Silica Fillers For Elastomer Reinforcement: Article

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Silica Fillers for Elastomer Reinforcement
Article · May 2008

DOI: 10.1201/9781420007183.ch17
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Bhowmick/Current Topics in Elastomers Research 7317_C017 Page Proof page 505 29.11.2007 10:40pm Compositor Name: JGanesan
17 Silica Fillers for Elastomer

Reinforcement
Doug J. Kohls, Dale W. Schaefer, Raissa Kosso,
and Ephraim Feinblum
CONTENTS
17.1 Introduction ........................................................................................................................ 505

17.2 Small-Angle Scattering ...................................................................................................... 506
17.2.1 Scattering Experiments......................................................................................... 506
17.2.2 Scattering Data Analysis ...................................................................................... 508
17.3 Small-Angle X-Ray Studies on Silica Powders ................................................................ 509
17.4 Mechanical Testing of Filled Elastomers .......................................................................... 511
17.5 Conclusion ......................................................................................................................... 516
References ..................................................................................................................................... 517
17.1 INTRODUCTION
This article summarizes recent work to investigate the structure of precipitated silica used in the
reinforcement of elastomers. Silica has a unique morphology, consisting of multiple structural levels
that can be controlled through processing. The ability to control and characterize the multiple structures
of precipitated silica is one example of advanced filler for reinforcement applications. In this summary
of some recent research efforts using precipitated silica, small-angle scattering techniques are described
and their usefulness for determining the morphology of silica in terms of primary particles, aggregates,
and agglomerates are discussed. The structure of several different precipitated silica samples are shown
as well as the mechanical properties of elastomers reinforced with these silica particles.
The study of the mechanical properties of filled elastomer systems is a challenging and exciting
topic for both fundamental science and industrial application. It is known that the addition of hard
particulates to a soft elastomer matrix results in properties that do not follow a straightforward rule
of mixtures. Research efforts in this area have shown that the properties of filled elastomers are
influenced by the nature of both the filler and of the matrix, as well as the interactions between them.
Several articles have reviewed the influence of fillers like silica and carbon black on the reinforce-
ment of elastomers.1–4 In general, the structure–property relationships developed for filled elasto-
mers have evolved into the following major areas: Filler structure, hydrodynamic reinforcement,
and interactions between fillers and elastomers.
In the rubber industry there is specific interest in understanding how fillers reinforce elastomers.
There is a wealth of knowledge regarding the synthesis of these fillers, the mechanisms that govern the
synthesis, and the characterization of the resulting filler structures.5–9 There is interest in using fillers
that are both highly dispersive and highly reinforcing as evidenced by new fillers that have been
marketed over the last decade.10–13 Different approaches have been used in improving end-use
properties of filled elastomers that include refinement of particle structure, filler surface chemistry,
and elastomer chemistry.1,2,4,14 With regard to fillers, the goal has been to have a filler that is highly
structured, weakly agglomerated, and that has improved surface compatibility with the elastomer.13,14
505
506 Current Topics in Elastomers Research
Presented here is the use of small-angle scattering for determining the morphology of several
different silica samples and the mechanical testing of filled elastomers. The primary particle and
aggregate structures are studied using ultra small-angle x-ray scattering (USAXS) while the
agglomerate structures are studied using small-angle light scattering. The studies quantify the
complex silica structure in each of these structural regimes.
17.2 SMALL-ANGLE SCATTERING

Particles are characterized by a variety of techniques to determine particle size, shape, and surface
structure. Microscopy allows for a quick visualization of the particles and can give information on a
broad range of sizes, from nanometer to millimeter particle diameters. Another approach to particle
characterization uses the scattering of light, x-rays, and neutrons. Small-angle scattering is useful for
examining intermediate sizes, nanometer–micrometer, of the particles and it is possible to probe the
internal structure of the sample. Small-angle scattering techniques are well known and established
for characterizing the morphology of micron and submicron polymeric and ceramic materials.15–24
17.2.1 SCATTERING EXPERIMENTS

A scattering experiment involves a source of monochromatic radiation that interacts with electrons
of the sample and a detector that measures the scattered radiation. Figure 17.1 shows a schematic of
a scattering experiment.
The scattering angle u, is the angle between the transmitted beam and the scattered beam. The
scattered intensities are measured at different angles for the given sample and a plot of intensity
verses angle (u) or scattering vector (q) is made. The scattering vector is the direction of the
scattered wave and is related to the scattering angle by:
4psin(u=2)
q¼ (17:1)
l
where
u is the scattering angle
l is the wavelength of the x-ray
q is inversely related to size and has the units of 1=size
Figure 17.2 shows a combined small-angle light and x-ray curve for a precipitated silica sample,
A1. For particle characterization, the range of q typically probed falls between 104 < q < 1 Å1 for
x-rays and 106 < q < 104 Å1 for light.24 The q range shown corresponds to the complex
structures of fillers that are made up of primary particles at the smallest-size scale (high q) and
agglomerates at larger sizes (low q).
Detector
l q
Incident beam Transmitted beam
FIGURE 17.1 Schematic of a small-angle scattering experiment showing the incident x-ray striking a sample
with the main ‘‘transmitted beam’’ passing straight through the sample. X-rays are also scattered from the
sample at an angle u. The expanded region shows cartoon of an aggregated structure that is within the sample.
Silica Fillers for Elastomer Reinforcement 507
1013
Precipitated silica
1011
Relative intensity 109

10 nm
107
105
100 µm
103
100 nm
101
Light x-ray
10−1
10−6 10−5 10−4 10−3 10−2 10−1
q (Å−1)
FIGURE 17.2 Combined plot of small-angle x-ray and light scattering for a precipitated silica sample. The
silica sample is Dimosil 288, produced by Dimona Silica Ltd.
By measuring the scattered intensity as a function of q over multiple decades in q, information

from multiple structural levels can be obtained. Two distinct scattering features distinguish each
structural level, a power–law region and a ‘‘knee’’ region in a log–log plot of I(q) versus q. An
example of power–law scattering is shown in Figure 17.2. For particles with a smooth surface the
scattering intensity varies as25
I(q) BP q4 where B ¼ 2pN(Dr)2 S (17:2)
where
r is the scattering length density of the particle
S is the total area of the boundary between the two scattering phases
N is the number density of particles within the scattering volume26
The Porod27 scattering has a power–law feature in a log–log plot of intensity versus q. When the
scattering is from the interface of a sphere, the scattering intensity decays as I ~ q4. The Guinier28
region is noted by a change from power–law scattering, to a bend or ‘‘knee’’ as the intensity changes
with q. The location of this knee in q relates to the radius of gyration of the particle. The generic
relationship is that I ~ (Rg)2 and Guinier’s law is given as28:

1
I(q) G exp q2 R2g where G ¼ N(Dr)2 V 2 (17:3)
3
where
r0 is the average scattering length density of the particle
V is the volume of the particle
Rg is the radius of gyration
The Porod and Guinier regions are shown in Figure 17.3 for a precipitated silica sample. The plot
shows two Guinier regions and three power–law regions. The Guinier at higher q(Rg1), q ~ 0.04 Å1,
is the Rg of the primary particle with a value of 66 Å. The Guinier region at lower q(Rg2), q ~ 0.004
Å1, is the radius of gyration for the iron aggregates. The first power–law region (P1), slope ¼ 4,
108
107 Rg2
106
G2 P2
105
Relative intensity Rg1
104
G1
103
102 P1
101
B1
100
10−1
3 4 5 67 2 3 4 5 67 2 3 4 5 67 2
0.001 0.01 0.1
q (Å−1)
FIGURE 17.3 Log–log plot of I versus q for precipitated silica particles. The plot shows two distinct regions of
power–law decay noted as P (Porod’s law) and Guinier scattering, noted by Rg. The subscripts indicate the
structural level associated with the scattering curve. The Guinier ‘‘knee’’ at higher q indicates the radius of
gyration (Rg1) of the primary particle. At lower q the second ‘‘knee’’ indicates the size for the aggregates (Rg2).
The solid line is the fit line obtained from using a unified model for the entire scattering curve. The two dashed
lines highlight the Guinier fits for each structure level.
indicates scattering from the surface of the primary particles. The second power–law region (P2) is
from the organization of the particles into aggregates. This is the power–law region that can give
information about the structure of the aggregates.
17.2.2 SCATTERING DATA ANALYSIS

Power–law scattering features will be discussed in relation to mass–fractal scaling laws. Fractal
scaling concepts used to interpret the power–law decay are well published in the literature.19–21,29–31
The slope of the power–law decay of intensity with q gives fractal dimensions that are related to the
surface of particles as well as the arrangement of primary particles into aggregates. While there are
other methods for determining the fractal dimension of aggregated particles such as microscopy
(TEM, SEM), the primary tool used in measuring the fractal dimension in this work is small-angle
x-ray scattering.
The scattering data collected was analyzed using a Unified Fit Model, established by Beauc-
age.20,32 The model fits the power–law and Guinier regions of the scattering plot of I versus q, like
the one shown in Figure 17.3. The model is capable of fitting multiple levels observed in some
scattering curves where more than one Rg and power–law scattering are present. The model was
used to obtain the values for Rg1, Rg2, and the power–law values displayed in the figure.
The power, P, in the fractal power–law regime is given as the fractal dimension, df. For each
level of the fit, the parameters obtained using the unified model are: G, Rg, B, and P. P is the
exponent of the power–law decay. When more than one level is fitted, numbered subscripts are used
to indicate the level—i.e., G1—level 1 Guinier pre-factor. The scattering analysis in the studies
summarized here uses two-level fits, as they apply to scattering from the primary particles (level 1)
and the aggregates (level 2).
For the analysis of primary particles it is possible to calculate the spherical diameter for a
particle from Rg described above as R ¼ (5=3)1=2Rg or d ~ 2.6 Rg. It is also possible to calculate a
hard radius or diameter for a particle through the volume=surface ratio called the ‘‘Sauter mean
diameter.’’ With the parameters obtained from the unified fit this diameter, dv=s is calculated using
the Porod invariant, Q. If the scattered intensity is integrated over all scattering angles for a
particular structure, primary particles in this case, the Porod invariant related to the scattering
power of the structure is calculated as:
ð1
Q¼ q2 I(q)dq ¼ 2p2 N(Dr)2 V (17:4)
0
The value for dv=s is then calculated for spheres as:
6Q 6 2p2 N(Dr)2 V 6V
dv=s ¼ ¼ ¼ (17:5)
pB1 p 2pN(Dr)2 S S
Calculating the particle diameter through the volume=surface ratio (ratio of the third moment to the
second moment) is the same moment for particle size calculation measured by nitrogen adsorption
(BET). The close correlation between dv=s and dBET was demonstrated by Kammler and Beaucage.18,33
Aggregates can be described by the number of primary particles that they contain and this
description is termed the degree of aggregation, z. Beaucage has shown several ways for calculating
the average number of primary particles which make up an aggregate from small-angle scattering
data.15,16,18 For aggregates two ratios are expressed that give the degree of aggregation, z. The value
for z can be expressed as a ratio of the Rg values obtained from a two-level unified fit or a ratio of the
G values from a two-level fit and they express different orders of moments.15,18 However, certain
assumptions are made when calculating z by a ratio of Rg. The ratio is scaled to the mass–fractal
dimension, df, and it is assumed that Rg is a measure of size for both the primary particle and the
aggregate, with the distribution of those sizes being narrow.16 The degree of aggregation may also
be calculated by the ratio of the Guinier pre-factors G, from a two-level unified fit where G1 is the
Guinier pre-factor for the primary particles and G2 is the Guinier pre-factor for the aggregates. The
calculation for z by the ratio of the Guinier pre-factors is given by:
G2
z¼ (17:6)
G1
17.3 SMALL-ANGLE X-RAY STUDIES ON SILICA POWDERS

A series of precipitated silica samples were studied using small-angle scattering and elastomer
compounds were made to test the reinforcing effects of the silica. The small-angle x-ray scattering
data presented in this paper was obtained using the ultra small-angle scattering instrument at the
Advanced Photon Source (beam line 32-ID-B), Argonne National Laboratory. The small-angle
scattering results for three different silica samples are plotted in Figure 17.4. Four levels of
structure are present that related to the primary particle, aggregate, and two agglomerate structures.
The samples shown in Figure 17.4 include A1-Dimosil 288 (Dimona Silica), A2—Ultrasil 7005
(Degussa), and A3—Zeosil 1165 (Rhodia).
The multi-level features of the silica scattering curves shown in Figure 17.4 are quantified in
Table 17.1. The values in the table are obtained using the scattering analysis presented in the
previous section. The A1 sample shows larger Rg for the primary particle and aggregate.
The A2 and A3 samples showed similar sizes and dimensions at each level. The A1 sample has
a larger primary particle size, indicated by an Rg1 of 126 Å, while the A2 and A3 samples showed
smaller primary particles with Rg1 values of 85 Å for A2 and 96 Å for A3.
The four fit parameters for the first two structural levels are shown because it is possible
to describe the aggregates of these samples in more detail using the Guinier and power–law
1016
116 µm
A1
1014
7.1 µm A2
A3
1012
300 nm
1010 133 µm
1.63 126 Å
Relative intensity
108
2.37
106 4.8 µm
104 123 nm
2.13
102
96.5 Å
100
10−2
10−6 10−5 10−4 10−3 10−2 10−1
q (Å−1)
FIGURE 17.4 USAXS and SALS results for samples A1, A2, and A3 described in the text. Each sample
shows four structural levels with the Rg for some of the levels indicated in the graph. The power–law value for
the second level, corresponding to the mass–fractal dimension, df, is also indicated.
pre-factors. The Guinier pre-factor, G, from the primary particle and aggregate fits is used to
calculate the degree of aggregation, z, as described by Beaucage.16 The degree of aggregation is
calculated as the ratio of the Guinier pre-factor of the aggregates to the pre-factor of the primary
particles. The degree of aggregation represents the number of primary particles that make up the
TABLE 17.1
Unified Fit Parameters Obtained for the Three Silica
Samples Shown in Figure 17.4
Level 1 A1 A2 A3
Rg (Å) 126.4 85.2 96.5

P 4 4 4
G 2659 592 1028
B 2.87 3 104 7.36 3 105 1.02 3 104
Level 2 A1 A2 A3
Rg (Å) 295 123 125

P 1.63 2.37 2.13
G 1.97 3 106 5.41 3 105 5.87 3 105
B 11.9 0.07 0.30
TABLE 17.2
Some Physical and Chemical Properties
of Three Silica Samples
Measurement A1 A2 A3
BET surface (sm2=g) 148 174 164

CTAB surface (sm2=g) 144 165 158
DBP adsorption (g=100 g) 234 228 236
DBP=BET 1.58 1.31 1.44
OH-groups, OH=nm2 4.02 2.86 3.31
aggregates. This parameter gives additional information about the morphology of the aggregates
beyond the simple measure of size that is obtained through the radius of gyration. The A1 sample
showed a degree of aggregation of 742 while A2 and A3 showed degree of aggregation values of
914 and 571, respectively.
Table 17.1 also displays the mass–fractal dimension, df, given by the power–law value, P, for
the second level (aggregate). The df ¼ 1.63 for A1 is less than that, and is less than 2.37 for A2 and
2.1 for A3. The lower value of df could indicate a more open structure of the A1 sample,34 but it
could also arise from less interpenetration of the silica aggregates occurring during drying.35
Table 17.2 presents results of physical–chemical testing of the silica powders. The A1 sample
has the lowest CTAB and BET surface area, higher structure (DBP) and more silanol (–OH) groups AQ1
on surface per unit area.
A second study was performed in which the reactor conditions were manipulated to make silica
powders with a range of structural sizes. The powders from this study are labeled with the letter
‘‘B.’’ Figure 17.5 shows the small-angle x-ray scattering results for the B-series powders and the
unified fit parameters for the scattering curves are shown in Table 17.3. The scattering results show a
range of primary particle sizes, Rg1, from 96.6 to 3500 Å. The aggregate size, Rg2, had values
ranging from 958 to 38,400 Å. Following the distribution in particle and aggregate sizes, the degree
of aggregation, z, showed a range of 92–606 particles per aggregate. Rubber compounds containing
the B-series powders should show variations in mechanical properties. The test results are discussed
in the following section.
For the B-series of samples, the goal was to synthesize silica containing various particle sizes.
The scattering curves for this series of samples are shown in Figure 17.5. Sample B1 had the
smallest primary particle size followed by sample B3, with Rg values of 96.6 Å for sample B1, and
108.8 Å for B3. Both of these samples are close in size to samples A2 (Rg ¼ 85.2 Å) and A3
(Rg ¼ 96.5 Å). The B1 through B8 samples showed a range of sizes with B8 being much larger
while the rest of the samples were between 100 and 460 nm. The aggregate sizes for B1 and B3
samples varied slightly from the aggregate size of the A2 and A3. The aggregate size for B1 was
Rg ¼ 1100 Å, and for B3 the aggregate size was Rg ¼ 1590 Å. There is also similarity in the degree
of aggregation for B1, B3, A2, and A3 (Table 17.3). No trend in the degree of aggregation with
particle size is observed for the B1 through B8 samples as samples with similar primary particle
sizes have different aggregation numbers.
17.4 MECHANICAL TESTING OF FILLED ELASTOMERS

Rubber compounds were made using A1 and A2 shown in Table 17.2 and using a model tire recipe
shown in Table 17.4. The ingredients listed in Table 17.4 are in grams per 100 g of rubber (PHR).
The mixing procedure used for the samples presented in Table 17.5. Both cured and un-cured
compounds were tested and the mechanical testing results are shown in Table 17.6.
1012
1011 Rg = 350 nm
1010 B8
B7
109 B4
B3
108
B1
107
Relative intensity
106
105
104
103
102
101 Increasing size

Rg = 96.6 Å
100
10−1
10−2 2 4 6 8 2 4 6 8 2 4 6 8
10−4 10−3 10−2 10−1
q (Å−1)
FIGURE 17.5 Silica samples B1, B3, B4, B7, and B8. The samples at the bottom of the figure have the
smallest primary-particle size. The increasing size is revealed by a shift of the ‘‘knee’’ of the curve to smaller q.
MDR 2000 and Mooney Viscometer studies at 1008C and 1208C show lower viscosity of the
A1-filled gums. Lower viscosity compounds require less energy input for extrusion. Comparative
results on the dynamic mechanical properties, measured using a rubber process analyzer (RPA), show
TABLE 17.3
Unified Fit Parameters Obtained for Eight Precipitated Samples Provided
by Dimona Silica Ltd.
Level 1 B1 B2 B3 B4 B5 B6 B7 B8
Rg (Å) 96.6 166 108 464 214 143 240 3500

P 4 4 4 4 4 4 4 3.73
G 701 4290 1720 42900 7760 2230 7740 1.77 3 108
B 7.3 3 105 3.8 3 105 1.1 3 104 1.1 3 105 2.4 3 105 3.3 3 105 1.9 3 105 1.7 3 105
Level 2 B1 B2 B3 B4 B5 B6 B7 B8a
Rg (Å) 1100 958 1590 2340 1030 992 1840 38400

P 2.40 2.85 2.11 3.37 3.20 2.84 2.51 2.87
G 4.3 3 105 6.5 3 105 1.2 3 106 4.6 3 106 9.7 3 105 6.5 3 105 1.8 3 106 1.6 3 1010
B 8.7 3 102 9.5 3 103 5.2 3 101 1.6 3 104 1.4 3 103 8.6 3 103 4.5 3 102 1.7 3 105
Z 606 151 716 108 125 293 227 92
a
Level 2 fit values for sample B8 were obtained from light scattering data.
TABLE 17.4
Rubber Compound Formulation
Ingredient phr
SBR 120
BR 25
Silica filler 80
Silica coupling agent 6.3
Stearic acid 2.5
Mineral oil 3.5
Zinc oxide active 2.5
DPG 2
CBS 1.7
Sulfur 2.1
that at the 0.5%-strain dynamic modulus of the A1 compound is about 15% higher than reference
compound. This difference is an indication of higher filler–filler interaction of the A1 particles.
The reinforcing properties measured as M300=M100 are similar for the two vulcanized samples.
However, the cured A1 compounds show lower ultimate elongation at break, higher curing rate
(T90) and shorter breakdown time (T2), which are the signs of lower adsorption of accelerators on
the A1 particles surface.
‘‘Energy loss under low frequency conditions’’ is often used as a key factor for evaluating
elastomer compositions. In this respect, the rolling resistance and skidding properties are usually
evaluated by tan delta (tan d) at 608C and 08C, where the 608C value correlates with low frequency
loss and 08C correlates with skid resistance (high frequency loss).
TABLE 17.5
Mixing Procedure
First mixing stage

Chamber load coefficient, 0.75
Initial chamber temperature, 608C
Initial rotor speed, 60 rpm
Load rubber, close the ram, 0–20 s
Open the ram, load 2=3 silica, 2=3 of aromatic oil, stearic acid, 50–70 s
Open the ram, load 1=3 of silica, 1=3 aromatic oil, 1=3 TESPD, 130–150 s
Open the ram, shape off the remaining silica, close the ram
Increase the rotor speed up to 80 rpm, 210–220 s
Unload the compound at the temperature 1608C, 260–300 s
Mixing stage 2 is repeated three times:
Load the compound, 0–30 s
Unload the compound when temperature reaches 1508C or mixing time 150 s is reached
Third mixing stage
Load the compound, 0–30 s
Open the ram, load sulfur and accelerants, close the ram, 50–70 s
Unload the compound at the temperature 1008C–1108C, 160–180 s
TABLE 17.6
Rubber Testing
A1 A2
Rheometer MDR 2000, 1608C

Torque: max, f=d 16.52 17.39
Torque: min, f=d 1.95 2.30
DM, f=d 14.6 15.0
t2 (s) 308 393
t90 (s) 751 1078
Mooney viscosity, 1008C 69.6 71.1
Mooney scorch, 1208C t35 (s) 2158.8 2879.8
Minimum viscosity 28 31.2
Extrusion:
Density (g=cm3) 1.163 1.162
Conveyor energy (KNm=cm) 19.85 20.86
Conveyor volume (cm3=s) 0.41 0.42
Storage modulus, RPA, 608C, G0 , e—0.5% (kPa) 603.3 524.9
Tan d, RPA, 608C, e—0.5% 0.322 0.360
M300%=M100% 5.27 5.33
Tensile strength (MPa) 17.1 17.7
Ultimate elongation (%) 348 410
Tear resistance (kN=m) 8.6 7.9
Hardness shore A 61.0 59.0
Rebound, 238C (%) 35.7 33.5
Wear resistance:
Loss in weight (mg) 108 124
Abrasion (mm3) 87 103
Density (g=cm3) 1.178 1.180
Compression set, 70 yo8C (%) 12.28 10.61
Friction coefficient (pendulum method):
Wet skidding 60. 6 57.3
Dry skidding 99.3 98.2
Dynamic tests:
Tan d at 08C 0.41 0.35
Tan d at 608C 0.095 0.098
The operational-factor tests performed with A1 filled compounds in comparison with A2 filled
compounds revealed higher predicted wear resistance and wet traction with the same level of rolling
resistance. At the same time the graph of tan d versus temperature in Figure 17.6 shows that tan d is
higher than that of the A2 compound at low temperatures.
The B-series of silica samples were also blended with rubber and the compound formulation is
shown in Table 17.6. The uncured gums were then tested according to ISO 5794-2 1998. The
uncured samples were tested using a Mooney viscometer and a RPA, which measures the dynamic
mechanical properties as the samples cure. Figure 17.4 shows the results of these two tests for the
Mooney viscosity at 1008C, storage modulus, loss modulus and tan d.
In all of the rheometer testing of the uncured compounds, the commercial silica showed the
highest values with the B1 and B3 samples having the highest values among the B-series silica
samples. The Mooney viscosity at 1008C increases as the number of particles in the aggregates
increases. The same compounds were cured and tested, measuring tensile properties, tear resistance,
1.0
A1
0.8 A2
0.6
Tan d
0.4
0.2
0.0
−100 −50 0 50 100
Temperature (⬚C)
FIGURE 17.6 Plot of tan d versus temperature for A1- and A2-cured compounds measured using a rubber
process analyzer (RPA).
hardness, and wear resistance. The values from these tests are shown in Figure 17.7. The mechanical
testing on the vulcanized compounds is shown in Figure 17.8.
The mechanical test data show an increase in ultimate elongation for several of the B1 through
B8. Samples B1, B3, and B6 in particular showed similar tensile strength and elongation as the A2
and A3 samples. The tear resistance values were also similar for the B1 and B3 samples compared to
A2 and A3 samples.
The stress–strain curves for the two commercial samples and the B1 through B4 samples are
plotted in Figure 17.9. The samples B1, B3, and B6 are plotted with the commercial silica samples,
showing the similarity in the stress–strain behavior (Figure 17.9a). As the primary particle size and
2500
120
Mooney viscosity (100⬚C)
Storage moduls (MPa)
100 2000
80 1500
60
1000
40
500
20
0 0
B1 B2 B3 B4 B5 B6 B7 B8 A2 A3 B1 B2 B3 B4 B5 B6 B7 B8 A2 A3
0.10
140
120 0.08
Loss moduls (MPa)
100
Tangent d
0.06
80
60 0.04
40
0.02
20
0 0.00
FIGURE 17.7 Results for the B1 through B8 and A2 and A3 silica samples showing the Mooney viscosity at
1008C, and the dynamic mechanical properties measured by rubber process analyzer (RPA) during curing of the
compounds.
25 800
Tensile strength (MPa)
Tensile elongation (%)

20
600
15
400
10
200
5
0 0
50 60
Tear resistance (kN/m)
40 58
Shore hardness
30 56
20 54
10 52
0 50
FIGURE 17.8 Mechanical testing results for cured compounds showing tensile, hardness, and tear properties.
degree of aggregation decreases for the B-series samples (Table 17.3), the tensile elongation and
ultimate stress decrease as well.
17.5 CONCLUSION
The purpose of the summary of recent research was to demonstrate the application of small-angle
scattering to study silica. Using small-angle x-ray scattering it was possible to measure the
morphological characteristic of primary particles, aggregates and agglomerates. In addition to
primary particle size, the degree of aggregation is also a parameter controllable by synthetic
25 25
A2 B3
A3 B4
20 B1 20 B5
B3 B7
B8
Stress (MPa)
Stress (MPa)
B6
15 15 Decreasing z and Rg
10 10
5 5
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
(a) Strain (%) (b) Strain (%)
FIGURE 17.9 Stress–strain curves for the eight B-series silica samples and the A2 and A3 silica samples. B1,
B3, B6, and the two commercial silica compounds. A, The effect of particle size and the degree of aggregation
on the stress–strain properties for the B-series samples is shown B, with the elongation and ultimate stress
decreasing with decreasing particle size and degree of aggregation.
protocol. Structural information for several types of precipitated silica showed that a range of
morphologies is present among the samples. The relative comparison of mechanical properties of
the rubber compounds showed that the testing values varied with the aggregate structure.
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[AQ1] Please provide expansion for CTAB and BET.
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17 Silica Fillers for Elastomer

17.1 Introduction ........................................................................................................................ 505

506 Current Topics in Elastomers Research

17.2 SMALL-ANGLE SCATTERING

17.2.1 SCATTERING EXPERIMENTS

Incident beam Transmitted beam

Silica Fillers for Elastomer Reinforcement 507

Relative intensity 109

By measuring the scattered intensity as a function of q over multiple decades in q, information

I(q) BP q4 where B ¼ 2pN(Dr)2 S (17:2)

508 Current Topics in Elastomers Research

17.2.2 SCATTERING DATA ANALYSIS

Silica Fillers for Elastomer Reinforcement 509

The value for dv=s is then calculated for spheres as:

17.3 SMALL-ANGLE X-RAY STUDIES ON SILICA POWDERS

510 Current Topics in Elastomers Research

Rg (Å) 126.4 85.2 96.5

Rg (Å) 295 123 125

Silica Fillers for Elastomer Reinforcement 511

BET surface (sm2=g) 148 174 164

17.4 MECHANICAL TESTING OF FILLED ELASTOMERS

512 Current Topics in Elastomers Research

101 Increasing size

Rg (Å) 96.6 166 108 464 214 143 240 3500

Rg (Å) 1100 958 1590 2340 1030 992 1840 38400

Silica Fillers for Elastomer Reinforcement 513

First mixing stage

514 Current Topics in Elastomers Research

Rheometer MDR 2000, 1608C

Silica Fillers for Elastomer Reinforcement 515

Storage moduls (MPa)

516 Current Topics in Elastomers Research

Tensile elongation (%)

Silica Fillers for Elastomer Reinforcement 517

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