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ARTICLE NO.
CS975143
INTRODUCTION
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
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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
TABLE 2
Fumed Silicas Used in the Adsorption Study
Aerosil 130
(A130)
Modified Silica 1
(MS1)
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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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
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
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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).
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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
a
b
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
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
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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. 3. DRIFT spectra of an untreated silica (Aerosil 130, dashed line), and the same silica with adsorbed 88K (continuous line).
1
1
(cm3 /g) 1
(g/m 2 ) 1 10 3 ,
rpolym
Sp
r 2g (nm)
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
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118K
323K
2.06
2.10
1.49
0
1.62
0
12.45
12.45
8.30
8.00
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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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REFERENCES
1. Aranguren, M. I., Mora, E., De Groot, J. V., and Macosko, C. W., J.
Rheol. 36, 1165 (1992).
2. Aranguren, M. I., Mora, E., Saam, J., and Macosko, C. W., Rubber
Chem. Technol. 67, 820 (1994).
3. Rwei, S. P., Manas-Zloczower, I., and Feke, D. L., Polym. Eng. Sci.
31, 558 (1991).
4. Takahashi, A., and Kawaguchi, M. Adv. Polym. Sci. 46, 1 (1982).
5. de Gennes, P. G., Adv. Colloid Interface Sci. 27, 189 (1987).
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