RCT, Bhowmick Et Al.

EFFECT OF SILICA LOADING AND COUPLING AGENT ON WEAR AND
FATIGUE PROPERTIES OF A TREAD COMPOUND
HARINI SRIDHARAN,1 ABHILASH GUHA,2 SANJAY BHATTACHARYYA,1 ANIL K. BHOWMICK,2,*

R. MUKHOPADHYAY1
Downloaded from http://meridian.allenpress.com/rct/article-pdf/92/2/326/2443343/rct_18_81570.pdf by Rhythm RCAT Access, Anil Bhowmick on 16 September 2022
1
HARI SHANKAR SINGHANIA ELASTOMER AND TYRE RESEARCH INSTITUTE, MYSURU, 570016, INDIA
2
RUBBER TECHNOLOGY CENTER, INDIAN INSTITUTE OF TECHNOLOGY, KHARAGPUR, 721302, INDIA
RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 92, No. 2, pp. 326–349 (2019)
ABSTRACT
The effects of highly dispersible silica and the nature of silane in a tire tread cap compound were studied with particular
reference to dynamic mechanical properties, abrasion resistance, side force coefficient, and fatigue crack growth (FCG)
properties. The rubber matrix chosen was a blend of solution grade styrene butadiene rubber and polybutadiene rubber. Six
different loadings of silica were used. Bistriethoxysilylpropyltetrasulfide (S) was taken as the coupling agent. In addition, the
potential of two new generation silanes, 3-octanoylthio-1-propyltriethoxysilane (N) and 3-mercaptopropyl-di [tridecan-1-
oxy-13-penta ethyleneoxideethoxysilane] (V) was also explored at 70 phr silica loading. Optimum properties were obtained
at 50 phr loading of silica (S50). The tensile moduli for the compounds increased sharply with silica loading. Higher values of
tan d, indicating higher hysteresis, were obtained in compounds containing higher filler dosage. However, enhanced abrasion
resistance and side force coefficient were observed at higher loadings of silica due to an increased reinforcement
phenomenon. The crack growth exponent (b) was lowest for S50. Among the silanes tested, V showed a 22% drop in tan d at
70 8C, 11% drop in abrasion loss, and an increase in FCG rate. N exhibited a lower FCG rate as compared with the silane S.
[doi:10.5254/rct.18.81570]
INTRODUCTION
A large amount of silica is used by the tire industry to reduce the rolling resistance of tires. As
compared with carbon black (CB), the addition of silica results in major property changes:
improvement in vulcanizate properties, such as tensile strength and elongation at break, and
improvement in dynamic properties and tear strength accompanied by certain process difficulties,
such as increase in viscosity, agglomeration due to strong polar interactions among the silica
particles, and deactivation of accelerator system due to absorption of moisture on the hydrophilic
silica surface.1–4 These difficulties, which mainly arise because of a difference in polarity between
rubber and silica, are now overcome by the addition of bis [3-triethoxysilylpropyl tetrasulfane]
(TESPT) as silane, which aids in silica–rubber interaction by reacting chemically with silica and
establishing a bond with rubber. The triethoxysilyl groups of the silane react with the silanol groups
on the silica surface, and the rubber-reactive group on the silane (sulfur) forms a bond with the
rubber during vulcanization.5,6 Both the reactions need to be carried out under controlled conditions
to achieve the desired results. This introduces a double network in the matrix; silica rubber bonds
via silane bridges and sulfur bonds due to vulcanization. Solution grade styrene butadiene rubber (s-
SBR) is used to enhance particular properties of the compound such as rolling resistance and filler
dispersion by controlling its microstructure, molecular weight distribution, and styrene sequence,
which otherwise cannot be achieved using conventional polymers.7 It is now established that the
silane coupling reaction occurs efficiently in silica–rubber technology when the vinyl content of the
participating s-SBR lies in the range of 20–70%.8 But the lower rolling resistance calls for reduced
mixing stress, which can be satisfied using a highly dispersible grade of silica (HD silica) to achieve
desirable vulcanizate properties.
*Corresponding author. Email: anilkb@rtc.iitkgp.ernet.in
326
EFFECT OF SILICA COUPLING AGENT ON TREAD WEAR 327
The silica loading plays a role in altering the cure characteristics of the compound by reacting
with the compounding ingredients.9 Silanes are also known to modify the number and nature of
chemical cross-links in the matrix;10 new generation silanes are expected to be different from the
conventional silanes.
The physical properties are altered due to the dispersion of silica in rubber matrix and nature of
polymer–filler interaction.11 The dynamic properties of a compound filled with silica and silane
vary from those of CB12, since the stability of the covalent silica polymer network results in a lower
rate of breaking and reformation of the silica–polymer bonds compared with the CB–polymer
network during a deformation cycle, which results in a decrease of loss modulus.13,14 A low value of
loss modulus together with a high value of storage modulus results in a drop in tan d, which then
subsequently affects the fatigue15 and abrasion properties. The tread surface of a tire experiences
cyclic loading during the service life of a tire, that too at a very high frequency. Fatigue loading thus
has major importance in the study of fracture of tread compounds. The use of fracture mechanics
approach, based on the strain energy release rate, is applied to account for the crack growth and
fatigue properties of vulcanized rubbers.15 Fatigue failure occurs much before tensile failure does,
since the cracks under static load are under uniform stress, which stabilizes, whereas cracks cannot
completely relax under fatigue loading. The factors that affect the fatigue life of rubber are: type of
rubber, filler and curing package, environmental conditions (temperature, ozone etc.), constitutive
behavior (strain crystallization, viscoelasticity, and hysteresis) and mechanical loading history
(frequency, waveform etc.).15 The work by Rivlin and Thomas16 set the foundation of fracture
mechanics of rubber. The controlling parameter in the propagation of cracks in an elastomeric
matrix is the strain energy release rate.17–19 Tearing energy is the elastic strain energy lost by the
elastomer per unit area of new surface formed or the energy required to form a unit area of crack
surface. Lake20 has developed a fracture mechanics approach for predicting rubber fatigue life
based on tearing energy. In Eq. 1, the number of cycles taken (n) for a crack to grow from length c1 to
c2 is given. f(T) is a function of tearing energy, which depends on the sample shape and deformation
type. Equation 2 is the tearing energy relation for an edge crack.
Zc2
n¼ dc=f ðTÞ ð1Þ
c1
T ¼ 2kcW ð2Þ
In Eq. 2, W is strain energy density, c is the crack length, and k is a slowly varying function of
strain.
There exists a threshold tearing energy for every elastomer when the crack growth
characteristics are primarily governed by molecular parameters. Young21 explained that blending
of different polymers can control the power law exponent on the energy release rate. Beatty22
examined the effect of cyclic fatigue on rubber blends, which has shown that the blends exhibited
superior fatigue properties, as compared with the individual polymer, e.g., blends of SBR and
polybutadiene rubber (BR) showed that fatigue resistance of the blend continuously improved with
increasing amounts of BR, which was also reported by Ghosh et al.17 Fillers play a vital role in
deciding the fatigue properties of rubber blends.15,18,23 The effect of filler on the fatigue properties
includes increase in effective initial flaw size due to filler–filler agglomeration, inhomogeneity of
the rubber–filler composite resulting in crack tip blunting and deviation, and pronounced changes in
stiffness and hysteresis properties induced by fillers. Addition of silica as filler leads to a strong
increase of the tear strength and fracture toughness of vulcanizates. This is attributed to strong filler
328 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 92, No. 2, pp. 326–349 (2019)
networking of silica, which arises because of its polar nature and ability to form hydrogen bonds.
Fillers also change the size of crack precursors within the compound matrix, which subsequently
leads to crack initiation and then propagation. A higher loading of filler increases the agglomerate
size, which subsequently increases the effective initial flaw size.15 The effect of crack precursor size
on fatigue crack growth (FCG) was studied by Mars et al.24,25
Reincke et al.26 emphasized the effect of silica and layered silicate on the polymer–filler
interaction, which in turn affects the fracture behavior of rubber vulcanizates. Elastomers with the
highest loadings of silica have the strongest crack resistance. Ansarifar et al.27 showed that cyclic
fatigue life and stored energy varied with different dosage of silane coupling agent for silica filled
rubber matrix, even though their results showed a large scatter. The influence of increasing amount
of TESPT on the cyclic fatigue life of passenger car tire tread compounds was studied, and inclusion
of silane in the silica filler compounds initially had a detrimental effect on the fatigue crack growth
properties, and there existed an optimum dosage of silane (7.5 phr) that gave the best fatigue life of
the compound.28
Wear of tires is a common phenomenon that mainly takes place when tires come in contact with
the road patch during rolling or sliding, and this mainly correlates with the peeling off of rubber
debris due of sharp asperities on rough roads. El-Tayeb and Nasir29 stated that abrasion of rubber
involves the removal of small particles from the surface (1–5 lm), which leaves behind pits,
subsequently leading to removal of large particles (.5 lm) and is a manifestation of localized
stresses in rubber. FCG and mechanical strength play a major role in determining the abrasion
properties of a tread compound, since tire abrasion is a classic cyclic stress loading scenario, which
leads to a temperature rise in the tire, and the crack growth increases. It is also a temperature
dependent phenomena.30,31 The elastic energy stored in every point in a tire is converted to heat
owing to the viscoelastic nature of the tire, which aids the crack growth occurring from the stress
initiators within a tire. The abraded surfaces were studied by Schallamach,32 who explained the
formation of ridges perpendicular to the direction of abrasion. Grosch33 reviewed the abrasion of
rubber. Bhowmick34 used scanning electron microscopy (SEM) to explore the ridges formed and
related these to coalescence of particles. Bhowmick also studied the surfaces of gum and filled NR
vulcanizates abraded to different degrees. Thavamani and Bhowmick35 studied the mechanism of
wear of tank track pads composed of NR and hydrogenated nitrile rubber (HNBR) on different
rocks and investigated the pattern abrasion of the fractured surface.
The properties of silica filler along with different silanes in NR6,27–28,36 and SBR matrix have
been studied by many authors.9,19 Passenger car radial tires extensively employ s-SBR and BR
blend in their tread cap compound owing to its superior traction and rolling resistance properties. A
correlation between abrasion and FCG properties of a s-SBR and BR blend has not been established
to date. Hence, this paper gives us a deeper insight into this topic. The perennially increasing
demands of low volatile organic compounds (VOC) emissions and rolling resistance have led to the
development of new generation silanes such as N and V. Since they have a markedly different
chemical structure, they provide very diverse properties as compared with the conventional S silane.
Therefore, the change in mechanical and viscoelastic properties is explored in this study with a
special focus on FCG and abrasion characteristics in TFA and LAT100, respectively. A correlation
was attempted among the viscoelastic properties, FCG, side force coefficient, and abrasion data.
EXPERIMENTAL
MATERIALS
All the mixing ingredients were used as obtained. s-SBR with a styrene content of 35.51%,
vinyl content of 30.81%, ML (1þ4) at 100 8C 81, and oil content of 37.5 phr was procured from
Asahi Kasai, Japan. Polybutadiene (Neodium catalyzed) with 96% cis content was supplied by
Lanxess International (Pittsburg, PA, USA). Other compounding ingredients used were highly
dispersible silica having a nitrogen surface area of 175 m2/g and SiO2 content of 97% procured from
Insilco India Pvt. Ltd. (Evonik Industries, Wesseling, Germany), N339 carbon black (Phillips
Carbon Black Ltd., India), oil of low polycyclic aromatic (PCA) grade (Raj Petro, Chennai, India),
zinc oxide (rubber grade; Zinc-o-India, India), stearic acid (Godrej Soap Ltd., India), silane
coupling agents: [1] bis (triethoxysilylpropyl) tetrasulfide having 50% carbon black (Evonik
GmbH); [2] 3-octanoylthio-1-propyltriethoxysilane (Momentive Performance Materials, Water-
ford, NY, USA); [3] 3-mercaptopropyl-di (tridecan-1-oxy-13-penta (ethyleneoxide)) ethoxysilane
(Evonik GmbH), N-phenyl-N 0 -(1,3-dimethylbutyl) p-phenylene-diamine (6PPD; National Organ-
ic Chemicals Industries Ltd., India), N,N 0 -diphenyl-p-phenylenediamine (DPPD; Acmechem India
Pvt. Ltd., India), micro crystalline wax (Gujrat Paraffins Pvt. Ltd., India), soluble sulfur (Jain
Chemicals Ltd., India), N-cyclohexylbenzothiazolsulfenamide (CBS; National Organic Chemi-
cals, India Ltd., India), and diphenyl guanidine (DPG; National Organic Chemicals, India Ltd.,
India) for the compound preparation.
HD Silica and Silane Coupling Agent. — The highly dispersible silica used had a white
colored powdery appearance, was odorless, and had a free flowing tendency with the following
properties: pH, 5–7; surface area, 175 m2/g; density, 2.04 g/cm3; SiO2 content of 97%; volatile
loss on ignition, 5% (maximum). The surface area [Brunauer–Emmett–Teller (BET) method was
in accordance with ASTM D 6556] and heat loss characteristics (ASTM D 1509) were measured
in the laboratory, and remaining characteristic parameters were obtained from the supplier’s
catalogue.
The silane coupling agents used include bis (triethoxysilylpropyl) tetrasulfide [S]; 3-
octanoylthio-1-propyltriethoxysilane [N] and 3-mercaptopropyl-di (tridecan-1-oxy-13-penta
(ethyleneoxide)) ethoxysilane [V]. The percentage sulfur content of each silane (S, 11.5%; N,
6.5%; and V, 6.3%) was measured in accordance to ASTM D 3280, and the residual ash content was
found ranging between 11 and 13% for respective silanes and was tested in the laboratory following
ASTM D 6740. Structure of various silanes is given in Scheme 1.
FORMULATIONS AND MIXING
Formulation. — The basic formulations used with different silica loadings are given in Table I,
and those having variation of different silane coupling agents are given in Table II.
Mixing. — The mixing was carried out in a 1.5 L capacity Laboratory Banbury mixer (Stewart
Bolling, Hudson, OH, USA) having a two wing tangential rotor. The mixing of the compounds was
done in three stages. The mixing sequence is given in Table III.
Mixing in stage I was done by setting the temperature control unit (TCU) at 90 8C and
variable rotor speed starting at 60 rpm. The rubbers were added at 0 s. One third of dry HD silica
was added at 30 s followed by CB and half of oil when the temperature of mixing reached 120 8C.
The judicious use of CB was done here to reduce the contact electrification generated by silica
fillers and also to reduce the scattering of the lump while dumping. A problem encountered during
the addition of silica, CB, and oil during first stage of mixing was the tendency of silica to escape
the downward movement of the ram due to its fluffy nature. With precise care the ram was swiped
up and down to ensure that all the silica reached the mixing chamber. After a total of 7 min of
mixing, the master batch was dumped. The display dump temperature was found to be between
145 and 150 8C.
Mixing in stage II was carried out by feeding the stage I mixed compound into the Banbury
mixer. Mixing temperature, mixing time, and condensation of ethanol were the factors that needed
precise control for the interaction of the surface hydroxyl groups of silica to the rubber matrix during
SCHEME 1. — Structure of various silanes used.
the silanization reaction. The TCU was kept at 90 8C and the rotor speed at 60 rpm. Mixing was done
for 360 s and the silanization reaction was carried out for 120 s. The dump temperature was
measured by a pyrometer and was found to be in the range of 145 to 150 8C.
The curing package, viz. accelerators and sulfur, was added in the third and final mixing step on
the same Banbury mixer where the temperature controller unit was kept at 70 8C and the rotor speed
at 30 rpm. The stage II compound along with the curative package was added at 0 s, and the batch
was dumped after 3 min. The discharge temperature of the batch was found to be between 95 and 97
8C.
FILLER DISPERSION STUDY
RPA 2000 from Alpha Technologies (Bellingham, WA, USA) was used to study the
temperature dependent nonlinear strain dependence of elastic moduli (Payne effect). Measurement
of shear storage modulus (G 0 ) at low and high strain amplitudes was done following certain test
configurations:
1. In order to reduce the built in stresses developed as the instrument was closed, preheating
of sample was done at 0.01% strain and 1.67 Hz frequency for 2 min at 50 8C.
2. At 50 8C, strain sweep was conducted from 0.01 to 100% strain.
The value of the difference of shear storage modulus between high strain (100%) and low strain
(0.01%) was expressed as DG 0 .
TABLE I
FORMULATION OF COMPOUNDS USING BLEND OF S-SBR AND BR AT
VARIOUS SILICA LOADINGS
Ingredients, phra S0 S30 S50 S60 S70
s-SBR 75 75 75 75 75
BR 25 25 25 25 25
HD silica — 30 50 60 70
Carbon blackb 5 5 5 5 5
Sc — 6 10 12 14
Oil 7 7 7 7 7
Zinc oxide 2.5 2.5 2.5 2.5 2.5
Stearic acid 1 1 1 1 1
6PPDd 1 1 1 1 1
DPPDe 1 1 1 1 1
Microcrystalline wax 1.5 1.5 1.5 1.5 1.5
Sulfur 1.8 1.8 1.8 1.8 1.8
CBSf 1.5 1.5 1.5 1.5 1.5
DPGg 1 1 1 1 1
a
phr, parts per hundred rubber by weight.
b
CB grade used is N339 to prevent static electric charges, which generate as a
result of non-conductivity of silica when present in high amounts used for
dynamic applications; a minimal amount of carbon black is maintained in the
formulation.
c
S is a blend of 50 parts carbon black and 50 parts TESPT.
d
N-phenyl-N 0 -(1,3-dimethylbutyl) p-phenylene-diamine.
e
N,N 0 -diphenyl-p-phenylenediamine.
f
N-cyclohexylbenzothiazolsulfenamide.
g
Diphenyl guanidine.
CURE CHARACTERISTICS
The cure characteristics of the rubber compound were tested using an RPA 2000 from Alpha
Technologies at 160 8C for 30 min in accordance with ASTM D 6204. The cure rate index is given
by the following formula.
100
CureRateIndex ¼ ð3Þ
tc90 ts2
tc90 and ts2 in Eq. 3 are time taken to achieve 90% of maximum torque and 2 units above the
minimum torque, respectively. The D Torque values obtained from the rheometric curve indicate
the degree of cross-linking. The delta torque is calculated by the following equation.
DTorque ¼ MH ML ð4Þ
where MH and ML are the maximum torque and minimum torque obtained from the rheometric
curve, respectively.
TENSILE PROPERTIES
The test samples (green rubber compounds) for testing physical properties were cured in
accordance with ASTM D 3182 in an electrically heated hydraulic curing press from Hind
TABLE II
FORMULATION OF COMPOUNDS AT 70 PHR SILICA LOADING WITH DIFFERENT
SILANE COUPLING AGENTS
Ingredients, phr S70 S70-N S70-V
s-SBR 75 75 75
BR 25 25 25
Zinc oxide 4 4 4
Stearic acid 2 2 2
Carbon black 5 5 5
HD silica 70 70 70
S 14 — —
N — 7
V — — 7
Oil 6 6 6
6PPD 1 1 1
DPPD 1 1 1
Microcrystalline wax 1.5 1.5 1.5
Sulfur 1.8 1.8 1.8
CBS 1.5 1.5 1.5
DPG 1 1 1
Hydraulics using a compression molding technique at 150 kg/cm2 molding pressure. Tensile slabs
were molded at 160 8C for twice tc90. Tensile properties were determined in accordance with ASTM
D 412 using a Zwick UTM 1445 from Germany and Die C dumbbell-shaped specimens obtained
from punching vulcanized sheets. Hardness of the compounds was measured following ASTM D
2240 using a Shore A Durometer from Prolific Engineers.
TABLE III
MIXING SEQUENCE IN STAGE I, STAGE II, AND FINAL STAGE
Time, s Temperature, 8C Actions
Mixing action: Master I

0 51 Add rubber (s-SBR and BR)
30 67 Add one-third of dry silica
110 110 Add carbon black (N330) and half of oil (Low PCA)
370 135 Ram sweep for 30 s
490 150 Dump Master I
Mixing action: Master II
0 46 Master I þ two-thirds of HD silica þ
(ZnO/stearic acid/S or N or V/6PPD/DPPD/MC wax)
110 90 Ram sweep (30 s)
250 120 30 g of silica and remaining half of oil (low PCA)
400 135 Ram sweep (30 s)
490 150 Dump master II
Mixing action: Final
0 44 Master II þ curative package (sulfur/CBS/DPG)
220 100 Mix for 3 min and dump
TABLE IV
TEST CONDITIONS FOR LAT 100
Test condition Values
Disk type 60 corundum

Speed, km/h 15
Load, N 75
Slip angle, 8 5
Powder dosage, % 5
Distance, meter 250
SWELLING TEST
A swelling test was performed on vulcanizate weighing ~0.2–0.3 g in toluene for 48 h at 25 8C,
and the swelling index was calculated from the ratio of swollen weight divided by the initial weight.
DYNAMIC MECHANICAL PROPERTIES
Dynamic mechanical testing was done using a Metravib Viscoanalyzer VA 4000, R.D.S.,
Limonest, France, in tension compression mode to determine the storage modulus (E 0 ), loss
modulus (E 00 ), and tan d at 30, 70, and 100 8C. The tests were performed at 5% strain and 11 Hz
frequency, and the sample thickness was 2.0 6 0.2 mm. The glass transition temperature (Tg) was
measured in the same equipment under tension–compression mode in the temperature range from
70 to 70 8C at 0.1% strain at 11 Hz.
ABRASION CHARACTERISTICS
Abrasion properties were tested using a Laboratory Abrasion Tester (LAT 100) from VMI,
Epe, Holland. The side force coefficient and abrasion loss were determined on a Corundum 60 type
disc and a powder mixture of aluminum oxide and magnesium oxide (2:1) was used to avoid the
formation of debris.
The experiments were conducted on a circular disk sample having an outer diameter (do) of 80
mm, an inner diameter (di ) of 35 mm, and a thickness (t) of 18 mm. The specimen wheels were
loaded pneumatically with the aid of compressed air, and the load was maintained up to 0.1 N
precision. The conditions followed for compound testing are given in Table IV.
FATIGUE CRACK GROWTH MEASUREMENT
The crack propagation rate of the compounds was determined by testing in pure shear mode at
different strain percentages in the tear and fatigue analyzer (TFA) from Coesfeld, Germany (Figure
1). The pure shear specimens for testing were cured at 160 8C for twice tc90. Three specimens with
notches on both sides were simultaneously analyzed at room temperature. The geometry of standard
pure shear test specimen was unstrained length l0 ¼ 15 mm, width ¼ 120 mm, and thickness ¼ 1.5
mm as given in Figure 2. Each pure shear specimen was notched with notch length a0 ¼ 21 mm on
either side. The test conditions followed the FCG experiments of the silica filled compounds and are
given in Table V.
The crack growth was measured with the help of a charge-coupled device camera, which
measured the crack length every 200 cycles. Images were captured when 20% of the maximum
stroke was attained by the linear drive. The crack length was half of contour length. This enabled the
FIG. 1. — Coesfeld tear and fatigue analyzer.
measurement of accurate crack growth rate even when the crack deviated from a straight path.37 The
tearing energy was calculated by the following equation.
0
]W
T¼ ð5Þ
]A l
FIG. 2. — Dimensions of pure shear sample for FCG testing in TFA.

TABLE V
TEST CONDITIONS FOR TFA
Test condition Values
Strain (%) 10, 15, 20, 25

Repeating frequency (Hz) 4
Pulse frequency (Hz) 10
Waveform Gaussian
where T is the tearing energy (N/mm), W 0 is the elastic strain energy, and A is the interfacial area of
the grown crack. The subscript l indicates that the measurement was done at constant displacement.
For pure shear specimens, the tearing energy is independent of crack length38 and is calculated by
Eq. 6. Since the sample geometry has a low height to width ratio, there is no edge effect close to the
crack tip. Thus, tearing energy does not depend on the crack length.
T ¼ Wl0 ð6Þ
l0 in Eq. 6 is the unstrained length (grip separation) of the sample and W is the strain energy per unit
volume in that region of the test piece that is in a state of pure shear. In the ranges of tearing energy
tested, the crack growth follows a power law.17,19
dC
¼ BT b ð7Þ
dN
B and b are constants characteristic of the region of crack growth. b is known as the crack growth
exponent and is dependent on the material used. A logarithmic plot of Eq. 7 is drawn for the variants.
RESULTS AND DISCUSSION

EFFECT OF SILICA LOADING AND TYPES OF SILANE ON FILLER DISPERSION, CURE CHARACTERISTICS,
AND MECHANICAL AND DYNAMIC PROPERTIES
The basic formulations used with various doses of silica and S as silane are given in Table I. S0
is the control compound. The amount of silica was gradually increased up to 70 phr in the
formulations. On analyzing the cure characteristics depicted in Table VI, the minimum torque
achieved at higher loadings of silica is significantly amplified as compared with lower loadings,
which indicates polymer–filler interaction. This was further supported by swelling data discussed
later. There exists a trend of decreasing cure rate with increasing silica loading. This is consistent
TABLE VI
DG 0 AND CURE CHARACTERISTICS WITH VARIOUS SILICA LOADINGS
S0 S30 S50 S60 S70
DG 0 , MPa 0.03 0.24 0.63 1.36 5.35

Minimum torque ML, dN m 0.86 1.90 2.57 2.97 5.08
Maximum torque MH, dN m 5.69 10.20 13.53 16.21 26.74
D Torque, dN m 4.83 8.3 10.96 13.24 21.66
ts2, min 2.6 4.3 3.6 2.8 1.6
tc90, min 3.9 7.1 8.6 10.2 12.9
Cure rate, min1 76.92 35.71 20.00 13.51 8.85
FIG. 3. — Variation in storage modulus (G 0 ) across a strain sweep at various silica loadings.
with the earlier findings by Ramier et al.,9 where they emphasized the polar nature of silica attracting
all the chemicals, such as zinc oxide, stearic acid, amine antioxidants, glycols, and accelerators,
which are also polar in nature. The strong adsorptive action forms a layer on the silica surface, which
results in a delay in the curing process. The adsorbed layer of chemical prevents the direct wetting
between the silica and rubber and reduces the extent of silica–rubber interactions. The increase in
silica loading also increases the acidity content in the compound, which reduces the rate of curing.
To minimize the absorption of the accelerator on the silica surface and to improve cure
characteristics, either glycols or amines are added into the rubber compounds. Diphenylguanidine
(DPG) is the commonly used amine for this purpose, which acts as a synergistic secondary
accelerator for sulfenamide accelerated sulfur vulcanization as well as a catalyst for silica–silane
silanization. However, the difference between MH and ML (delta torque) is proportional to the
degree of cross-linking reaction taking place, which increases on increasing the dose of silica,
despite slow curing.10
As stated by Payne and Whittaker,39 on addition of filler to any rubber matrix, it forms an
extensive network inside the rubber matrix and causes the mechanical behavior to become highly
nonlinear in nature. The rubber ‘‘trapped’’ within the filler network acts as a filler itself, thus
decreasing the effective volume of polymer in the matrix. Silica displays a higher hydrodynamic
effect as compared to CB due to the polarity of silanol functional groups on the silica surface.12 The
DG 0 values, which are representative of filler–filler flocculation, are thus higher for a silica filled
compound as compared with CB. DG 0 of the control compound, S0, is significantly lower than the
filled compounds due to the absence of filler (Figure 3 and Table VI). An increase in silica loading
from 0 to 70 phr is causing a concurrent increase in DG 0 values, which was also achieved by
Luginsland et al.40 This confirms the reaggregation tendency of silica at higher loadings. On
comparison with the experimental data by Luginsland, it can also be observed that the DG 0 of a s-
SBR/BR compound without silane is almost 5 times higher than a compound treated with a silane
coupling agent. This will be discussed later in detail.
Mechanical properties of silica filled compounds exhibit complete dependence on filler
loading variables as seen in Table VII. The moduli at 100% and 300% elongation along with the
TABLE VII
MODULI, TENSILE STRENGTH, ELONGATION AT BREAK AND HARDNESS WITH VARIOUS SILICA LOADINGS
S0 S30 S50 S60 S70
Modulus at 100%, MPa 0.6 1.2 1.8 2.2 3.8

Modulus at 300%, MPa — 5.5 8.4 10.7 15.3
Tensile strength, MPa 1.8 10.0 17.9 17.8 17.2
Elongation at break, % 279 426 509 431 326
Hardness, Shore A 32 48 55 61 65
Swelling index 3.83 2.91 2.55 2.37 2.27
tensile strength increased on increasing loading, but the elongation at break reduced at higher
loadings due to an increase in stiffness and cross-link density.12 The swelling index, which is a
measure of interaction between rubber and filler, decreases with concurrent increase in silica
loading. A similar study was conducted by Ray et al.,41 who deduced a model for polymer–filler
interactions at various extension ratios as seen in Eq. 8.
E
¼ aebU ð8Þ
E0
In Eq. 8, E and E0 are the moduli of filled and gum vulcanizate, respectively. U is volume
fraction of filler. The parameters a and b are strain level and temperature dependent constants.
Similar results are obtained in this experiment also (Figure 4 and Table VIII). As Eq. 8 suggests, an
increase in E/E0 is obtained with an increase in volume fraction of filler. E/E0 also increases with
increase in elongation due to a better polymer–filler interaction in silane-treated silica compound.
Fillers are known to drastically alter the elastic and viscous moduli of a rubber compound. As
studied by Wang,12 silica offers great advantages over CB in dynamic mechanical properties. His
work concludes that silica provides a better wet traction and lower rolling resistance as compared
with CB. From the application point of view of tires, repeated straining of the compound during
rotation and braking is similar to constant energy input across various temperatures and frequencies
and thus studying the change in these properties across a temperature sweep gives an accurate
understanding of the performance characteristics of a tire. Table IX represents the viscoelastic
properties of the compounds measured at 0, 30, and 70 8C. Payne and Whittaker39 studied the
variation of storage modulus with strain and temperature of compounds with variable CB loading.
FIG. 4. — Variation of E/E0 with filler volume fraction U.

TABLE VIII
VALUE OF CONSTANTS A AND B AT VARIOUS EXTENSION RATIOS
Extension ratio a b
0.05 0.95 0.22

0.2 1.49 7.18
0.5 1.02 6.07
1 1.05 7.10
2 1.13 8.92
3 1.08 10.25
Our findings in silica also coincided with theirs, i.e., elastic modulus (E 0 ) and viscous energy losses
(E 00 and tan d) are directly proportional to filler loading. S0 exhibited a very low elastic modulus and
viscoelastic energy losses compared with the filled compounds. The temperature dependence of
viscoelastic properties also stated a decrease in physisorption or chemisorption of the polymer
molecules on filler surface, which are responsible for viscoelastic properties. Raising temperature
reverses the molecular immobilization of the adsorbed molecules and has resulted in a decrease in
modulus.12 On following the trend of E 00 and tan d, an increase can be noticed with growing silica
loading. This correlates with the DG 0 trend obtained as seen in Figure 5, where an increase in tan d
leads to an increase in DG 0 . As studied by Wang,12 an increase in filler loading leads to a decrease in
tan d at lower temperatures, whereas the converse is true at higher temperatures. A similar trend has
been obtained at various silica loading as seen in Figure 6. A lower rubber fraction at lower
temperatures causes a decrease in energy dissipation, whereas higher filler loading causes an
increase in breaking and reformation of aggregates.
The next study was conducted to investigate the impact of the new generation silanes such as N
and V on high loading of silica and compare their properties with those of S. S70 was considered as
the reference formulation, and the coupling agent S was replaced by N and V silanes in the same
proportion (see Table II).
The cure characteristics mentioned in Table X clearly throw light upon the differences in
DTorque and cure rate among the silanes. Ko et al.10 concluded that the bifunctionality of S leads it
to facilitate a higher number of cross-links as compared with compounds containing a new
FIG. 5. — Relationship between DG 0 and tan d measured at 50 8C.

TABLE IX
VISCOELASTIC PROPERTIES AT VARIOUS SILICA LOADINGS
0 8C 30 8C 70 8C
Tg, E0, E 00 , tan E0, E 00 , tan E0, E 00 , tan

8C MPa MPa d MPa MPa d MPa MPa d
S0 19 2.05 0.88 0.43 1.45 0.09 0.06 1.49 0.05 0.04
S30 15.6 5.94 2.72 0.46 3.10 0.31 0.10 2.97 0.18 0.06
S50 17.5 11.50 4.58 0.40 4.92 0.71 0.15 4.48 0.40 0.09
S60 17.4 20.51 7.85 0.38 6.07 1.10 0.18 5.40 0.57 0.11
S70 16.4 29.70 10.66 0.36 7.34 1.53 0.28 6.34 0.86 0.14
generation monofunctional silanes. Bifunctionality enables the silane to form twice the number of
cross-links in the matrix when compared with monofunctional silane. Since DTorque is an indicator
of cross-link formation, S70 exhibits a higher DTorque value. Sengloyluan et al.6 studied the
behavior of different silanes in a NR matrix, where they concluded that a higher sulfur rank of S may
cause it to ‘‘donate’’ a part of its sulfur to increase the proportion of free sulfur in the matrix, which
consequently leads to additional cross-links. Similar behavior is being exhibited by the silanes in a
s-SBR/BR matrix too; however, the values are lower by 30% as compared with an NR matrix. The
cure rate exhibited by S70-N and S70-V is higher than S70, especially S70-V, which shows an
unnatural rise (around two times the cure rate of S70). This may be attributed to the high reactivity of
mercapto group,42 which when combined with 1,3-diphenylguanidine (DPG) used as an
accelerator shortens the scorch time. To overcome the issue of short scorch time, tetrabenzylth-
iuramdisulfide is used as an accelerator instead of DPG.42
The Payne effect of the compounds with different silane coupling agents used is given in Figure
7 and Table X. S70 displays a very high DG 0 , thus, increased filler–filler interaction as compared
with S70-N and S70-V. The markedly different chemical structure of the latter (Scheme 1) has a
FIG. 6. — Variation in tan d across a temperature sweep at various silica loadings.

TABLE X
DG 0 AND CURE CHARACTERISTICS AT 70 PHR SILICA LOADING WITH DIFFERENT SILANE COUPLING AGENTS
S70 S70-N S70-V
DG 0 , MPa 0.95 0.71 0.60

Minimum torque ML, dN m 5.08 2.96 5.16
Maximum torque MH, dN m 26.74 18.12 20.52
D Torque, dN m 21.66 15.16 15.36
ts2, min 1.6 3.5 0.8
tc90, min 12.9 13.4 5.9
Cure rate, min1 8.85 10.10 19.61
significant role to play in this, as previously studied by Luginsland and Röben.43 Bulky groups such
as octanoylthio ester group in N and long chain poly alkyl ether alcohols in V generate a shielding
effect of the reactive mercapto group, which lends reduced filler–filler interaction by effectively
hydrophobizing the silica surface. This stops the silica from reagglomerating in the rubber matrix
and lowers the DG 0 . The data obtained in the current experiment coincides with theoretical evidence
and previous findings.
The mechanical and viscoelastic properties of the compounds are presented in Tables XI and
XII. S70 exhibits the highest moduli both at 100% and 300% elongation due to its sulfur donating
capability and higher cross-link density. The lower bond dissociation energy of S when compared
with N and V results in a faster interaction with the rubber. The dissociation energy of the sulfur
containing silanes is S–S » 134 kJ/mol, whereas C–S–C » 285 kJ/mol, which leads to easier cross-
link formation in S70.6 S70-V and S70-N exhibited a higher tensile strength and a higher elongation
at break even though the modulus was lower. New generation silanes displayed a stronger polymer–
filler interaction as seen from DG 0 data (Table X) due to the mercaptosilane group that provide a
higher coupling efficiency, which consequently leads to better ultimate properties.
S70 as compared with the compounds having new generation silanes exhibited a higher
dynamic storage modulus (E 0 ) by 40 to 70% across temperatures due to a higher proportion of
FIG. 7. — Variation in storage modulus (G 0 ) across a strain sweep at 70 phr silica loading with different silane coupling
agents.
TABLE XI
MODULI, TENSILE STRENGTH, ELONGATION AT BREAK AND HARDNESS AT 70 PHR OF SILICA FILLER LOADING WITH
DIFFERENT SILANE COUPLING AGENTS
S70 S70-N S70-V
Modulus at 100%, MPa 3.8 2.5 2.3
Modulus at 300%, MPa 15.3 11.0 12.3
Tensile strength, MPa 17.2 18.1 18.4
Elongation at break, % 326 446 394
Hardness, shore A 65 65 62
chemically bound rubber6 (Table XII). This facilitated the compound exhibiting stiffer
characteristics as seen from the higher moduli and a higher E 0 . E 00 , tan d, and Tg of S70 were
also higher than the new generation silanes. As stated by Wang,12 viscous dissipation is a function
of filler agglomerates; breakdown and reformation in a particular range of stress results in a higher
heat buildup due to physical interaction with the polymer. Higher filler networking in S70 has thus
translated into a higher loss modulus and tan d. Diminished filler–filler interaction in S70-N and,
especially, S70-V reduced the viscous dissipation, which directly translated into very low rolling
resistance of tires. Hall and Moreland44 studied the viscoelastic properties of tire bead, sidewall, and
tread compound and concluded that the tan d and E 00 of the tread compound cause the maximum
impact on rolling resistance. Thus, S70-V used as a tread cap compound will exhibit a very low
rolling resistance owing to its 30% lower tan d at 70 8C as compared with S70. Figure 8 shows that
tan d exhibited by S70-V is the highest at subzero temperatures, which also lends it excellent ice
traction capabilities.12 The chemically bound rubber in S70 elevates the Tg of the compound by ~4
8C. The steric hindrance and efficient shielding triggered by the long chain alkyl groups in N and V
enhances the mobility of polymer chains within the compound, which lowers its Tg.6
EFFECT OF SILICA LOADING AND SILANE TYPE ON FATIGUE CRACK PROPAGATION PROPERTIES
A logarithmic plot of rate of crack propagation against tearing energy is shown in Figure 9. It
was evident that the tearing energy increased from 0 to 70 phr loading. Ellul18 also observed an
increase in tearing energy on increase in filler loading because of augmented hysterestic loss and
crack tip blunting. The effect of silica loading on crack growth rate in a s-SBR matrix was studied by
Reincke et al.,26 who concluded that the rate of crack growth decreases with increase in filler
loading. Our observations are also in accord with the results. However, the coefficient b in Eq. 7 is
affected by silica loading (plotted in Figure 10). A decrease in slope can be observed from 0 to 50
TABLE XII
VISCOELASTIC PROPERTIES AT 70 PHR OF SILICA FILLER LOADING WITH DIFFERENT SILANE COUPLING AGENTS
0 8C 30 8C 70 8C
Tg, E0, E 00 , tan E0, E 00 , tan E0, E 00 , tan

8C MPa MPa d MPa MPa d MPa MPa d
S70 16.4 29.70 10.66 0.36 7.34 1.93 0.28 6.34 0.86 0.14
S70-N 20.3 23.6 7.72 0.33 6.74 1.33 0.20 5.98 0.79 0.13
S70-V 18.5 18.5 6.71 0.36 5.78 0.92 0.16 5.35 0.56 0.11
FIG. 8. — Variation in tan d across a temperature sweep at 70 phr silica loading with different silane coupling agents.
phr loading, whereas at 70 phr, the value of b almost becomes 1.6 times that of S50. This
phenomenon was also studied by Klüppel,23 who noticed an increase in b at higher loadings of
carbon black and silica in a s-SBR matrix and concluded that there exists an optimum filler loading
of around 40 phr of carbon black or silica that gives us the lowest crack propagation rate. Above this,
a secondary mechanism dominates, i.e., an effect at the crack tip region that amplifies at higher
tearing energies in compounds with more filler present.23 S30 and S50 compounds show a b value
of 1.8, which translates into a lower FCG rate.18 The b value of NR has been reported to be ~2 in
earlier reports.18 Thus, s-SBR and BR blends at low loadings of silica behave similar to an NR
matrix with respect to FCG properties. The crack growth rate increases with increase in tearing
energy, as reported for other systems. On comparing the compounds at a particular tearing energy,
FIG. 9. — Fatigue crack growth rate at various tearing energy at different silica loadings.
FIG. 10. — Trend of crack growth exponent (b) values at different silica loadings.
the crack growth rate decreases with increase in filler loading except at 70 phr in the higher tearing
energy ranges.
The influence of crack precursor size on FCG rate was probed. Ultramicrotomy was performed
on the vulcanizate wherein the compound was sliced to a thickness of ~5 lm using a Leica
ultramicrotomy slicer. The slicing takes place at70 8C. The samples were then investigated using
an SEM (images are uploaded in a separate word document for ready reference). The low thickness
of the specimen enables a thorough study of the agglomerates present in the compound. S0 showed
no agglomerates, though the filled specimens up to 60 phr loading (S60) revealed agglomerates in
the range of 1–4 lm. However, S70 showed a sudden jump in the agglomerate size (~14 lm). This
was reflected in the FCG of S70 at higher tearing energy ranges and the crack growth exponent (b)
value increased by 55% from S50 to S70.
The change in FCG characteristics with change in silane can be seen in Figure 11. Though the
change was not as distinguishable, it can be clearly observed that S70 exhibited the lowest crack
growth rate. However, it is very interesting to note that S70-V, which gave superior properties in all
FIG. 11. — Fatigue crack growth rate at various tearing energy at 70 phr silica loading with different silane coupling agents.
FIG. 12. — (a) Abrasion loss; (b) side force coefficient; (c) abrasion loss and tearing energy at 10% strain various silica
loading.
spheres in earlier sections, showed a very high crack growth rate. The trend of silane change from V
to S is similar to increasing filler loading. This may be due to the crack path deviation phenomenon
at higher filler loadings, which led to a decrease in crack growth rate.
EFFECT OF SILICA LOADING AND SILANE TYPE ON ABRASION CHARACTERISTICS
Grosch studied the abrasion behavior of a tire tread compound of various polymers and
declared it to be closely related to FCG properties.30 This correlation holds more precisely for non-
strain crystallizing rubbers such as SBR and BR as compared with strain crystallizing rubbers. On
observing Figure 12a, it can be noted that a higher filler loading has facilitated a lower abrasion loss.
The improvement in reinforcement, which is evident in its mechanical properties, has led to a rise in
abrasion resistance. Grosch had studied the effect of filler loading on abrasion loss and concluded
that an increased filler loading often leads to a better abrasion resistance.45 He also studied the
relationship between traction of tread compound and the side force coefficient generated, which is
shown in Figure 12b. A steady rise in traction on increase in filler loading up to 60 phr silica loading
can be perceived. This zone of filler loading, which gives optimum traction and low abrasion loss,
very interestingly correlates with the trend of b in the FCG characteristics in Figure 10. This further
cements the point that there exists a percolation limit on filler loading above which properties show
FIG. 13. — Representative optical microscope images (a) S0; (b) S30; (c) S50; (d) S60; (e) S70. Magnification 403.
a decline due to reduced polymer–filler interaction and subsequent stress concentrations. Some
more observations can be made that link the tensile strength to abrasion loss as studied by Grosch
and Schallamach;46 yet another correlation can be found between E 00 or tan d at room temperature
and side force coefficient. S60 and S70, which show the highest tan d, generate the highest side force
coefficient too, as the adhesion between surface and rubber is dependent on the viscoelastic
dissipation of the rubber.32,47
FIG. 14. — (a) Abrasion loss; (b) side force coefficient; (c) tearing energy at 10% strain at 70 phr silica loading with different
silane coupling agents.
Since the morphology of the abraded surface can give insight into the mechanisms of abrasion
as studied by Schallamach32 and Bhowmick,34 the surfaces were subject to optical microscopy, and
the micrographs are shown in Figure 13. As the roughness decreases on increase in silica loading,
our results match with those of Bhowmick,34 who had stated that gum vulcanizates initially display
unordered annular rings, followed by ribs much later. An increase in periodic patterns is evident on
surfaces with higher filler loadings.
When the same experiments were performed on compounds with different silanes (Figure 14),
the results showed a 11% decrease in abrasion loss in S70-V as compared with S70. The increased
abrasion resistance (Figure 14a) can be attributed to a higher tensile strength and polymer–filler
interaction in S70-V.48 Side force coefficient was lowest with S70-V (Figure 14b). On studying the
optical microscopy images in Figure 15, a finer abrasion pattern can be observed in S70-V (Figure
15c). Lower width between the ridges has translated into lower abrasion loss in S70-V.
FIG. 15. — Representative optical microscope images (a) S70; (b) S70-N; (c) S70-V. Magnification 403.
CONCLUSIONS
The loading of silica in a blend of s-SBR and BR was varied from 0 to 70 phr. Mechanical
properties such as tensile strength showed a nine times increase from 0 phr loading to 50 phr; the
values displayed a decline at 70 phr loading. FCG properties, too, showed the best performance in
the same range of silica loading. The value of b gave an abrupt rise (~56%) after 50 phr. This has
been attributed to optimum filler content, leading to lower filler networking and higher polymer–
filler interaction. A four times increase in tan d, indicating higher hysteresis, was obtained in
compounds containing higher filler dosage. The abrasion loss fell by 91%, and the side force
coefficient was enhanced by 61% due to an increased reinforcement phenomenon.
The effect of various silanes such as N and V was compared with the conventional silane S.
New generation silanes such as V exhibited considerably less filler networking, i.e., lower DG 0 by
37% due to bulky groups, which caused a better shielding effect and improved the hydrophobizing
capability of silica particles. V also ensured a lower rolling resistance (by 21%) as observed by the
lower tan d value at 70 8C. N and V also improved the abrasion resistance over the conventional
silane. Nevertheless, the FCG properties shown by V are poor, whereas the conventional silane
exhibits the highest crack growth resistance.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the support received from MHRD for sponsoring an
Ucchatara Yojana Program on development of high performance rubber composites using new
generation materials for application in tires for collaboration between HASETRI and IIT
Kharagpur. The authors would also like to thank Prasenjit Ghosh, Jagannath Chanda, and Ramesh
Shilavant of HASETRI for their assistance in conducting the experiments and for their valuable
suggestions.
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[Received January 2018, Revised April 2018]

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EFFECT OF SILICA LOADING AND COUPLING AGENT ON WEAR AND

FATIGUE PROPERTIES OF A TREAD COMPOUND

HARINI SRIDHARAN,1 ABHILASH GUHA,2 SANJAY BHATTACHARYYA,1 ANIL K. BHOWMICK,2,*

*Corresponding author. Email: anilkb@rtc.iitkgp.ernet.in

FORMULATIONS AND MIXING

FILLER DISPERSION STUDY

Ingredients, phra S0 S30 S50 S60 S70

Ingredients, phr S70 S70-N S70-V

Time, s Temperature, 8C Actions

Mixing action: Master I

Test condition Values

Disk type 60 corundum

DYNAMIC MECHANICAL PROPERTIES

FATIGUE CRACK GROWTH MEASUREMENT

FIG. 2. — Dimensions of pure shear sample for FCG testing in TFA.

Test condition Values

Strain (%) 10, 15, 20, 25

RESULTS AND DISCUSSION

S0 S30 S50 S60 S70

DG 0 , MPa 0.03 0.24 0.63 1.36 5.35

S0 S30 S50 S60 S70

Modulus at 100%, MPa 0.6 1.2 1.8 2.2 3.8

FIG. 4. — Variation of E/E0 with filler volume fraction U.

0.05 0.95 0.22

FIG. 5. — Relationship between DG 0 and tan d measured at 50 8C.

Tg, E0, E 00 , tan E0, E 00 , tan E0, E 00 , tan

FIG. 6. — Variation in tan d across a temperature sweep at various silica loadings.

S70 S70-N S70-V

DG 0 , MPa 0.95 0.71 0.60

S70 S70-N S70-V

Modulus at 100%, MPa 3.8 2.5 2.3

Tg, E0, E 00 , tan E0, E 00 , tan E0, E 00 , tan

EFFECT OF SILICA LOADING AND SILANE TYPE ON ABRASION CHARACTERISTICS

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