JOURNAL OF COLLOID AND INTERFACE SCIENCE

ARTICLE NO.

195, 329337 (1997)

CS975143

Compounding Fumed Silicas into Polydimethylsiloxane:

Bound Rubber and Final Aggregate Size
Mirta I. Aranguren, 1 Elsi Mora, 2 and Christopher W. Macosko 3
Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455
Received April 21, 1997; accepted August 19, 1997

The properties of mechanically mixed suspensions of fumed

silicas in polydimethylsiloxane (PDMS) were studied. The work
focuses on two aspects: (i) Adsorption of PDMS onto silicas by
means of the mechanical mixing of the bulk polymer and untreated
or chemically modified fumed silicas. The silicaPDMS suspensions were completely dispersed or only swollen by a solvent, depending on the filler concentration, the silica surface chemistry,
and the polymer molecular weight. The bound rubber content of
the different preparations was determined by a weight difference
technique and by carbon analysis of the samples and was compared
with previously reported values in similar systems. (ii) The effect
of the mechanical mixing on the final aggregate size of the silica
and on the polymer molecular weight distribution. One PDMS
and silicas of different surface area and surface chemistry were
used. The final size of the aggregates after a long mixing time with
the bulk polymer was approximately the same in all cases. q 1997
Academic Press

Key Words: silicaPDMS suspensions; compounding; bound

rubber; aggregation.

INTRODUCTION

The fumed silicapolydimethylsiloxane (PDMS) system

has not only academic importance in the area of polymer
adsorption onto solids but also a practical one: mechanically
prepared highly filled polymeric suspensions are the starting
materials in the manufacture of silicone rubbers. A detailed
description of the type of interactions that occur between
filler and polymer in these suspensions is still lacking. The
type and number of adsorption sites and bonds created play
an important role in the rheology of the uncured material,
which is related to the material behavior during processing
and to the final properties of the cured rubber (1, 2).
Fumed silicas are aggregates of spherical particles, ca. 10
to 20 nm in diameter, essentially monodisperse for a given
1
Current address: INTEMA Facultad de Ingeniera, Juan B. Justo
4302, 7600 Mar del Plata, Argentina.
2
Current address: Escuela de IngenierB a QuB mica, Universidad de Costa
Rica, San Jose, Costa Rica.
3
To whom all correspondence should be addressed.

silica, which are fused together. These aggregates are assumed to be the primary structure of the filler in the suspensions. Agglomerates are clusters of aggregates linked by
physical forces.
Dispersion and attrition of agglomerated fillers during rubber compounding has been treated previously. In most of
the literature the mixing times reported are shorter than those
used in this paper (2040 min). Rwei et al. show that the
extent of erosion of the clusters is linear with time at short
mixing times but changes to an exponential behavior for
long mixing times (3).
Most of the previous work focused on the adsorption from
polymer solutions onto solids (4, 5). One of the reasons,
which will be further discussed, is that there are no simple
techniques to measure adsorption from the bulk. Indirect
measurements of bound rubber are the most common results
reported for systems similar to those used here (69). Viallat et al. proposed that in mechanically induced sorption the
macromolecules are only partially adsorbed as a consequence of the strong entanglements formed with other chains
in the bulk (7). Thus, mechanically mixed suspensions must
be distinguished from those prepared from polymer solutions
because the interactions generated will be different, and consequently, the rheological behavior will also differ.
The present work has a dual purpose:
(i) To characterize the type of bonds (chemical or physical) formed between polymer and filler by adsorption from
the bulk and the variables that affect their strength. Fumed
silicas are attractive to use because it is relatively easy to
modify their surface. Surface chemical groups in the silica,
as well as polymer molecular weight, were the variables of
this study. Both have a strong effect on the amount of bound
rubber (adsorbed polymer) and, thus, on the complete dispersion (liquid-like behavior) or the swelling (gel-like behavior) of the suspensions in a solvent and, finally, on the
suspension rheology (1).
(ii) To discuss the effects of the long mechanical mixing
time on the aggregate size of the filler and on the polymer
molecular weight distribution. The structure of the filler has
been considered of great importance in the performance of

329

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0021-9797/97 $25.00
Copyright q 1997 by Academic Press
All rights of reproduction in any form reserved.

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ARANGUREN, MORA, AND MACOSKO

TABLE 1
Molecular Weights and Polydispersity of the Used
Polydimethylsiloxanes

Mn
Mw
Mw/Mn

325Ka

118Kb

17Kb

88Kc

146,000
325,000
2.2

66,400
118,000
1.8

8,900
16,500
1.9

22,600
87,600
3.9

Measured in our laboratories, Waters GPC Model 150-C ALC/GPC

(1% solution in THF).
b
Measured in Dow Corning Laboratories (Midland, MI), PDMS calibration was used.
c
A mixture of 118K and 17K, 70:30 wt% respectively; Mn and Mw
calculated.

Fumed silicas shown in Table 3 were used to study the

effect of mixing on the structure of filler aggregates. These
silicas differ in their initial aggregate structure due to differences in surface area and surface chemical groups.
Figures 1a and 1b show micrographs of one of the silicas
obtained by transmission electron microscopy (TEM) and
scanning electron microscopy (SEM), respectively. In the
first one, the size and shape of the individual particles can be
observed as well as the internal structure of the aggregates. In
the second one, the clusters observed are identified with the
aggregates (primary structure in the suspensions) (13).
I. PDMS ADSORPTION ONTO FUMED SILICA

Methods: Silica Surface Treatment

these materials after curing (1012). Thus, variation of
structure due to mixing (compounding) was investigated.
MATERIALS

The characteristics of the polydimethylsiloxanes used are

shown in Table 1. PDMS 325K was purchased from Petrarch
Systems (Bristol, PA) and is a methyl-terminated linear
polymer. PDMS 118K and 17K (supplied by Dow Corning,
Midland, MI) are vinyl-terminated linear polymers. It was
previously shown that vinyl groups are only important in
the reacted materials but do not affect the behavior of the
suspensions (13).
To study the type and strength of the fillerpolymer interactions, fumed silicas shown in Table 2 were used. These
silicas have similar structure and surface area, but different
chemical treatments. They were obtained from an initial
batch of Aerosil 130 (Degussa Corp., Teterboro, NJ). Two
different modified silicas (MS) were obtained by reaction
under mild conditions with disilazanes (1). Aerosil R972
was also included in the study. This is a commercial modification of Aerosil 130 obtained by treatment with dimethyldichlorosilane.

An untreated fumed silica and chemical modifications of

it were used (Table 2).
Diffuse reflectance Fourier transformed infrared (DRIFT)
and methyl red adsorption techniques (14, 15a) showed that
the surface modification was complete in the cases of Modified Silica 1 (MS1) and Modified Silica 2 (MS2), but it
was only partial in the case of Aerosil R972 (commercial
modification of Aerosil 130). In the last case, DRIFT
showed a very small peak at 3750 cm01 (isolated silanols),
and methyl red adsorption indicated that about 90% of the
original silanols, present in Aerosil 130, were reacted.
Elemental carbon analysis of the silicas are shown in Table 4. The data were used to calculate the fraction of reacted
sites on the starting silica, assuming the same reactivity for
the hexamethyldisilazane (HMDS) and the tetramethyldivinyldisilazane. The value calculated for the modification with
HMDS (MS1) was 2.43 sites/nm2 , which is in excellent
agreement with the value 2.45 OH/nm2 reported by Iler as
the maximum coverage of an amorphous hydroxylated silica
by HMDS (15b). The other calculated coverages were 2.28
sites/nm2 for Aerosil R972 and 2.19 sites/nm2 for MS2. The
lower coverage in these silicas is due to partial treatment
and to the bulkier-than-methyl vinyl group, respectively.

TABLE 2
Fumed Silicas Used in the Adsorption Study

BET surface (m2/g)a

Bulk density (g/cm3)
Size average particle (nm)
% Hydroxyl treatedb
Type of treatment

Aerosil 130
(A130)

Modified Silica 1
(MS1)

Modified Silica 2 (MS2)

133
0.05
16
0
No treatment

112

114

16b
100
Hexamethyl disilazane

16b
100
Tetramethyldivinyldisilazane (67 wt%) /
hexamethyldisilazane (33 wt%)

Note. Aerosil R972 was also used in this study (see Table 3).
a
Measured by Micromeritics, Inc. (Norcross, GA).
b
Measured in our laboratory by methyl red adsorption.

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COMPOUNDING FUMED SILICAS INTO PDMS

TABLE 3
Fumed Silicas Used to Study the Effect of Mechanical Mixing
Aerosil R972
BET surface (m2/g)
Bulk density (g/cm3)
Size average particle (nm)
% Hydroxyl treated
Base product
Type of treatment

Aerosil VT345

108a
0.05
16
70 (90d)
Aerosil 130
Dimethyldichlorosilane

188b
0.041c
12
Aerosil 200
Vinyltriethoxysilane

Cab-o-sil TS720
100 { 20
0.0320.048

Organosilicones

Measured by Micromeritics, Inc. (Norcross, GA).

Provided by Degussa (Teterboro, NJ) for the specific batch in use.
c
Measured in our laboratory in noncompacted samples.
d
Measured in our laboratory by methyl red adsorption.
b

Master batch suspensions were prepared in a Haake Rheomix 600 with a chamber capacity of 6070 cm3 using sigma
blades at 35 rpm. Further dilutions were made in the same
equipment. One of the samples (Aerosil R972 and 88K) used
for the mixing study was also used in adsorption studies.
Results and Discussion

Dispersion and Swelling

After mixing the suspensions were placed in chloroform.
Use of MS1 and MS2 resulted in suspensions that could be
completely dispersed in chloroform at any concentration of
the silicas in PDMS. Suspensions prepared with untreated
silicas did not disperse completely in chloroform. Translucent blobs, such as those seen during the first stages of
chemical gelation, were visible to the unaided eye. At 10
phr, the blobs were not larger than 1 mm and very fragile.
The amount and size of these large blobs increased with
silica concentration. 325K / Aerosil 130 (20 parts of silica
per hundred parts of polymer, phr), on the other hand,
swelled in chloroform, maintaining its shape. After it was
dried in air, it recovered its original size and retained the
appearance of a silicone rubber (white translucent). The
piece behaved as a cured rubber and could be reswollen
without breakage. However, it could be permanently deformed under pressure.
Cohen-Addad et al. (16) found a similar behavior for
silicasilicone suspensions. At high concentrations of silica,
these materials showed a tendency to swell and not to be
dispersed, which he interpreted as an increased chainbridge
formation between the aggregates.
The behavior of suspensions made with partially treated
silicas was between those of untreated and completely
treated silicas. The suspension 118KR972 (20 phr) in chloroform produced fragile blobs of 5 to 10 mm. After eliminating the supernatant, the material was left to dry in air, which
caused the complete breakage of the sample, leaving a granulated white powder of dry appearance. A sample of 0.95 g
of 118KR972 (30 phr) in solvent gave a large blob of 10

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to 15 mm and many small ones. All the blobs were fragile

and broke very easily during drying or handling.
Bound Rubber
Bound rubber is defined as the percentage of the polymer
that cannot be extracted from an uncured filled rubber using
a good solvent, usually, at room temperature. The amount
of bound rubber is a function of the interactions between
polymer and filler, the surface area of the filler, the molecular
weight of the polymer, the solvent used in the extraction,
the time and temperature of the extraction and the concentration of filler in the composite.
The composites used for this test were all prepared with
silicas from Table 2. The parameters varied were the silica
surface treatment, silica concentration and polymer molecular weight. The proportion of filler used ranged from 4 to
15% by volume (10 to 40 phr). Chloroform was the solvent
used for the PDMS extractions.
Samples of 2 g of uncured silicone rubber were immersed
in 20 ml of chloroform in 50 ml capped centrifuge tubes.
The samples were kept in contact with the solvent for one
week and the solvent was renewed twice during that period.
The solids were separated from the supernatant by centrifugation at 13,000 rpm for 45 min.
Another measurement was done on the samples containing
Aerosil 130, by solvent extracting the polymer from a Soxhlet thimble immersed in chloroform for one week with three
solvent renewals.
The amount of adsorbed polymer is calculated as the difference between the weight of the recovered solids and the
calculated amount of filler in the suspension.
Finally, carbon elemental analysis was performed on these
solids. The percentage of carbon in these samples and those
obtained from the original silica allowed us to calculate how
much PDMS was adsorbed on the silica (the calculation
considered only dimethyl units).
Table 5 shows percentage of adsorbed polymer (bound
rubber) at three different silica concentrations. Results are

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ARANGUREN, MORA, AND MACOSKO

FIG. 1. (a) TEM photograph of the internal structure of fumed silica clusters before compounding (Cab-o-sil TS720). (b) SEM photograph of
aggregates of fumed silica before compounding (Cab-o-sil TS720).

also shown as weight of adsorbed polymer per unit weight

of filler. For a given silica and PDMS, and assuming perfect
wetting, the amount of polymer adsorbed per unit weight of
silica is independent of the concentration of filler. The situation should be different at high silica concentration due to
incomplete wetting of the silica surface and due to a larger
number of shared chains (PDMS adsorbed onto more than
one aggregate). In both cases, the amount of adsorbed polymer would be comparatively less.

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Table 6 shows the effect of polymer molecular weight and

silica surface chemistry on the bound rubber. The results obtained by the weighing and the carbon analysis techniques are
in very good agreement, except for the composites made from
MS1 and MS2, which could be explained by the following:
(i) incomplete washing of the samples used for carbon
analysis and the impossibility of repeating the measurement
for the lack of material, or

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COMPOUNDING FUMED SILICAS INTO PDMS

TABLE 4
Elemental Analysis of Silicas

TABLE 6
Variation of the Amount of Adsorbed PDMS with Varying
Molecular Weight and Silica Surface Treatment

Silica

%C

%H

Aerosil 130
Aerosil R972a
Modified silica 1b
Modified silica 2

0.16
0.98
1.63
1.61

trace
0.27
0.49
0.45

PDMSads /silica (wt/wt)

a
b

Two methyl groups per reacted site.

Three methyl groups per reacted site.

17K

88K

118K

325K

Modified Silica 1

16,500
0.196
0.26
0.055
0.064

87,600
0.653
0.410.63
0.283
0.26

325,000
1.610
1.61
0.871
0.84

Modified Silica 2

118,000

0.216
0.22
0.151a
0
0.167a
0

Mw
Aerosil 130
Aerosil R972

(ii) incomplete sedimentation of the solids in the

weighing technique. Agglomeration is very low in these
samples according to the observations reported in the Dispersion and Swelling section. Consequently, centrifugation was
not strong enough to produce complete sedimentation and
some silica was lost in the supernatant. The solids recovered
were always 1020% less than the calculated initial amount.
Results from any of the two techniques indicated that the
bound rubber was very low in those samples.
Table 6 shows that for a given silica the amount of polymer attached to it increases with increasing molecular weight
and that at a given molecular weight the amount adsorbed
increases with the increasing silanol concentration in the
silica. These observations are coincident with a strong adsorption of siloxanes onto silicas by hydrogen bonding between the SiOSi of the polymer backbone and the isolated
silanols of the silica surface (1720). Figure 2 shows similar
results (reduced to silica unit area for easier comparison)
obtained by Cohen-Addad et al. (19) for suspensions made
with untreated fumed silica. In both cases, the amount of
adsorbed polymer increases with the PDMS molecular
weight. The amount of adsorbed PDMS measured in this
work is higher than that reported by these researchers, but
the trends are similar. The partially modified silica (Aerosil
R972) shows a similar correlation, but the adsorbed polymer
is comparatively less. Other researchers have also reported
that the amount of adsorbed PDMS decreased with increased
degree of silica treatment (7, 9, 18).
DRIFT of the solids recovered in the bound rubber test
(silica / adsorbed PDMS) was also performed. Figure 3

Note. Numbers in regular font were calculated from the results of carbon
analysis of the silica before and after the polymer adsorption. Numbers in
italics were obtained with a weighing technique (see text).
a
There was incomplete washing of the free polymer. Numbers are included to show the trend.

shows the spectrum for Aerosil 130 with adsorbed 88K. The
spectrum of the silica with bound rubber shows a double
peak at 29602970 cm01 which corresponds to the methyl
groups of the polymer, and the disappearance of the peak
assigned to isolated silanols at 3750 cm01 . The adsorption
could be physical or chemical. However chemical reactions
between PDMS and silica surfaces have been reported to
occur at or above 1507C (20). Since adsorption was carried
out at room temperatures, chemical bonding was ruled out.
Measurements of layer thicknesses of polymers adsorbed
onto solids are usually done using ellipsometry or hydrodynamic methods (4), but these measurements require flat sur-

TABLE 5
Bound Rubber vs Silica Concentration (Aerosil R972 / 88K)
Silica
concentration
(phr)
20
30
40

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PDMSads
1 100
PDMStot

PDMSads
silica

5.3 { 0.1
6.1 { 1.6
11.8 { 3.0

0.26 { 0.01
0.20 { 0.05
0.29 { 0.08

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FIG. 2. Weight of polydimethylsiloxane adsorbed per unit of BET area

of the silica. Data are shown as follows: filled circles, adsorption onto
untreated silica (Aerosil 130); filled squares, adsorption onto partially
treated silica (Aerosil R972). Lines are included to show the trend. Open
circles are data from Ref. 19 and correspond to untreated silicaPDMS
suspensions at two different concentrations.

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ARANGUREN, MORA, AND MACOSKO

FIG. 3. DRIFT spectra of an untreated silica (Aerosil 130, dashed line), and the same silica with adsorbed 88K (continuous line).

faces or regular shape particles respectively and, therefore,

are inapplicable in this case. However, an estimation of the
thicknesses of the adsorbed layers can be obtained if one
assumes that:
(i) All the silica surface can be reached by the polymer.
(ii) The density of the adsorbed polymer is equal to the
density of the bulk polymer.
This simplified model leads to the following expression:
thickness (nm)

mass of adsorbed polymer (g)

mass of silica (g)
1

1
1
(cm3 /g) 1
(g/m 2 ) 1 10 3 ,
rpolym
Sp

where rpolym is the density of the bulk polymer and Sp is the

BET area of the silica.
Results obtained with the above equation are reported in
Table 7.
The sizes of the polymer coils can be calculated using the
radii of gyration of the chains. For PDMS chains (21),
q

r 2g (nm)

of the chain. Assuming that the longest

q chains are preferentially adsorbed, the size of the coil (2 r 2g ) can be estimated.
Results obtained using the weight average molecular weight
of the PDMS are reported in Table 8. A chain probably has
more than one segment adsorbed onto the silica, so that the
layer thickness should be smaller than the size of the polymer
coil, and it should be closer to this last value at high adsorption (untreated silicaPDMS suspensions). This was observed in the results of Table 7.
The polymer adsorption has an irreversible character,
since the chains are not desorbed in the presence of pure
solvent at room temperature. However, it has been proposed
that in these systems the adsorbed chains could be desorbed
(pulled loose) (22) or slip at the filler surface (23) to release
externally applied stresses. These observations do not contradict each other. The unifying idea, explained by de Gennes
TABLE 7
Thicknesses of the Layers of Adsorbed Polymer (nm)
17K

88K

Modified Silica 1

1.52
2.01
0.52
0.61

5.05
3.174.87
2.70
2.48

Modified Silica 2

Aerosil 130
2

r
16 [0.073 M],
6

Aerosil R972

where M is the molecular weight of the polymer, r is the

end-to-end distance of the coils, r 2g is the radius of gyration
of the coils, and 0.073 is an experimental constant that takes
into account the size of the backbone bonds and the rigidity

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Note. Fonts have the same meaning as in Table 6.

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118K

323K

2.06
2.10
1.49
0
1.62
0

12.45
12.45
8.30
8.00

COMPOUNDING FUMED SILICAS INTO PDMS

335

in the case of adsorption from solution, is called saturation

condition (5). To keep the coverage constant and equal to
that of saturation, the chains can be extracted from the solid
surface only if other chains are adsorbed to replace them.
This concept can explain some of the observations made on
mechanically mixed compounds:
(i) The existence of bound rubber, i.e., the impossibility
of extracting all the polymer present in the composite by
solvent extraction.
(ii) The relaxation of stresses in filled melts and rubbers
that can occur through interchange between adsorbed
stretched chains and nonadsorbed chains, at least when the
adsorption is mainly physical.
II. EFFECT OF MIXING ON THE SILICA STRUCTURE

Fumed silicas reported in Table 3 were used in this study.

Suspensions were prepared at Dow Corning in a Baker Perkins mixer of 1 liter capacity using helical rollers (35 rpm).
The suspension of Aerosil VT345 was prepared in a kitchen
mixer for bread dough (Montgomery Ward, Chicago, IL).
The compounding of master batches (40 phr) was done by
steps, as follows:
(i) Three quarters of the polymer was initially loaded in
the mixer, and the silica added incrementally. After each
addition the sample was mixed for about 20 min. The procedure was continued until all the silica was added and dispersed.
(ii) The rest of the polymer was added and mixing was
continued until the sample became homogeneous by visual
inspection.
The complete process took 3 h. No processing aids were
used. PDMS 88K was used in these preparations.
Results and Discussion

Aggregate Size Distribution

SEM was used to study the effect of the compounding
on the size of the aggregates. This technique gives enough
resolution to determine the size of the aggregates but does
not allow their internal structure to be observed. Suspensions
of silica in chloroform (0.025% by weight) were prepared
and mixed in an ultrasonic bath for about 45 min to destroy
agglomeration (24). A drop of the suspension was placed
TABLE 8
Size of PDMS Coils of Different Molecular Weights

Mqw
2 r2g (nm)

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17K

118K

325K

16,500
3.2

118,000
8.4

325,000
13.9

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FIG. 4. Aggregate size distribution before (from 49 aggregates) and

after compounding (from 76 aggregates) of Aerosil R972 with 88K.

on an SEM stub, the solvent was evaporated, and the sample

was coated with AuPd. No reduction in the size of the
clusters was observed by using more diluted suspensions or
longer times in the ultrasonic bath. To observe the silica
aggregates after the compounding, the free polymer was
extracted in chloroform. The sample was then prepared as
described above.
The shape of the aggregates was digitized from the micrographs using a Hi-Pad digitizing tablet, Houston Instruments.
From the numerical analysis of the data (software developed
by the Biology Sciences Department of the University of
Minnesota), the diameter of the sphere with the same projected area was obtained. About 50 to 100 aggregates were
used for the calculations.
The comparison of the aggregate size before and after
compounding shows that the distribution is narrowed and
shifted toward smaller sizes. Figure 4 shows the size distribution curve for Aerosil R972. The curve presents a tail
toward large size clusters. The aggregates recovered from
the silicaPDMS suspensions have smoother shapes than
the originally branched aggregates. This observation is in
agreement with a mechanism in which the breakage of the
clusters occurs at weak joints, and, thus, small fragments
originate from larger clusters (3).
Aerosil VT345 is a partially treated silica with a relatively
large hydroxylated area as measured by methyl red adsorption and DRIFT. In the dry state, there exist clusters larger
than 1 mm, which were considered to be agglomerates (secondary structure), probably formed by hydrogen bonding.
These clusters were not included in the distribution. In spite
of this difference with respect to the other silicas, the average
size of the aggregates after mixing is very similar for all the
samples (Fig. 5). This is surprising when one considers the
many differences between the silicas and specially the fact

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ARANGUREN, MORA, AND MACOSKO

FIG. 5. Aggregate size distribution after compounding for different

fumed silicas with 88K.

that Aerosil VT345 was compounded in a different type of

mixer. The use of long mixing times probably makes it
possible to reach a limiting aggregate size, but the nature of
such a process is still unknown. The results may differ for
short mixing cycles. The disappearance of the agglomeration
in Aerosil VT345 also indicates that the silica is well wetted
by the polymer.
Manas-Zloczower et al. (25) studied the rupture of carbon
black agglomerates due to the stresses generated by the hydrodynamic forces generated by the flow field during compounding. They reported that cluster break up is a process
that continues until an ultimate particle size is reached,
which can no longer be reduced by hydrodynamic forces.
Later, Rwei et al. treated the erosion of carbon black in
SBR (3). They define erosion, a breakage mechanism for
dispersion of the carbon black, as the continuous detachment
of small fragments from the outer shell of a cluster. They
reported that at large extents of erosion (long compounding
time) the change of cluster size tends exponentially to zero.
These authors also report that there exists a critical stress
below which no erosion occurs. The extent of the attrition
was correlated by means of a parameter proportional to the
viscosity and shear rate and inversely proportional to a constant that scales with the particleparticle interaction force
and the volume fraction of solids within the cluster.
Hydrodynamic forces are a function of the polymer molecular weight (viscosity), geometry of the mixer, and turning
rate of the blades. The polymer molecular weight was kept
constant in this study, and the mixing conditions were the
same in all cases, except for the suspensions prepared with
Aerosil VT345. However, the final size of the aggregates
was the same for all the samples, including this silica. Aerosil VT345 was initially more agglomerated, due to larger
extent of hydrogen bonding between the aggregates (higher
concentration of surface silanols). However, since the diameter of the fused SiO2 spheres that form aggregates is about
the same as that of the other silicas (Table 3), the aggregate
structure should be similar in all samples.

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Thus, a rupture process (abrupt splitting of a cluster into

smaller fragments) may be responsible for the breakage of
agglomerates into aggregates during the first stages of mixing, but the ultimate dispersion of the silica would be due
to the erosion of the aggregates (primary structure). It is
proposed that the similar strength of these aggregates (covalently bonded SiO2 spheres) is the most important factor in
determining the final size of the clusters for long mixing
times.
Compounding introduces some changes in the silica structure, and one might expect that some changes also occur to
the polymer. Adsorption onto solids has been reported (8)
to lead to the fractionation of the polymer, which changes
the composition of the matrix. GPC curves obtained from
the original polymer and the extracted (nonadsorbed) polymer were compared, for the suspension 88KR972 (20phr).
There was a small difference between the two curves in the
region of high molecular weights. This can be explained if
no fractionation occurs, but also if the amount of adsorbed
polymer is small (Table 6). Actually, about 5% of the polymer was adsorbed in this preparation, which could be responsible for the small difference observed at high molecular
weights.
SUMMARY

Analysis of the bound rubber results presented in this

work shows the following:
The weighing technique and the elemental carbon analysis show good agreement with each other. Centrifugation
at high rpm is a good method to separate the solids (silica
and adsorbed polymer) from the supernatant (solvent and
free polymer). The exceptions to this observation are the
suspensions prepared from completely treated silicas, in
which there is no agglomeration.
The amount of polymer adsorbed is independent of the
silica concentration as long as the silica surface is completely
wetted and there is not a high number of bridging chains
(high silica concentration).
Untreated silicas (high OH concentration) adsorb larger
amounts of polymer than treated silicas. The PDMS chains
have a strong affinity for the surface silanols that are lost
during surface treatment.
Polymer chains are strongly adsorbed onto the silica
through more than one segment. Some chains can form bridges between different aggregates, which explains the incomplete dispersion of some samples in chloroform and the
swelling of others.

It was also shown that there is breakage of the silica

aggregates during mixing. The aggregates in silicas of different surface areas and states of agglomeration showed approximately the same final size after a long mixing time (3 h)
with the same polymer. We advance the idea that a limit

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COMPOUNDING FUMED SILICAS INTO PDMS

size is reached, which in this case would be mostly related

to the structure and strength of the aggregate cores and not so
much on their branched outer structure or surface chemistry.
More detailed study is needed to explain the phenomenon.
In such study, the silica characteristics should be varied one
at a time and the effect of the polymer molecular weight
(MW ) and of the molecular weight distribution (MWD) on
the final aggregate size should also be addressed.
ACKNOWLEDGMENTS
The authors thank the Office of Naval Research, Grant N00014-88-K0366, and Dow Corning (Midland, MI) for the grant and for providing the
materials used for this work. Thanks are also due to Degussa and Cabot
for supplying the fumed silicas. Dr. John Saams suggestions as well as
the valuable discussions with him were very much appreciated. M.I.A. also
thanks CONICET (Argentina) for the fellowship that supported her stay
in U.S.A.

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