranged. I ncreasi ng the carbon
bl ack vol ume fracti on to
CB
)0.025 (Fi gure 15c) further
decreases the di fference i n the l ateral force l oop between
V
PS
and V
dPB
unti l fi nal l y the two vol tages are equal at

CB
) 0.15. These resul ts are summari zed i n Fi gure 16
where we pl ot F
dPB
vs
CB
or
SF
. From the fi gure we
fi nd that the l ateral force decreases wi th i ncreasi ng
CB
and reaches saturati on at
CB
0.05. I n addi ti on, the
si l i ca fi l l er reduces the l ateral force, but to a l esser
extent. The decrease i n the l ateral force i ndi cates that
dPB i s becomi ng harder and more gl assy i n i ts rheo-
l ogi cal response to the movi ng ti p. Cl earl y, carbon bl ack
has a more pronounced effect. These resul ts are con-
si stent wi th the sl ower dynami cs observed for the same
concentrati on range i n the i nterfaci al measurements.
I n Fi gure 15d we al so show the topographi cal and
l ateral force l oop scans of dPB fi l l ed wi th hydrophi l i c
si l i ca parti cl es of
SF
) 0.025. From the fi gure we can
see that the surface appears much smoother, and no
l arge aggregates are present. The l ateral force l oop i s
seen to change onl y sl i ghtl y wi th si l i ca fi l l er fracti on.
The l ateral force vs
SF
resul ts are al so pl otted i n Fi gure
16. From the fi gure we can see that the reducti on of
F
dPB
as a functi on of
SF
i s much smal l er than that of

CB
. Furthermore, the decrease of F
SF
wi th concentra-
ti on i s much more gradual , and saturati on i s not
reached wi thi n the experi mental concentrati on expl ored
i n thi s study, i .e.,
SF
) 0.15. Fi gure 15e shows the
topography and l ateral force scans of a dPB sampl e wi th
Figure14. AFM i mage of an anneal ed BI MS-1/dPB (50/50) fi l m of 500 (a) wi th carbon bl ack fi l l er CB ) 0.025 (4 m by 4 m
i mage) and (b) wi thout carbon bl ack fi l l er (6 m by 6 m i mage).
7062 Zhang et al . Macromolecules, Vol. 34, No. 20, 2001
carbon bl ack and si l i ca parti cl e mi xtures of
CB
)
SF
) 0.01. From the fi gure i t i s cl ear that the surface
morphol ogy as wel l as fri cti on resembl es that of the
sampl es contai ni ng onl y si l i ca even though the carbon
bl ack content i s si mi l ar to sampl e Fi gure 15b. The
rel ati ve fri cti on of thi s sampl e i s pl otted as a tri angl e
i n Fi gure 16 where we can see that i t overl aps the data
poi nts on the si l i ca fi l l er curve. These resul ts are i n
agreement wi th the neutron refl ecti vi ty data whi ch
showed that the i nterfaci al properti es were more si mi l ar
to the sampl es contai ni ng onl y the si l i ca fi l l er.
The effect of carbon bl ack observed i n both NR and
AFM measurements can be attri buted to the adsorpti on
of the el astomer chai ns onto the fi l l er parti cl e surfaces.
These adsorbed chai ns are usual l y descri bed as bound
rubber i n the l i terature. Bound rubber was previ ousl y
i nvesti gated and confi rmed by extracti on and atomi c
force mi croscopy.
24,25
These studi es i ndi cated that the
di spersed fi l l er parti cl es act l i ke a vul cani zi ng agent
formi ng a cross-l i nked 3-di mensi onal el astomer net-
work. I n thi s network, each fi l l er parti cl e i s adsorbed
by a certai n number of pol ymer chai ns. The number of
bound chai ns i s a functi on of the fi l l er si ze and hence
can vary for a gi ven vol ume fracti on of carbon bl ack i f
aggl omerati on of the parti cl es occurs. Thi s model as-
sumes that onl y chai ns i n di rect contact wi th the fi l l er
parti cl es are i mmobi l i zed.
The average i nterparti cl e di stance T for a fi l l er/
pol ymer matri x may be esti mated as fol l ows:
26
where d and are the average di ameter and vol ume
fracti on of fi l l er parti cl es and i s a geometri c constant
cl ose to 1. The val ues of the i nterparti cal di stance T as
a functi on of vol ume fracti on are pl otted i n Fi gure 17.
Three curves for d ) 50 nm (i .e., pri mary parti cl e si ze
of carbon bl ack characteri zed by the manufacturers
TEM), d ) 120 nm (i .e., USANS resul t for the average
radi us of gyrati on of the carbon aggregates i n our
sampl es), and d ) 0.5 m (i .e., mi ni mum si l i ca ag-
gregate si ze) are shown i n thi s fi gure. Both NR and
Figure 15. SFM (scanni ng force mi croscopy) and LFM (l ateral force mi croscopy) i mages and l ateral force l oops of a 690 dPB
fi l m (a) wi thout fi l l er, (b) wi th CB ) 0.005, (c) wi th CB ) 0.025, (d) wi th SF ) 0.025, and (e) wi th CB ) SF ) 0.01. A 230 PS
l ayer parti al l y covers the dPB surface.
T ) d[(/6)
1/3
- 1]
Macromolecules, Vol. 34, No. 20, 2001 Fi l l ers i n El astomer Bands 7063
AFM i ndi cate that the pol ymers behave as i f they were
cross-l i nked for
CB
> 0.025. At thi s vol ume fracti on we
can extrapol ate from Fi gure 17 that the average i nter-
parti cl e di stance i s approxi matel y 87 nm (for d ) 50
nm) and 211 nm (for d ) 120 nm). These val ues are
si gni fi cantl y l arger than the esti mated si ze of the dPB
chai ns (R
g
) 14 nm). Si nce we do not see both a mobi l e
and bound vol ume fracti ons of chai ns, we can concl ude
that the i nteracti on between the parti cl es and the
el astomers are not l i mi ted to di rect contact. I t has been
establ i shed by several groups that an attracti ve pl anar
i nterface can drasti cal l y reduce the di ffusi on of pol ymer
chai ns for di stances on the order of 100 nm, or 10R
g
.
7,9,27
The nature of thi s l ong-range i nteracti on i s not wel l
understood, but i t i s bel i eved to be medi ated by en-
tangl ements wi thi n the bl end.
27
The pl anar i nterface
has been approxi mated by a two-fl ui d model as i l -
l ustrated i n Fi gure 18a. One fl ui d i s i rreversi bl e bound
to the surface formi ng a densel y cross-l i nked matri x
(shown as green chai ns i n Fi gure 18a), wi th a cross-
l i nki ng densi ty scal i ng as N
1/2
, N
e
, where N
e
i s the
number of entangl ements. Hence, chai ns trapped wi thi n
thi s matri x (shown as bl ue chai ns i n Fi gure 18a) are
strangul ated and di ffuse much sl ower than the free
chai ns (shown as red i n Fi gure 18a) of the bul k
l i qui d.
28
I t i s reasonabl e to assume that a si mi l ar
phenomenon al so occurs i n the vi ci ni ty of the attracti ve
fi l l er parti cl es (Fi gure 18b). Hence, the fi l l ed system i s
the three-di mensi onal anal ogue of the pl anar thi n-fi l m
sampl es. Fol l owi ng thi s anal ogy, the parti cl es are
covered by a bound l ayer of pol ymer (green chai ns)
whi ch then traps subsequent l ayers (bl ue chai ns) and
hi nders thei r di ffusi on. Onl y the l ayers i n di rect contact
are i rreversi bl y bound and detected by sol vati on meth-
ods descri bed i n the l i terature.
29
The other l ayers are
entropi cal l y bound wi thi n the mel t network but are
easi l y removed wi th sol vent.
When the attracti ve surface i s covered by organi c
surfactants, as i n the case of pyrogeneous si l i ca fi l l ers,
where onl y van der Waal s i nteracti ons wi thi n the
pol ymer are present, i t was shown that a much smal l er
decrease i n the pol ymer dynami cs occurs.
7
I n addi ti on,
the range of the i nteracti on i s much shorter and affects
onl y chai ns i n di rect contact wi th the surface. Even
though the bare si l i con surface i s known to i nteract
strongl y wi th PB,
30
the surfactant used to di sperse the
col l oi dal si l i ca fi l l ers can screen the surface i nteracti on.
Hence, onl y a smal l effect on the dynami cs i s observed
Figure16. Rel ati ve fri cti on of 690 thi ck fi l l ed-dPB fi l m vs
CB and SF i n the dPB l ayer. The val ue of the sampl e wi th
mi xed fi l l ers CB ) SF ) 0.01 i s pl otted as the fi l l ed tri angl e.
Figure 17. I nterparti cl e di stance (T) as a functi on of fi l l er
vol ume fracti on () for fi l l ers wi th parti cl e si ze (d) of 500 ,
1200 , and 0.5 m.
Figure18. Schemati c drawi ngs of the pol ymer chai n structure i n (a) an el astomer thi n fi l m on a fl at attracti ve substrate, (b) a
secti on of a carbon-fi l l ed el astomer, and (c) a secti on of an el astomer wi th mi xed carbon bl ack and col l oi dal si l i ca fi l l ers. The
bound, strangul ated, and free chai ns are shown as green, bl ue, and red chai ns. The carbon and col l oi dal si l i ca aggregates
are desi gnated by smal l and l arge spheres, respecti vel y. Note that the si ze of the si l i ca rel ati ve to carbon i s reduced by a factor
of 2 i n order to show the segregati on of el astomer chai ns at the free surface.
7064 Zhang et al . Macromolecules, Vol. 34, No. 20, 2001
even though the fi l l er vol ume fracti on used i s si mi l ar
to those of carbon bl ack. Furthermore, as can be seen
from Fi gure 17, i f the si l i ca aggl omerates are i n excess
of 0.5 m, then the i nterparti cl e di stance i s too l arge to
affect the overal l dynami cs.
I t i s i nteresti ng then to specul ate as to what i s
occurri ng i n the sampl es when the two fi l l ers are mi xed.
The SANS data on bul k sampl es where carbon and si l i ca
fi l l er were mi xed wi th BI MS show a hi gh scatteri ng
i ntensi ty whi ch i s comparabl e to that of the sampl es
wi th onl y carbon bl ack fi l l ers.
31
Si nce i t i s not possi bl e
to di sti ngui sh whi ch fi l l er produces the scatteri ng, we
can onl y state that the number of scatterers i s si mi l ar
to that of the pure carbon bl ack sampl es, whi ch i ndi -
cates that the carbon bl ack fi l l ers do not form l arge
aggregates wi th the si l i ca such as those reported where
the two fi l l ers were premi xed wi thout pol ymer.
29,32
We suspect that i n the mi xed fi l l er systems pol ymer
chai ns bound to carbon bl ack parti cl es are trapped
(shown as green) or have hi ndered mobi l i ty (shown as
bl ue) whereas the chai ns i n the vi ci ni ty of the col l oi dal
si l i ca fi l l ers behave i n a manner si mi l ar to free
pol ymer (shown as red). The proposed model i s shown
i n Fi gure 18c. The carbon fi l l er acts as an effecti ve
cross-l i nki ng agent of the pol ymer due to the strong
i nteracti on wi th the chai ns. When col l oi dal si l i ca fi l l er
i s present, we assume the si l i ca and carbon bl ack
aggregates are randoml y si tuated i n the bul k pol ymer
matri x. I t i s enti rel y possi bl e that i f a si l i ca aggregate
i s wi thi n a few chai n di mensi ons, i .e., R
g
, then l ess of
the pol ymer matri x can i nteract wi th the carbon bl ack
surface, whi ch essenti al l y rel eases these chai ns from the
constrai nts i mposed on i t by the more strongl y i nteract-
i ng surface (Fi gure 18c). The free chai ns are then
entropi cal l y excl uded from the matri x and mi grate to
the free surface or i nterfaces i n anal ogy to the segrega-
ti on observed of homopol ymer i n a cross-l i nked matri x.
33
Conclusions
We successful l y measured the i nterdi ffusi on dynami cs
between two di ssi mi l ar el astomers by the neutron
refl ecti vi ty techni que. Strong adsorpti on of el astomer
chai ns to carbon bl ack parti cl es i s i ndi rectl y observed
by both neutron refl ecti vi ty and LFM techni ques. Cal -
cul ati on of the cri ti cal vol ume fracti on i ndi cates the
pol ymer/fi l l er i nteracti on i s l ong range. Percol ati on
was therefore observed at
CB
much bel ow the amount
used i n the i ndustry. LFM measurement on the surfaces
of fi l l ed dPB fi l ms shows an i ncrease i n vi scosi ty wi th
as l i ttl e as
CB
) 0.005 fi l l er. The i ncrease saturates at
a vol ume fracti on of
CB
) 0.025. Weaker confi nement
effects, i .e., i nterfaci al narrowi ng or vi scosi ty i ncrease,
were observed wi th ei ther NR or LFM for systems fi l l ed
wi th pyrogeneous si l i ca. Thi s was attri buted to screen-
i ng of the pol ymer/fi l l er surface i nteracti ons by the
surfactants used to stabi l i ze the parti cl es. When both
carbon and si l i ca were i ncorporated i nto the dPB l ayer,
both the surface vi scosi ty and the i nterfaci al broadeni ng
were si mi l ar to the sampl es fi l l ed wi th onl y pyrogeneous
si l i ca. Thi s was attri buted to segregati on of the free
pol ymer and associ ated si l i ca parti cl es to the surface
and i nterfaces. Thi s i s anal ogous to the segregati on of
free homopol ymer from a cross-l i nked network, whi ch
i n thi s case i s formed by the physi cal cross-l i nks of
pol ymers adsorbed to attracti ve carbon bl ack parti cl es.
Acknowledgment. Thi s work was supported by
NSF MRSEC program. H.A. and S.G.U. are supported
by NSF Young I nvesti gator Award DMR-9458060.
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Macromolecules, Vol. 34, No. 20, 2001 Fi l l ers i n El astomer Bands 7065