Tire tread compounds with reduced rolling resistance and improved

wet grip
Viviane Dall’Agnol Veiga,1 Taline Marchesini Rossignol,1 Janaina da Silva Crespo,1
Larissa Nardini Carli2
1
Area do Conhecimento de Cie
^ ncias Exatas e Engenharias, Universidade de Caxias do Sul, Rua Francisco Getu
 lio Vargas, 1130,
Caxias do Sul RS 95070-560, Brasil
2
Campus Blumenau, Universidade Federal de Santa Catarina, Rua Pomerode, 710, Blumenau SC 89065-300, Brasil
Correspondence to: J. S. Crespo (E - mail: jscrespo@ucs.br) and L. N. Carli (E - mail: larissa.carli@ufsc.br)

ABSTRACT: The aim of this work is to investigate the replacement of carbon black by silica-organosilane coupling agent system and
the number of processing steps on the mechanical properties, rolling resistance, and wet grip of truck tire treads. Eight compounds
were prepared: two formulations based on carbon black, five formulations with the partial replacement of carbon black by a silica-
organosilane coupling agent system, and one formulation with the total replacement of carbon black with silica. The rolling resistance
decreased by 10% and the wet grip increased by 18.5% for the compound with 15 phr of silica, 3 phr of organosilane, and three
processing steps compared to the standard compound. The processing steps also promoted an improvement in these properties for
the composition with 50 phr of carbon black. The partial use of silica reduced the abrasion loss, thus confirming the durability of the
compound. V C 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45334.

KEYWORDS: elastomers; mechanical properties; rubber; structure-property relationships

Received 21 February 2017; accepted 23 May 2017

DOI: 10.1002/app.45334

INTRODUCTION
One of the major challenges in the rubber industry today is the
relationship among durability, safety, and economy for tire
applications.1,2 These requirements are achieved in tire treads by
improving the abrasion resistance, wet grip, and rolling resis-
tance properties. Although they are antagonistic, achieving an
equilibrium among these characteristics is essential for the
manufacturing and performance of tire tread compounds. The
abrasion resistance contributes to the life of the tire, the wet
grip contributes to safety, and rolling resistance contributes to
the total fuel efficiency.3
Fuel consumption and tire wear in all types of automobiles
have become increasingly important because of adverse environ-
mental effects and economic costs.4 The rolling resistance of
tires is responsible for 1/3 of the fuel consumption of a truck.
The tire tread alone is responsible for approximately half of the
hysteresis energy loss, which in turn represents 80% to 95% of
the rolling resistance losses.3 In recent decades, many govern-
ment departments have enacted laws and regulations requiring
improved fuel efficiency for automobiles. In this context, the
tire industry has responded by developing fuel-efficient tires by
reducing the tire rolling losses.4
Since the development of the green tire by Michelin in the early
1990s,5,6 important progress in rolling resistance reduction with
good wet grip was achieved by replacing carbon black with
silica-organosilane coupling agent system. Coupling agents are
commonly used to obtain a better dispersion of the silica and
reinforce the rubber, thereby decreasing the filler-filler interac-
tion and increasing the filler-polymer compatibility.2,7–12 In
addition to the use of a coupling agent, high levels of mixing
energy as well as some resting time under no shearing or tem-
perature are required to the complete development of rubber-
filler interactions, and this can be achieved through various
steps of processing.13
Dierkes2 and Ren et al.14 evaluated different organosilanes
focusing on the interaction of the silica with the coupling agent
as the first step in the formation of a stable network between
the filler-coupling agent-polymer. The studies reported that
replacing carbon black with a silica-organosilane coupling agent
system results in changes mainly in the tear strength, abrasion
loss, heat resistance, hardness, modulus, viscosity, and resil-
ience.2 Furthermore, as demonstrated by Cichomski et al.,7 the
presence of sulfur in some organosilane structures also plays an
important role in the dynamic properties of the compounds.

C 2017 Wiley Periodicals, Inc.

V

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The most commonly used coupling agents are organosilanes
such as bis(triethoxysilylpropyl)tetrasulfide (TESPT), which has
an inorganic fraction that interacts with the filler, an organic
fraction that reacts or is compatible with the elastomeric matrix,
and sulfur within its structure, which may increase in the cross-
linking density of the final product. Ansarifar et al.1 used
TESPT in their studies of natural rubber compounds. The best
results for hardness, tear and tensile strength were obtained
with 7 phr of organosilane. However, the filler-polymer interac-
tion was more effective with 5 phr. The influence of the storage
time, temperature, and organosilane content in the polymer-
filler interaction of SBR compounds was also analyzed by
Choi.15 In these studies, the carbon black was totally replaced
by silica-organosilane coupling agent, resulting in rubber com-
pounds with better wet grip16 and rolling resistance.17 However,
some limitations were reported regarding the poor processabil-
ity of the compounds and the effectiveness of the silanization
process.1,2 To overcome these drawbacks, the partial replacement
of carbon black by silica-organosilane was considered by Ratta-
nasom et al.17 However, the influence of the organosilane con-
tent and the number of processing steps was not studied in
detail in the literature.
In this work, the combination of both fillers was studied aiming
to achieve the good mechanical properties of carbon black with
the reduction of the rolling resistance and an improvement in
the wet grip provided by silica. Thus, the organosilane and sul-
fur content, and the influence of processing steps were evaluated
in elastomeric compounds for truck tire treads. The elastomeric
compounds were prepared and characterized by physicochemi-
cal and mechanical analyzes, and the results were compared to a
standard formulation containing only carbon black.
EXPERIMENTAL
Materials
The materials used in this study included: natural rubber with a
Mooney viscosity of 80 ML 1 1 4 at 100 8C (Borrachas Quir-
ino); styrene-butadiene rubber 1712 with a Mooney viscosity of
50 ML 1 1 4 at 100 8C and 23% styrene (Lanxess); high-cis
polybutadiene rubber with a Mooney viscosity of 40 ML 1 1 4
at 100 8C (Goodyear); carbon black N330 with an average parti-
cle size of 26 to 30 nm and a surface area of 70 to
99 m2 g21(Columbian Chemicals); amorphous precipitated sil-
ica with a surface area of 160 to 190 m2 g21 (Rhodia); zinc
oxide (Companhia Mineira de Metais); stearic acid (JBS); sulfur
(Intercuf); N-t-butyl-2-benzothiazylsulfenamide (Flexsys); 1,3-
diphenylguanidine (Lanxess); TESPT SCA 98 with a sulfur con-
tent of 21% to 23% (Struktol); acetone (Neon, Brazil, 99.5%);
and toluene (Din^amica Quımica Contempor^anea Ltda, Brazil,
99.8%). All chemicals were used without further purification.
Preparation of the Compounds
Figure 1 describes the scheme of preparation of the eight com-
pounds. The formulations were prepared in an internal mixer
(Banbury, Cope) run at 155 8C and 450 rpm for 150 s for the
systems containing carbon black and for 300 s for the com-
pounds containing silica. In this case, 300 s are necessary to
allow the system to reach the desired temperature and to the
organosilane to receive enough activation energy to react with
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Figure 1. Flow sheet diagram of the preparation of the compounds.
the silica particles, thus allowing the occurrence of the silaniza-
tion reaction to completion. The curing agents were added to
the formulations in a laboratory-size open two-roll mill (Cope)
at 90 8C for 150 s and 1000 rpm speed at the rear roll and 1300
at the front roll. To promote a better filler-polymer interaction,
some formulations were processed in three steps, as indicated in
the compounds’ codes (n 5 1 or n 5 3). When the processing
occurred in one step, the compounds were mixed according to
the procedure described above. When three steps were per-
formed, the mixture obtained in the first step, without the addi-
tion of curing agents and after rest for 16 h, underwent a new
processing both in the internal mixer and in the open two-roll
mill under the same conditions. This procedure was repeated
twice. In this case, the vulcanizing agents were added in the last
step to avoid prevulcanization.
Eight compounds were prepared according to Table I, and the
properties obtained were compared to a standard formulation
of rubber used in the fabrication of truck tire treads. The for-
mulations are identified as follows: phr of carbon black/phr of
silica/phr of organosilane-number of processing steps. Two for-
mulations were based on carbon black (varying the processing
conditions): 50/0/0.0–1 and 50/0/0.0–3. Four formulations with
the partial replacement of the carbon black using a silica-
organosilane coupling agent system were examined (varying the
processing conditions and the organosilane content): 35/15/1.5–
1, 35/15/1.5–3, 35/15/3.0–3, and 35/15/0.0–3. One formulation
with the total replacement of the carbon black by silica 0/50/
0.0–3 was examined, and one formulation varying the amount
of sulfur to use the same amount as the standard formulation
(considering the sulfur present in the organosilane) 35/15/3.0–3
(-S) was examined. In the last case, (-S) indicates that the sam-
ple had a reduced sulfur content.
Curing Properties and Mooney Viscosity
The cure characteristics were obtained using a moving die rhe-
ometer (MDR 2000—Alpha Technologies) at the vulcanization
temperature (150 8C), according to ASTM D5289. The scorch
time (ts2) was determined as the time needed to increase the
torque by 2 dN m, while the vulcanization time (t90) was the
time to reach 90% of the maximum torque.
The cure rate index (CRI) was determined by eq. (1):
100
CRI5 (1)
t90 2ts2
where CRI is the cure rate index (min21), ts2 is the scorch time
(min), and t90 is the optimal cure time (min).
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Table I. Composition of the Formulations

Codification of the compoundsa

Component content (phr) 50/0/0.0-n 35/15/1.5-n 35/15/3.0–3 35/15/0.0–3 0/50/0.0–3 35/15/3.0–3 (-S)
Natural rubber (NR) 34 34 34 34 34 34
Butadiene rubber (BR) 33 33 33 33 33 33
Styrene-butadiene rubber (SBR) 45.4 45.4 45.4 45.4 45.4 45.4
Carbon black 50 35 35 35 0 35
Silica 0 15 15 15 50 15
Silane (TESPT) 0 1.5 3.0 0.0 0.0 3.0
ZnO 5 5 5 5 5 5
Stearic acid 2 2 2 2 2 2
Sulfur 2 2 2 2 2 1.34
N-t-butyl-2-benzothiazylsulfenamide 1.2 1.2 1.2 1.2 1.2 1.2
(TBBS)
1,3-Diphenylguanidine (DPG) 0.15 0.15 0.15 0.15 0.15 0.15
a
phr of carbon black/phr of silica/phr of silane-number of processing steps; (-S) indicate the sample with reduction in the sulfur content.
n, number of processing steps (1 or 3).

The viscosity characteristics were obtained in a Mooney visco-
simeter (MV 2000—Alpha Technologies), using a large rotor
(ML) at 100 8C with a test time of 5 min and 1 min of preheat-
ing, according to ASTM D1646.
Characterization of the Compounds
The specimens for the physical–mechanical analyses were
obtained by compression molding at 150 8C with a pressure of
7.5 MPa in a Shultz PHS 15T electrically heated hydraulic press
using an optimum cure time (t90) determined by the MDR. The
physical (dispersion and density), chemical (swelling resistance),
mechanical (tensile and tear strength, hardness, abrasion loss,
resilience, and compression set), and dynamic mechanical prop-
erties were evaluated.
The analysis of the filler dispersion was performed on the cured
samples in a Dispergrader 1 (Alpha Technologies) using a mag-
nification of 1003, according to the ASTM D7723. This analysis
measures the macrodispersion of fillers in a rubber matrix by
quantifying the surface roughness of a freshly cut specimen
using an optical microscope in reflection mode. The method
focuses light at a 308 angle, and uses sensors to verify the
behavior of their reflection on the surface of the material tested.
The undispersed filler appears as white particles against a darker
background. Computer analysis of the image provides a quanti-
tative measure of the dispersion. In this study, Three scans of
different locations of the freshly cut surface were performed on
each formulation.
The morphology of the cryogenically-fractured samples was
evaluated by scanning electron microscopy (SEM) using a field
emission gun Tescan Mira 3 equipment at an acceleration of 15
kV. The samples were previously sputter-coated with gold to
increase their electric conductivity.
The absolute density test was performed using the hydrostatic
method with water as a solvent. This test was conducted in a
Wallace densimeter, based on the ASTM D297 standard. The
swelling resistance test was performed based on the ASTM D
3616 standard using three test specimens with dimensions of
approximately 1 3 1 3 2 mm. The oil contained in the samples
was previously extracted with acetone for 8 h. The initial weight
of the specimens was measured prior to immersing them in tol-
uene at 23 6 2 8C for 72 h. The swelling percentage was deter-
mined as the ratio between the mass of the swollen sample and
the initial mass of the sample.
For the tensile strength tests, dumbbell-shaped samples (Die C,
initial gage length of 33.0 mm) were cut from the molded
sheets according to the ASTM D412 standard. The experiment
was performed using a crosshead speed of 500 6 50 mm min21
on an Alpha Technologies instrument with a 5 kN load cell.
The tear strength test was carried out according to the ASTM D
624 standard using C-shaped test pieces (an un-nicked test piece
with a 908 angle on one side) using a crosshead speed of
500 6 50 mm min21 using the same equipment.
A Bareiss Shore A durometer was used to measure the hardness
according to the ASTM D2240 standard, using cylindrical speci-
mens (/ 5 30.0 mm, h 5 6.3 mm). Ten measurements were per-
formed at different positions on each specimen. The abrasion
resistance was measured using a Frank abrasion tester following
the DIN ISO 4649 method A. Cylindrical specimens
(/ 5 16.0 mm, h 5 6.0 mm) were subjected to a friction trajec-
tory of 40 m on an abrasive sheet with an applied force of 10 kN.
The resilience test was performed according to the ASTM D
7121 using cylindrical specimens (/ 5 40.0 mm, h 5 12.5 mm).
The percentage resilience, determined by a freely falling pendu-
lum hammer, is inversely proportional to the hysteretic energy
loss. The rebound resilience is determined by the ratio between
the apex height of the rebound and its initial height.
The compression set test was carried out according to the
ASTM D 395 (method B) and ASTM D 1349 standards. The
cylindrical specimens (/ 5 29.0 mm, h 5 12.5 mm) were

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Figure 2. Mooney viscosity and rheometric properties of the developed
compounds: maximum torque (MH) and minimum torque (ML).
compressed for 2 h at room temperature and then at 70 8C for
22 h. After 30 min at room temperature, the thickness of the
samples was measured.
All the tests described above were performed after 40 h of con-
ditioning at 23 6 2 8C and a relative humidity of 50% 6 5%.
Dynamic mechanical analyses (DMA) were performed using a
TA Instruments DMA Q 800. The tests were carried out with a
deformation of 0.06% and a frequency of 10 Hz over a temper-
ature range of 2100 8C to 100 8C and a heating rate of
2 8C min21. Rectangular test specimens (13.0 3 5.0 3
2.0 mm3) were used. By evaluating the amplitude of tan d at
specific temperatures (0 and 60 8C), it was possible to evaluate
the wet grip and rolling resistance, respectively.2,18
RESULTS AND DISCUSSION
Curing Properties and Mooney Viscosity
The Mooney viscosity and the curing characteristics are shown
in Figures 2 and 3.
Figure 3. Rheometric properties of the developed compounds: scorch
time (ts2), optimal cure time (t90), and cure rate index (CRI).
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The minimum torque (ML), a measure of stock viscosity, and
the Mooney viscosity tend to increase with the use of silica.
This behavior is mainly due to the strong interactions between
silica particles.1,19,20 Contrary to the carbon black, which exhib-
its a relatively low polar component, the siloxane and silanol
groups of the silica surface give rise to a polar and hydrophilic
filler, which reduces its interactions with the hydrophobic poly-
mer matrix.9,10,21–24 This promotes a high filler-filler interaction
that dominates in silica-filled compounds, thus leading to the
formation of silica networks and the associated difficulties in its
dispersion in nonpolar polymers.25 These values were reduced
in compounds with more than one processing step because of
the increased processing time, which can be related to the dis-
ruption in the filler agglomerates, ultimately resulting in a lower
viscosity.26
The maximum torque (MH) may be related to the crosslink
density of the compounds. The presence of high amounts of sil-
ica without a coupling agent in the compound (0/50/0.0–3) did
not contribute to the formation of crosslinks, as indicated by
the lower values of MH. Moreover, the effectiveness of the silica
as a reinforcing agent is limited in this case, as discussed below.
Compounds with 15 phr of silica have higher values of MH com-
pared to compounds that underwent similar processing but con-
tain only carbon black. This may be related to the chemical
structure of the organosilane added to these formulations
(TESPT). Because sulfur is contained in the structure, it may
lead to an increase in the crosslink density, and consequently, an
increase in the MH values.2,8 Furthermore, the presence of orga-
nosilane may promote the interaction between the rubber and fil-
ler, which plays a major role in the reinforcement of rubber.1,11
The compound containing a higher amount of TESPT (35/15/
3.0–3) exhibited a reduction in MH compared to 35/15/1.5–3,
likely because of a better distribution of the filler and a lower
amount of rubber occluded within the clusters, which resulted in
a smaller hydrodynamic effect.2,27 Furthermore, it is possible that
the better dispersion of the filler in the elastomeric matrix acted
as a physical barrier, increasing the spacing between the polymer
chains and resulting in a decrease in crosslink formation.
Comparing the processing steps for the compounds prepared
with carbon black (50/0/0.0–1 and 50/0/0.0–3), and the partial
replacement of carbon black by silica-organosilane (35/15/1.5–1
and 35/15/1.5–3), we observe a reduction in MH as the number
of processing steps increases. This behavior may be related to
the reduction in the size and number of agglomerates, as dis-
cussed above. Moreover, this may be related to the mastication
process when three steps of processing were performed, thus
decreasing the viscosity of rubber as a consequence of the
reduction in the molecular weight of the elastomer.28
Comparing the compounds with the same amount of sulfur
[35/15/0.0–3 and 35/15/3.0–3 (-S)], there was a slight increase
in MH for the compound that contained only elemental sulfur.
The compound that contained sulfur within the organosilane
molecule did not exhibit the same efficiency, which may have
occurred because the sulfur is not available in the same way as
it is in the elemental state. Furthermore, some of the organosi-
lane molecules may not have been broken, which makes the
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Figure 4. Scanning electron microscopy (SEM) micrographs of the developed compounds: (a) 50/0/0.0–1, (b) 50/0/0.0–3, (c) 35/15/1.5–1, (d) 35/15/1.5–
3, (e) 35/15/3.0–3, and (f) 35/15/0.0–3.
sulfur contained in the coupling agent molecule inactive. It is
worth noting that no reversion was observed in all the samples
analyzed for the test time considered.
It is widely known that the functional groups on the silica sur-
face tends to adsorb a significant amount of curing agents,
causing an increase in t90 and a decrease in the crosslinking
density of the compound.1,2,15,29,30 Compared to other com-
pounds, that containing silica as filler (0/50/0.0–3) exhibited a
lower scorch time (ts2) and an extremely high optimum cure
time (t90). This resulted in a much lower values of CRI, which
is a measure of the rate of vulcanization. In addition, its vulca-
nization curve (not shown here) indicated an incomplete curing
process, with a continuous increase of torque with time. The
explanation for this behavior is that the silica interacts with the
accelerators, thereby inactivating them.1,15,29,30 These effects
may be minimized through surface modification of the filler to
reduce the availability of silanol groups.2,11,21
The optimum cure time (t90) for the compounds containing the
combination of silica with the coupling agent was slightly
higher than the compounds developed with carbon black, which
exhibited a higher CRI. As discussed previously, this may be
related to the interaction between silica and the accelerators,
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which cause a delay in the curing rate. The compound 35/15/
0.0–3, which did not contain organosilane in the formulation,
also exhibited an increase in ts2 and t90, thus corroborating this
fact. The number of processing steps did not significantly affect
the curing time. The compound with lower elemental sulfur
content [35/15/3.0–3 (-S)] exhibited a similar behavior, with a
reduced vulcanization rate compared to that of compound 35/
15/3.0–3.
It is important to note that the higher CRI values are more
interesting from a technological point of view for products that
are obtained by compression molding. Therefore, it is possible
to perform some changes in the formulation by increasing the
amount of the curing agents to adjust the curing time for the
compounds containing silica.1,7
Physicochemical Properties
Morphology. The morphology of the samples was analyzed
qualitatively by SEM (Figure 4) and quantitatively by macrodis-
persion analysis (Table II and Figure 5). The morphology stud-
ies revealed that the number of processing steps was critical and
significantly improved the dispersion of both fillers, as evi-
denced by comparing SEM images for 50/0/0.0–1 and 50/0/0.0–
3, and for 35/15/1.5–1 and 35/15/1.5–3 [Figure 4(a–d),
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Table II. Dispersion and Density Values of the Developed Compounds

Compounds Dispersion (%) Density (g cm23)

50/0/0.0–1 57 6 2 1.114 6 0.002
50/0/0.0–3 95 6 1 1.113 6 0.001
35/15/1.5–1 57 6 1 1.155 6 0.001
35/15/1.5–3 89 6 3 1.152 6 0.001
35/15/3.0–3 99 6 1 1.119 6 0.002
35/15/0.0–3 79 6 7 1.114 6 0.002
0/50/0.0–3 89 6 5 1.127 6 0.003
35/15/3.0–3 (-S) 97 6 1 1.116 6 0.002

respectively]. The number and size of agglomerated structures

was reduced when more than one processing step was used due
to the increased processing time and shear forces that provide a
better dispersion of the fillers. The physical and mechanical
properties of the compounds are directly dependent on the dis-
persion of filler, since it provides higher specific area for the
interaction with the rubber matrix. These results were corrobo-
rated by the values of Table II.
The use of silane coupling agent did not significantly influenced
the dispersion of silica in a microscopic level, as can be
observed in SEM images [Figure 4(d-f)] and by the quantifica-
tion of dispersion in Table II. Therefore, the main role of silane
in this study was to improve the chemical compatibility between
silica and the polymer, while the processing steps were determi-
nant in the improvement of the dispersion and distribution of
fillers within the rubber matrices.
The compounds containing 50 phr of silica (0/50/0.0–3) and
the combination of carbon black/silica without organosilane
(35/15/0.0–3) exhibited a reduction in the dispersion values and
a high standard deviation. This result corroborates the fact that
the presence of high quantities of silica or the absence of a cou-
pling agent leads to a poor dispersion. Figure 5 illustrates differ-
ent levels of dispersion for two selected compounds from Table
II. In Figure 5(a), it is possible to observe a large number of
white particles, which is related to the agglomerated fillers pre-
sent in the rubber matrix and resulted in a poor dispersion
value (57% 6 1%). In Figure 5(b), only few particles are visible,
Figure 6. Swelling behavior of the developed compounds.
and this is related to a good dispersion of the fillers that
resulted in a value of 99% 6 1%.
Swelling Resistance. The swelling in an organic solvent is one
of the simplest methods of characterizing the structure of cross-
linked elastomers.31 Vulcanized rubber is insoluble in solvents
due to the presence of crosslinking. However, vulcanized rub-
bers can absorb liquids, resulting in an increase in their volume,
which is a phenomenon known as swelling resistance. Therefore,
the values obtained for a swelling resistance test (Figure 6) may
be related to the crosslink density. The lower the swelling is, the
higher the crosslink density of the sample will be.31
The presence of high amounts of silica (50 phr) did not con-
tribute to the formation of crosslinks, as can be seen for sample
0/50/0.0–3, which exhibited higher swelling. The poor disper-
sion of the silica and the adsorption of curatives (accelerators)
on its surface may lead to a decrease in the DM
(DM 5 MH–ML).15,27 The compound prepared with carbon
black/silica and without a coupling agent (35/15/0.0–3) exhib-
ited similar behavior, because the silica surface is free to adsorb
accelerators, thereby reducing its activity.

Figure 5. Optical micrographs of the developed compounds: (a) 35/15/1.5–1 (dispersion value 5 57% 6 1%) and (b) 35/15/3.0–3 (dispersion
value 5 99% 6 1%).

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Table III. Tear Strength, Hardness, Abrasion Loss, Resilience, and Compression Set Properties of the Developed Compounds

Tear strength Hardness Abrasion loss Resilience Compression

Compounds (kN m21) (Shore A) (mm3 40 m21) (%) set (%)
50/0/0.0–1 42.2 6 2.4 66 6 1 74 6 4 55 6 0 23.4 6 0.2
50/0/0.0–3 39.6 6 4.5 62 6 1 71 6 3 55 6 0 24.0 60.8
35/15/1.5–1 49.2 6 2.1 69 6 1 56 6 5 49 6 0 18.0 6 0.5
35/15/1.5–3 44.5 6 1.6 65 6 1 63 6 4 52 6 1 20.8 6 0.0
35/15/3.0–3 43.2 6 2.1 61 6 1 71 6 5 59 6 0 20.1 6 0.4
35/15/0.0–3 41.2 6 4.0 57 6 0 90 6 4 54 6 4 21.6 6 0.4
0/50/0.0–3 39.3 6 4.4 39 6 1 226 6 18 49 6 0 55.7 6 1.9
35/15/3.0–3 (-S) 42.2 6 2.4 58 6 1 95 6 4 53 6 1 28.1 6 0.4

The compound containing 3 phr of organosilane (35/15/3.0–3)
exhibited higher swelling compared to the compound with 1.5
phr. This result can be related to the better distribution of the
filler (higher dispersion values) and the lower amount of rubber
occluded within the clusters, which resulted in a smaller hydro-
dynamic effect.2
Comparing the results of compounds 35/15/3.0–3 and 35/15/
3.0–3 (-S), the latter exhibited higher swelling because of the
smaller amount of sulfur that reacted and promoted the cross-
linking. The swelling test demonstrated the lower crosslink den-
sity of this sample.
The compounds prepared with the combination of carbon black/
silica and organosilane exhibited similar or higher values com-
pared to the compounds containing only carbon black with simi-
lar processing. This may be related to the chemical structure of
the TESPT, because it promotes a better affinity between the silica
and elastomer and contributes to the increase in the crosslink
density.2,8 The compound prepared without the coupling agent
(35/15/0.0–3) exhibited unsatisfactory results because the nature
of the silica surface chemistry resulted in small amounts of effec-
tively immobilized rubber.26 This demonstrates the importance of
this coupling agent for compounds containing silica.

Density. Table II shows the absolute density values. The densities Similar results were found in the literature. Furtado et al.8
of the formulations containing silica were slightly higher because of observed an improvement in the tensile properties with the use
the higher density of this filler. This can be observed for com- of organosilane coupling agent and attributed this behavior to
pounds 50/0/0.0–1 and 50/0/0.0–3, compared to formulations 35/ two main factors: improved polymer-filler interaction and
15/1.5–1 and 35/15/1.5–3, respectively. The number of processing increased crosslink density because the organosilane contained
steps did not significantly influence the density of the compounds. sulfur. Ismail and Chia19 attributed the improvement in these
properties not only to the variation in the amount of crosslink
The density values may be related to the swelling resistance density, but also to the better dispersion of the silica in the elas-
results. The higher crosslink density (lower swelling) reflects a tomeric matrix.
lower free volume, because the chains have more connections
between them. This results in an increased density. This result is Considering the processing steps and comparing compounds
evident when comparing compounds 35/15/1.5–3 and 35/15/ 50/0/0.0–1 and 50/0/0.0–3 (carbon black processed one and
3.0–3, for which the increase in the organosilane content three times) with 35/15/1.5–1 and 35/15/1.5–3 (silica processed
resulted in a lower crosslink density and, consequently, a lower one and three times with the same amount of organosilane), we
density. For compounds with the same sulfur content that
exhibited similar swelling, the absolute density values showed
no significant variation.
Mechanical Properties
The mechanical behavior of elastomers depends strongly on the
crosslink density.20 However, these properties are also affected
by the type of crosslinking, the type of polymer, and the type
and amount of filler, among other factors.32 Table III and Figure
7 show the mechanical characterization results.
In general, we observe that the characteristics of tensile strength,
elongation at break, and modulus at 300% elongation are related
to the results obtained for MH, hardness, swelling, and conse-
quently, the crosslink density.20 The compound containing high
amounts of silica in the formulation (0/50/0.0–3) exhibited a
higher elongation and lower tensile strength and 300% modulus
values. This indicates incomplete vulcanization in this com- Figure 7. Tensile properties of the developed compounds: tensile strength,
pound, with the samples containing a certain degree of plasticity. 300% modulus, and elongation at break.

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observe that the tensile properties are similar or better when

more than one processing step was performed. This result cor-
roborates the filler dispersion results in the elastomeric matrix
promoted by the processing in three stages, which affected the
mechanical properties positively.
Comparing the compounds with different organosilane contents
(1.5 and 3.0 phr—35/15/1.5–3 and 35/15/3.0–3), no significant
variation in the tensile properties was noticed. For the com-
pound without a coupling agent, inferior properties were
obtained because of the decreased crosslink density, as previ-
ously discussed.
It is worth noting that in the compounds prepared with differ-
ent sulfur content [35/15/3.0–3 and 35/15/3.0–3 (-S)], the elon-
gation at break values were higher for the compound with the
lower sulfur content, whereas the tensile strength and 300%
modulus decreased. This result highlights the influence of the
crosslink density on the mechanical properties of the elasto-
meric compounds, thus corroborating the results obtained for
the swelling resistance.
Considering the tear strength results, the compounds showed
no significant variation between them, indicating that the
changes performed in the formulations and the processing steps
did not affect this property.
It is noted that the hardness values behave similarly to MH and,
consequently, the crosslink density. Similar results were found
by Furtado et al.8 and Ansarifar et al.1
The abrasion loss is an important characteristic for tire treads,
because it is an indicative of the wear and consequently deter-
mines the life cycle of the tire. The abrasion values are also
directly related to MH, because higher values of MH correspond
to a higher crosslink density and stiffness; these characteristics
are reflected in lower values of abrasion loss. The use of the
combination carbon black/silica and organosilane reduced the
abrasion loss, thereby reducing wear and increasing the durabil-
ity of the compound.
The resilience is related to the energy returned by the material
after an applied deformation, i.e., lower values of resilience
indicate a greater amount of energy dissipated into heat. The
resilience values did not exhibited significant changes compared
to the standard sample. This finding indicates that the energies
absorbed by the materials were similar. The use of organosilane
coupling agents tended to promote an increase in the resilience,
indicating more flexible molecular chains.2,33 This affirmation
was confirmed in this work by using 3 phr of TESPT (35/15/
3.0–3), which exhibited the best result. In this compound, the
energy absorbed by the rubber and transformed into heat was
lower, which is interesting for use in tire treads and may be
related to the increased interaction of silica and the elastomeric
matrix.
The samples containing silica and organosilane exhibited a
decrease in the compression set property. This is an interesting
result and indicates an improved elastic recovery of the matrix.
For sample 0/50/0.0–3, the values were higher than 50%, indi-
cating a high deformation and low elastic recovery. This
Figure 8. Dynamic mechanical analysis results for the developed com-
pounds: wet grip and rolling resistance. The values of the standard com-
pound (50/0/0.0–1) were considered equal to zero.
confirms the previous results obtained for an incomplete cure
of the material.
Dynamic Mechanical Properties
A better description of the viscoelastic behavior of the elasto-
meric compounds was obtained by analyzing the tan d values
(Figure 8) from a DMA. A literature search shows that cyclical
deformations of the tire tread compounds due to rotation and
braking can be approximated to a process with a constant
power supply but using different temperatures and frequen-
cies.2,18,34 It is well known that the hysteresis of tread compo-
sites, characterized by tan d at 60 8C, is a key parameter that
exhibits a good correlation with the tire rolling resistance.9 Con-
sequently, the interest is for lower values of tan d at 60 8C,
which correspond to the better performance of the compound.
In addition, the value of tan d at 0 8C is related to the high-
frequency nature of the dynamic strain involved in the skid
process. Therefore, the higher the value of tan d at 0 8C is, the
better the property will be.35
The compounds using 1.5 phr of organosilane exhibited unsatis-
factory results. It is possible that with the lower coupling agent
content, the filler did not interact sufficiently with the polymer.
This fact was corroborated by the increase in the organosilane
content in the compound 35/15/3.0–3, where the rolling resis-
tance decreased by 10% compared to the standard compound,
whereas the wet grip increased by 18.5%. This can be related to
the higher dispersion and the stronger interaction of the filler
with the rubber matrix by the increased content amount of
organosilane, as already discussed in the physico-mechanical
analysis. These results are related to higher fuel economy and
driving security, respectively.
The compound 50/0/0.0–3 also exhibited interesting results. As
observed in SEM image [Figure 4(b)], the three processing steps
led to a better dispersion of carbon black. Consequently, the
dynamic properties of the compounds were improved.

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ARTICLE WILEYONLINELIBRARY.COM/APP
Therefore, for the systems that exhibited a good compatibility
between the rubber and the filler (as with the use of carbon
black), the obtained morphology is dependent only on the opti-
mization of processing conditions. In the systems with a limited
compatibility, such as rubber-silica, the use of a coupling agent
together with the processing conditions is determinant in the
improvement of the dynamic response of the compounds. The
use of three processing steps allows the number and size of the
agglomerates to decrease, while the use of organosilane allows
the interaction of the silica with the rubber chains.
CONCLUSIONS
This study investigated the effect of replacing carbon black with
a silica-organosilane coupling agent system and altering the
number of processing steps on the cure and mechanical proper-
ties, rolling resistance, and wet grip of truck tire treads.
The use of silica increases the viscosity of the compounds. How-
ever, with the combined use of silica-organosilane (3.0 phr) and
carbon black, and a three-step process, it is possible to reduce
the viscosity by 37%, comparing to the standard compound.
Regarding the rheometric properties, the use of silica-
organosilane increased the vulcanization time by 2 and 3 min
compared to compounds that contained only carbon black.
The swelling resistance, which is related to the crosslink density,
corroborated the rheometric and mechanical results, where a
higher swelling resistance was associated with a stiffer com-
pound, with higher MH and 300% modulus. For the compound
with 15 phr of silica, 3 phr of organosilane, and three process-
ing steps, the rolling resistance decreased by 10% compared to
the standard compound, and the wet grip increased by 18.5%.
Furthermore, this compound exhibited similar or better
mechanical results than the standard compound. Therefore, the
great performance of the compounds can be directly related to
two factors: the good filler dispersion, provided by the process-
ing in three steps, and the strong rubber-filler interaction
observed when using carbon black, or promoted by the presence
of the organosilane molecule in the partial replacement of car-
bon black by silica.
ACKNOWLEDGMENTS
The authors thank CAPES for their financial support, Laborat
orio
Central de Microscopia Professor Israel Baumvol (FINEP
01.13.0359–00), and to Borrachas Vipal S.A. for providing the
materials and equipment to perform this work.
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