Composites: Part A 62 (2014) 52–59

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Effect of the temperature on surface modification of silica and properties

of modified silica filled rubber composites
Yan Li b, Bingyong Han a, Shipeng Wen b, Yonglai Lu b, Haibo Yang b, Liqun Zhang b, Li Liu a,b,c,⇑
a
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, PR China
b
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, PR China
c
Beijing Engineering Research Center of Advanced Elastomers, Beijing University of Chemical Technology, Beijing 100029, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The modified silica at different temperature (MSaDT) with bis(3-triethoxysilylpropyl)tetrasulfide (TES-
Received 17 December 2013 PT), and MSaDT filled solution styrene butadiene rubber (SSBR) composites were prepared to investigate
Received in revised form 28 February 2014 the effect of temperature on surface modification of silica. The results showed that TESPT was success-
Accepted 5 March 2014
fully bonded on the surface of silica by chemical bonds. The grafting degree (K) of MSaDT of 50 °C was
Available online 12 March 2014
62.2% and higher than that at the other temperatures. The thermal weight loss and the size distribution
of MSaDT showed that the silanol of TESPT hydrolysates reacted with the surface hydroxyl groups of
Keywords:
silica, decreasing the average size and agglomeration of modified silica. For 50 °C modified silica/SSBR
A. Nano-structures
A. Polymer–matrix composites
composite, the static mechanical properties and rubber–filler interaction of the composite were better
B. Mechanical properties than those of the others. As far as dynamic mechanical properties are concerned, the 50 °C modified
E. Surface treatments silica/SSBR composite owned a best combination of low rolling resistance and high wet skid resistance.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction and rubber in an open or internal mixer at high temperatures

[17] or combinations of room and high temperatures [18]. Other
In the rubber industry, nanosilica is one of the most important researchers applied pre-modification of silica with TESPT and then
reinforcing fillers and has been researched and applied in depth mixed the pre-modified silica with rubber according to compound-
[1,2], regarded as a replacement for carbon black [3], and applied ing procedures. Such pre-modification of silica is always accom-
in green tire preparation [4,5], since it can provide a combination plished by simply dipping the silica into organic solutions, for
of good mechanical properties [6], high wet skid resistance, and example ethanol [19], leading to the uncertain physical or chemi-
low rolling resistance [7]. cal adsorption of TESPT on the surface of silica. As is well known,
However, the compatibility between the rubber matrix and the most effective modification of silica with a kind of SCAs such
nanosilica is rather poor because of the large quantities of hydroxyl as TESPT involves the chemical bonding between the SCAs and
groups on the surface of nanosilica and high surface energy, result- silica particles, which is originated from the condensation of the
ing in severe agglomeration and weak rubber–filler interaction silanols of hydrolyzed TESPT with the surface hydroxyl groups of
[8,9]. Surface modification [10] of nanosilica can reduce the surface silica. However, the above mentioned modification methods do
hydroxyl density and thus improve the compatibility of nanosilica not definitely involve the hydrolysis of TESPT, making the modifi-
with the rubber matrix, leading to the improvement of filler cation reaction uncontrollable and difficult to identify. In our pre-
dispersion and performance of the rubber composite [11]. vious study [20], we investigated surface modification of silica by
The silane coupling agents (SCAs) are widely used in the Two-Step-Method and the influence of TESPT amount for the per-
modification of several kinds of fillers, such as nanotubes [12], formance of rubber composites, indicating that 8 wt% TESPT
glass fiber [13], and nanosilica [14]. Bis(3-triethoxysilylpropyl)tet- amount was the best to decrease the agglomeration of silica and
rasulfide (TESPT) has been successfully applied in the modification the processing energy consumption during the compounding of
of nanosilica [15,16]. Some researchers blended TESPT with silica rubber and silica. Nevertheless, we just analyzed the effect of
TESPT amount on the modification of silica at constant tempera-
ture. Furthermore, for surface modification of silica, many reports
⇑ Corresponding author at: Materials Science and Engineering, Beijing University
of Chemical Technology, 15 BeiSanhuan East Road, ChaoYang District, Beijing
focused only on the kinds of SCAs [21,22], paying hardly any
100029, PR China. Tel.: +86 10 64443413; fax: +86 10 64433964. attention to the effect of temperature during the modification
E-mail address: [email protected] (L. Liu). procedure. From the perspectives of chemical reaction kinetics,

http://dx.doi.org/10.1016/j.compositesa.2014.03.007
1359-835X/Ó 2014 Elsevier Ltd. All rights reserved.
 Y. Li et al. / Composites: Part A 62 (2014) 52–59 53

the high temperature may promote the grafting reaction between Table 1
hydrolyzed TESPT and silica. In other word, we considered that dif- Formulation of MSaDT/SSBR compounds.

ferences in the chemical reactivity of the hydrolysate of TESPT and Materials Amount/phra
silica at different temperatures resulted in different degrees of SSBR 137.5
grafting modification. MSaDT 75
In this study, we prepared the hydrolysates as same as our pre- Zinc oxide 3.5
vious study [20] at constant temperature firstly, mixed the hydrol- Stearic acid 2.0
N-Isopropyl-N0 -phenyl-1,4-phenylenediamine 1.3
ysates of TESPT with silica to prepare modified silica at different Paraffin wax 1.5
temperature (MSaDT) and investigated the effect of temperature N-Cyclohexyl-2-beozothiazole sulfonamide 1.5
on the surface modification of silica. The rubber composites filled 1,3-Diphenyl guanidine 2.0
with MSaDT were fabricated to evaluate the improvement in the Tetramethylthiuram disulfide 0.4
Sulfur 1.4
performances of the composites. The comparison of the silica
before and after modification was carried out by using Fourier a
Parts per hundred of rubber.
transform infrared (FTIR) spectroscopy, thermal gravimetric analy-
sis (TGA), and dynamic light scattering (DLS). For MSaDT/SSBR
composites, transmission electron microscope (TEM), rubber pro- obtained by a P3555B2 Disc Vulkameter (Beijing Huanfeng Chem-
cess analyzer (RPA), and dynamic mechanical thermal analysis ical Machinery Trial Plant, China). The composites were prepared
(DMTA) were used to determine the dispersion of MSaDT, filler by a XLB-D350  350-type Automatic Operation Vulcanizing Press
network structure, and dynamic mechanical properties of the com- (Huzhou Dongfang Machinery Co., Ltd., China). The compounds
posites, respectively. were vulcanized at 160 °C for t90 in a standard mold to produce
the MSaDT/SSBR vulcanizates.
2. Experimental
2.4. Characterizations
2.1. Materials
The difference in reactive groups between pure silica and
Commercial SSBR (Buna VSL 5025-2HM), composed of 75% MSaDT was identified on a Tensor 27 FTIR spectrometer (Bruker
butadiene with a 50% vinyl content, and 25% styrene content, Optik Gmbh Co., Germany). The samples were pressed into pellets
extended with 37.5 phr treated distillate aromatic extracts (TDAE) together with potassium bromide (KBr). The spectra were recorded
oil, was purchased from Lanxess Chemical Industry Co., Ltd. (Ger- in the wavenumbers range 500–4000 cm1. The organic degree
many). Precipitated silica of Tixosil 383 [median diameter (d50) [23,24] of MSaDT was obtained from the grafting degree, which
is 13.7 lm, DOP (dioctyl phthalate) oil absorption is 2.66 mL/g, is calculated according to Eq. (1):
CTAB (cetyltrimethyl ammonium bromide) specific surface area
is 163 m2/g] was produced by Rhodia France (Qingdao, China). K ¼ ðR  rÞ=R  100%; ð1Þ
Bis(3-triethoxysilylpropyl)tetrasulfide (TESPT) was obtained from
where K is the grafting degree of the hydroxyl, R is the ratio of the
Nanjing Shuguang Chemical Group Co., Ltd. (China). All other
hydroxyl peak areas at 3447.35 cm1 and 1108.32 cm1 in the spec-
materials were commercially available.
trum of pure silica, and r is the ratio of the hydroxyl peak areas at
3447.35 cm1 and 1108.32 cm1 in the MSaDT spectrum.
2.2. Surface modification of silica nanoparticles The weight loss measurements of pure silica and MSaDT were
performed on a TGA STARe system (Mettler-toledo Co., Switzer-
TESPT hydrolysates were prepared according to our previous land) under nitrogen atmosphere. The samples for TGA tests were
reported procedure [20]. Absolute ethanol 1000 mL and deionized heated at a heating rate of 10 °C/min.
water 30 mL were added to a beaker, and acetic acid was used to The particle size distributions of pure silica and MSaDT were
adjust the pH value to approximately 4.5. TESPT 8 g (mass ratio characterized by dynamic light scattering (DLS) on a Malvern
of TESPT to Silica = 8%) was added to the solution and hydrolysis ZEN3600 NanoZS Analyzer (Malvern Instruments Co., England).
of TESPT was allowed to proceed for 10 h, resulting in the transfor- The samples were dispersed in ethanol for 2 h by ultrasonic tech-
mation of ethyoxyl to hydroxyl. Silica nanoparticles 100 g were nology before it was put in the instrument for particle size distri-
dispersed in TESPT hydrolysate in a three-necked flask under stir- bution measurements.
ring for 48 h at different temperatures (30 °C, 40 °C, 50 °C, 60 °C, The filler dispersion was investigated on a Tecnai G2 20 TEM
and 70 °C). Finally, the slurry was dried in a vacuum oven to obtain (FEI Co., USA) with an accelerating voltage of 200 kV. The thin sec-
MSaDT powder. For the assessment of the surface modification of tions for TEM observations were cut by a microtome at 100 °C
silica, a part of MSaDT was extracted in a Soxhlet extractor by tol- and collected on copper grids.
uene for 48 h to remove the un-grafted TESPT, and then dried in a The static mechanical properties of the composites were mea-
vacuum oven at 70 °C for 24 h. The remainder of the MSaDT was sured according to ASTM D638 by a CMT4104 Electrical Tensile
compounded with rubber to prepare the MSaDT filled SSBR Tester (Shenzhen SANS Test Machine Co., China) at a tensile rate
composites. of 500 mm/min.
The dynamic rheological properties of the composites were ana-
2.3. Preparation of MSaDT/SSBR composites lyzed by RPA 2000 (Alpha Technologies Co., USA) at 60 °C. For the
rubber compounds, the strain amplitude was varied from 0.1% to
The formulation for the preparation of MSaDT/SSBR compounds 400% at the test frequency of 1 Hz. For the rubber vulcanizates,
is shown in Table 1. Firstly, the zinc oxide, stearic acid, N-Isopro- the strain amplitude was varied from 0.1% to 40% at the test fre-
pyl-N0 -phenyl-1,4-phenylenediamine, paraffin wax and MSaDT quency of 10 Hz.
were directly compounded with SSBR base gum, and then all of The viscoelastic properties of the composites were measured on
the other ingredients were uniformly blended on a 6-inch two-roll a VA3000 DMTA (01 dB-Metravib, France) in the tension mode. The
mill (Shanghai Rubber Machinery Works No. 1, China) at room temperature was from 60 °C to 100 °C, the heating rate was 3 °C/
temperature. The optimum cure time (t90) of the compounds were min, the frequency was 10 Hz, and the strain amplitude was 0.1%.
54 Y. Li et al. / Composites: Part A 62 (2014) 52–59

Table 2
Grafting degree (K) of MSaDT.

Modification temperature /°C 30 40 50 60 70

K/% 40.3 58.4 62.2 41.2 34.8

dispersion of silica in the rubber matrix after the surface modifica-

tion of silica.
The grafting degrees (K) of MSaDT are listed in Table 2. As the
modification temperature increases, the value of K increases,
reaches a maximum, and then decreases sharply. The value of K
at 50 °C is relatively the higher than the others, indicating that
the modification effect of modified silica is the best at the temper-
Fig. 1. FTIR spectra of pure silica and MSaDT. (For interpretation of the references to
ature of 50 °C. For the reasons, we consider that low-temperature
colour in this figure legend, the reader is referred to the web version of this article.) modification makes that the grafting reaction activity is low, so
as to obtain the low reaction probability between TESPT hydroly-
sates and silica. Moreover, high-temperature modification leads
3. Results and discussion the polycondensation among the hydroxyl groups of hydrolysates
of TESPT, producing the polycondensates of TESPT which is hard
3.1. Chemical structure characterization of MSaDT by FTIR to react with silica. So it is concluded that high or low tempera-
tures are both not benefit for the surface modification of silica,
Fig. 1 shows the FTIR spectra of the pure silica and MSaDT of resulting in the low grafting degree.
30 °C, 40 °C, 50 °C, 60 °C, and 70 °C, respectively. The absorption
peaks at 3440 cm1 and 1650 cm1, corresponding to the stretch- 3.2. Surface modification effect of MSaDT by TGA and DLS
ing and deforming vibration modes, respectively, are the H–O–H
bonds of the adsorbed water; the absorbance ranging from The thermal weight losses of pure silica and MSaDT were inves-
1000 cm1 to 1150 cm1, assigned to the Si–O–Si stretching mode tigated by TGA, and the results are presented in Fig. 2A. The pure
[25], is obvious. The surface modification of silica is realized by silica was dried in the vacuum oven together with the other
chemical reaction between the hydroxyl groups of silica and the modified ones, so all silica samples have the similar treating expe-
silanol groups of hydrolyzed TESPT. Therefore, the surface grafting riences. The curve of pure silica shows an obvious loss at 50–120 °C
reaction can be easily identified by the appearance of characteristic (first zone) because of the removal of the absorbed water and
bond, such as the peak for methylene (–CH2–) [26] at 2850– hydroxyl groups, but no significant weight loss after 120 °C (sec-
2900 cm1, in the FTIR spectra of MSaDT. As shown in Fig. 1, after ond zone). The weight loss of the sample about 2.5% is attributed
the removal of un-reacted TESPT by Soxhlet extraction, the strong to the dehydroxylation of the hydrogen bonds of pure silica in
absorbance peaks at 2855 cm1 and 2950 cm1 attributed to the – the second zone. However, the weight losses in the first zone of
CH2– vibration of TESPT appear for all samples except pure silica, all MSaDT samples are lower than that of pure silica as a result
indicating that TESPT is successfully bonded to the surface of silica. of the chemical bonding of the surface hydroxyl groups of silica
To further investigate the grafting reaction by comparison of the with the hydrolyzed TESPT after modification [28,29]. However,
position of Si-OH peaks near 3400 cm1, it can be found that the the relative weight loss of MSaDT in second zone is obviously
peaks in the FT-IR spectra of MSaDT have shifted in the direction higher than that of pure silica, which is due to the degradation of
of higher wavenumbers, in a so-called ‘‘blue shift’’ [27]. This ‘‘blue TESPT on silica surface. The MSaDT of 50 °C owns the largest
shift’’ suggests that the number of hydroxyl groups decreases after weight loss in second zone, indicating that the reaction extent
the modification of silica with TESPT, resulting in the destruction of between silica and TESPT is the highest, in consistence with the
hydrogen bonds on the surface of silica. Generally, the poor disper- result listed in Table 2.
sion of silica in the rubber matrix is mainly due to the large amount The size distributions of pure silica and MSaDT were character-
of hydrogen bonds formed among the hydroxyl groups on the silica ized by DLS, and the results are shown in Fig. 2B. The samples of
surface. Hence, the destruction of hydrogen bonds can improve the pure silica and MSaDT were ultrasonically dispersed before

Fig. 2. TGA curves (A) and Particle size distributions (B) of pure silica and MSaDT. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)
 Y. Li et al. / Composites: Part A 62 (2014) 52–59 55

Fig. 3. Schematic diagram of the modification mechanism of nanosilica. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

characterization. It can be seen that pure silica presents severe reaction of silica and TESPT. The suitable temperature can increase
agglomeration, with the primary and secondary aggregates at the collision probability between silica and TESPT; in addition lead
260 nm and 700 nm, respectively, and even larger aggregates at the modification effect better than the other low or high
5–6 lm. Compared with the pure silica, the MSaDT shows a smal- temperatures.
ler particle size and narrower particle size distribution. With the
increase of modification temperature, the peaks of particle size 3.4. Micromorphology of MSaDT/SSBR composites by TEM
shift toward small size at the temperatures below 50 °C, but the
shift reverses direction at the temperatures above 50 °C. The values The TEM images in Fig. 4 show the filler dispersion in MSaDT/
of average particle size are marked in Fig. 2B, indicating that the SSBR composites. The dispersion of silica in the rubber matrix is
MSaDT of 50 °C has the smallest particle size of 105 nm. It can be one of the important factors in determining the comprehensive
concluded that the modified temperature of 50 °C is beneficial to properties of the rubber composites. A homogeneous dispersion,
decrease the particle size and suppress the particle agglomeration. especially at the nanoscale, leads to superior properties. On the
contrary, the aggregated fillers in the rubber matrix form stress
3.3. Analysis of the modification mechanism of silica concentration points, resulting in inferior macroscopic properties,
such as the static and dynamic mechanical properties. In Fig. 4A
The modification essence of silica is the reaction between the and B, the large silica aggregates are observed distinctly in the rub-
hydroxyl from the surface of the silica and the hydroxyl from the ber matrix, implying poor rubber–filler interaction. At a modifica-
hydrolysis of the end group of TESPT. For the in-situ modification, tion temperature of 50 °C, the dispersion of silica becomes more
the nanosilica is directly mixed with rubber and TESPT together. homogeneous, as shown in Fig. 4C. The composite has fewer silica
During this process, the TESPT has limited chance to react with aggregates and gap cavities in comparison to the others. However,
the silica aggregates because parts of them also dissolve in the rub- as the temperature increases above 50 °C, the dispersion of silica
ber matrix [20]. Meanwhile, it is not clear whether the interaction deteriorates, with the samples showing large aggregates and gap
between silica and TESPT is simple physical absorption or the cavities, as shown in Fig. 4D and E. In other words, 50 °C is an opti-
chemical bonding during the condensation reaction of the hydro- mum temperature for silica surface modification, resulting in rela-
lyzed hydroxyl of TESPT and surface hydroxyl of silica, so the reac- tively uniform dispersion and better distribution of silica in the
tion degree between TESPT with silica aggregates is limited, as a rubber matrix.
result of the incomplete modification and severe agglomeration
of nanosilica in rubber matrix. The friction among silica is serious 3.5. Dynamic rheological properties of MSaDT/SSBR composites by RPA
during the mixing procedure; meanwhile, the TESPT cannot graft
on the surface of silica to play a part of ‘‘coupling bridge’’, leading The changes of the storage modulus (G0 ) of the MSaDT/SSBR
the strong silica–silica interaction. As shown Fig. 3, the pre-modi- composites with the strain amplitude are tested in order to analysis
fication of silica indicates that TESPT hydrolyzes firstly and then the filler network structure, as shown in Fig. 5, in which Fig. 5A rep-
reacts with silica, as a result of the organic functionalization on resents the curves of G0 vs. strain of the compounds and Fig. 5B rep-
the surface of silica by TESPT before compounding with rubber, resents that of the vulcanizates, respectively. In a filled rubber
increasing the compatibility of the rubber and silica. Moreover, compound and vulcanizates, the strain dependence of the dynamic
the reactivity of the silica and TESPT at low temperature is not high viscoelastic properties has been brought into clear focus by the
enough to realize the condensation of the hydroxyl groups success- study of Payne since 1960s, regarding as storage modulus is called
fully, resulting in the exposing of the hydroxyl groups on the the Payne effect [30]. The lower Payne effect indicates the higher
surface of silica. However, at the high temperature the self-poly- uniformity of the filler dispersion and the weaker filler network
merization can tend to happen among TESPT, leading to generate structure in rubber matrix. Fig. 5A shows that the MSaDT/SBBR
the oligomers, which can influence the probability of the grafting compound of 30 °C exhibits an obvious Payne effect. The Payne
56 Y. Li et al. / Composites: Part A 62 (2014) 52–59

Fig. 4. TEM images of MSaDT/SSBR composites with MSaDT of (A) 30 °C, (B) 40 °C, (C) 50 °C, (D) 60 °C, and (E) 70 °C.

Fig. 5. Strain amplitude dependence of storage modulus (G0 ) of MSaDT/SSBR composites: (A) compounds and (B) vulcanizates. (For interpretation of the references to colour
in this figure legend, the reader is referred to the web version of this article.)

effect of the compound decreases with increasing modification 3.6. Viscoelastic properties of MSaDT/SSBR vulcanizates by DMTA
temperature, reaches a minimum at a modification temperature
of 50 °C, and then increases as the modification temperature The temperature dependence of dynamic mechanical viscoelas-
increases from 50 °C to 70 °C. It is considered that the MSaDT/SSBR ticity of the MSaDT/SSBR vulcanizates is shown in Fig. 6. From
compound at 50 °C has the best modification effect, which Fig. 6A, it can be seen that the MSaDT/SSBR vulcanizate of 50 °C
improves the compatibility between rubber matrix and silica. shows the lowest storage modulus (G0 ) below the glass transition
Therefore, it can reduce the agglomeration of silica and increasing temperature (Tg), whereas G0 drops the slowest in the rubber state,
the rubber–filler interaction, leading to the weaker filler network thus ending up the highest in the temperature range 10–100 °C.
structure [31]. As shown in Fig. 5B, the strain amplitude depen- In fact, below Tg the filler network structure is the only factor to
dence of G0 of the MSaDT/SSBR vulcanizates shows the same varia- mainly contribute to the G0 of a filled rubber composite because
tion trend as that of the compounds. The filler network structure in the polymer chains are frozen and their segmental movements
MSaDT/SSBR vulcanizates is weakest at the modification tempera- are restricted. As shown in Fig. 6A1, the MSaDT/SSBR vulcanizate
ture of 50 °C, consistent with the TEM observation presented above. of 50 °C has the lowest G0 because it possesses the weakest filler
 Y. Li et al. / Composites: Part A 62 (2014) 52–59 57

Fig. 6. Temperature dependence of (A) storage modulus G0 and (B) loss factor tan d of various MSaDT/SSBR vulcanizates. (A1) and (A2) are enlargements of circled region of
(A), and (B1) and (B2) are the enlargements of circled region of (B). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version
of this article.)

network structure. In contrast, as the temperature increases to participating in chain segment relaxation, resulting in higher val-
ambient temperature or above, the mobility of the rubber chains ues of tan d and lower values of G0 , as shown in Fig. 6A. On the other
is enhanced, and the rubber–filler interaction and rubber network hand, it is well known that the hysteresis of tread composites,
structure (rubber chain entanglements and chemical crosslinked characterized by tan d at 60 °C, is a key parameter that shows a
network) become the main contributions to G0 . The highest G0 of good correlation with the rolling resistance of tires. In addition,
the MSaDT/SSBR vulcanizate of 50 °C observed in Fig. 6A2 in the the hysteresis at 0 °C is related to the high-frequency nature of
temperature range 40–100 °C suggests that this vulcanizate has the dynamic strain involved in the skid process. Therefore, high
the strongest rubber–filler interaction, which resulted from the performance rubber materials should have a combination of a high
uniform dispersion of silica in the rubber matrix and the strong tan d at 0 °C and a low tan d at 60 °C [34]. As shown in Fig. 6B1, the
interfacial interaction between the silica and the rubber [17]. values of tan d at 0 °C of the MSaDT/SSBR vulcanizates of 50 °C and
As shown in Fig. 6B, the MSaDT/SSBR vulcanizate of 50 °C has 30 °C are similar and both are higher than those of other vulcaniz-
the highest tan d at Tg because the MSaDT of 50 °C has the best ates. Meanwhile, as shown in Fig. 6B2, the tan d values at 60 °C of
dispersion in the rubber matrix, reducing the filler network struc- the various vulcanizates show the distinct differences, but the
ture [32] and the amount of rubber chains trapped in the filler net- value of MSaDT/SSBR vulcanizate of 50 °C is clearly the lowest,
work [12,33]. Therefore, there are more rubber molecular chains indicating the low rolling resistance of this vulcanizate. Thus, the
58 Y. Li et al. / Composites: Part A 62 (2014) 52–59

Fig. 7. Static mechanical properties of MSaDT/SSBR composites: (A) Modulus at 100% and 300% elongation; (B) Reinforcing index (RI) and tensile strength. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version of this article.)

silica modified at 50 °C has a high ability to reduce the rolling resis- modification study is crucial to the application of nanosilica in the
tance with the maintenance of a good wet skid resistance of rubber rubber industry as a kind of oil-independent filler. The modifica-
composites. tion is of great importance in the development of new approaches
for the surface modification of silica, and the modified silica has
3.7. Static mechanical properties of MSaDT/SSBR composites bright prospects in green tire applications.

The static mechanical properties, such as tensile strength, mod-

Acknowledgements
ulus at 100% and 300% elongation, and reinforcing index (RI) were
investigated, and the results are shown in Fig. 7. It can be observed
The research was supported by the Program for Changjiang
in Fig. 7A that with increasing modification temperature, the mod-
Scholars and Innovative Research Team in University (PCSIRT,
ulus at 100% elongation of the MSaDT/SSBR composites increases
IRT0807), the National Natural Science Foundation of China
obviously, reaches a maximum at 50 °C, and then decreases with
(51073008 and 51103005) and the Fundamental Research Funds
the modified temperature rising from 30 °C to 70 °C. The modulus
for the Central Universities in China.
at 300% elongation of the composites shows the same tendency as
the modulus at 100%. As shown in Fig. 7B, the tensile strength of
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