Zhang 2016

Materials Development for Lowering Rolling Resistance of Tires
PING ZHANG,* MICHAEL MORRIS, DHAVAL DOSHI

REINFORCEMENT MATERIALS R&D, BILLERICA BUSINESS AND TECHNOLOGY CENTER,
CABOT CORPORATION, BILLERICA, MA 01721
RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 00, No. 0, pp. 000–000 (0000)
ABSTRACT
Many countries are implementing regulatory programs to promote the use of transportation technologies that can
reduce greenhouse gas emissions and enhance fuel economy of vehicles. These regulatory programs create a need for more
durable and fuel-efficient tires. The increased cost of fuel for motor vehicles creates another driving force for improving
the fuel economy of vehicles. Commercial vehicle operators recognize that fuel cost is a major driver of the total operating
cost; therefore, they increasingly demand tires that are optimized for reducing the fuel cost of a trucking fleet. Rolling
resistance of truck tires accounts for about one-third of the power required to move a heavy-duty truck and is the second
most important contributor, after engine loss, to the total energy loss of heavy-duty trucks. Other than tire designs, rubber
compound hysteresis contributes to the rolling resistance of tires, which affects vehicle fuel economy. There is a
significant market demand, due to governmental regulations, concerns for the environment, and cost savings to the
consumers, for developing tread compounds or tread compound systems that can reduce tire rolling resistance while
maintaining the treadwear and durability of truck tires. This paper reviews materials technologies developed for reducing
the hysteresis loss of rubber compounds at high temperatures, hence lowering the rolling resistance of tires. Compounding
approaches that can be used to lower the hysteresis loss of rubber compounds and to reduce rolling resistance of tires also
are discussed. Developments in elastomers and reinforcing materials, including nanoparticles, are highlighted, with focus
on the benefits of those polymers and particles in reducing the hysteresis loss at high temperatures of rubber compounds.
[doi:10.5254/rct.16.83805]
CONTENTS
I. Tire Rolling Resistance and Compound Hysteresis . . . . . . . . . . . . . . . . . . . . . . . . . . 0
II. Origins of Hysteresis Loss from Use of Reinforcing Particles in Rubber . . . . . . . . . 0
III. Approaches to Reduce Hysteresis Loss of Rubber Compounds . . . . . . . . . . . . . . . . 0
A. Impact of Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
B. Use of Functionalized Elastomers with Reinforcing Particles . . . . . . . . . . . . . . . 0
C. Particle Morphology and Formulation Approaches . . . . . . . . . . . . . . . . . . . . . . . 0
D. Impact of Particle Dispersion on Compound Hysteresis. . . . . . . . . . . . . . . . . . . . 0
IV. Recent Development in Reinforcing Particles for Reduced Hysteresis . . . . . . . . . . . 0
A. Advanced Morphology Control: Aggregate Size Distribution . . . . . . . . . . . . . . . 0
B. Composition Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
C. Manipulation of Particle Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
D. Development of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
V. Challenges in Adopting New Materials for Reduced Rolling Resistance in the Tire Industry . 0
VI. Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
VII. Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
VIII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
I. TIRE ROLLING RESISTANCE AND COMPOUND HYSTERESIS

There is an increasing demand for improving fuel economy of both passenger and truck tires
due to the increased fuel cost for the consumers and trucking fleet operators as well as government
regulations on tire rolling resistance, vehicle fuel economy, and greenhouse gas emissions.1–3 The
mandatory implementation of the Environmental Protection Agency (EPA) greenhouse gas
*Corresponding author. Ph: ; email: ping.zhang@cabotcorp.com
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0 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 00, No. 0, pp. 000–000 (0000)
Fig. 1. — Fuel costs relative to vehicle costs for passenger and heavy-duty vehicles. (Reprinted from ref 6.)
emission standard in model year 2014 and of the National Highway Traffic Safety Administration
fuel consumption standard in model years 2016 and 2017 for trucks based on gasoline and diesel
engines, respectively, has forced truck manufacturers to seek technologies to improve fuel
economy for and reduce greenhouse gas emission from the vehicle. The SmartWay program
established by EPA to promote the fuel efficiency of truck tires will encourage the sale of truck tires
with reduced rolling resistance.4
With an average of 6.1 miles per gallon fuel economy for a typical class 8 combination tractor/
trailer, the cost of fuel on an annual basis is the number one cost for a trucking fleet.5 As is shown
from the U.S. Department of Energy statistics in Figure 1, the lifetime fuel cost for an average
passenger car is similar to the vehicle’s original purchase price. In contrast, the lifetime fuel cost for
a class 8 truck is multiple times that of the original purchase price for the vehicle.6 Fuel economy is
therefore a much larger concern for trucks than for passenger cars.
Rolling resistance loss of a tire is the mechanical energy consumed when the tire moves for a
unit distance over the road surface.7,8 Rolling resistance contributes significantly to the total energy
loss and directly impacts the fuel efficiency of a motor vehicle. Rolling resistance loss, for example,
accounts for about one-third of the power required to move a heavy-duty truck over a level road at
highway speeds.5 Rolling resistance loss is the second most important contributor, after the engine
loss, to the overall energy loss from a class 8 heavy duty truck when driven at a steady state speed of
50 miles per hour on a level road. At a higher speed of 65 mile per hour, rolling resistance loss ranks
a close third after engine and aerodynamic losses.9
Reducing the rolling resistance of tires has a significant impact on the fuel savings of vehicles.
Lowering the rolling resistance of tires by 30%, in general, leads to fuel savings of between 3 and
6% for a passenger vehicle, depending on the vehicle type, road conditions, and driving habits. In
contrast, for a heavy-duty truck designed to be driven mostly on highways, a reduction of 20% in
rolling resistance can reduce fuel consumption by around 6%.10
Energy loss from the rolling of tires not only affects the fuel economy of vehicles, but also
impacts the performance of tires through increased temperature of tires under cyclic deformation
due to relatively poor thermal conductivity of rubber compounds. The change in tire temperature
affects the viscoelastic properties of compounds that can impact the handling and traction
performance of tires. The temperature increase of tires also affects the strength of rubber
compounds, which will have a significant effect on treadwear and durability as well as tread block
LOWERING ROLLING RESISTANCE OF TIRES 0
tearing or chunking performance of tires.11 Heat buildup in the tire components also affects the
aging rate of rubber compounds, leading to the breakdown (softening) or more crosslinks
(hardening) of rubber molecules, depending on the type of elastomers used in rubber compounds.
The degradation of rubber compounds through thermal aging may result in reduced service and
casing life of tires, leading to reduced numbers of retreading for truck tires.12,13 A proper selection
of reinforcing particles in the rubber compounds can significantly influence the heat buildup
characteristics of rubber compounds in different parts of truck tires, hence affecting the
retreadability of the truck tires.13–16
Past reviews on different aspects of rolling resistance of tires are provided by Hall and
Moreland,8 Schuring and Futamura,17 and Schuring.18 Hall and Moreland8 provided a detailed
review on the impact of rolling resistance on vehicle fuel economy, measurements of tire rolling
resistance, effects of vehicle operating parameters on rolling resistance, and numerical modeling of
rolling resistance of tires, linking compound viscoelastic properties with rolling resistance of tires.
Schuring and Futamura17 gave a detailed account of the historical development in tire rolling
resistance and provided an extensive review on different aspects of tire rolling resistance, such as
measurements of rolling resistance, the impact of rolling resistance on fuel consumption, and the
influence of operational variables on rolling resistance as well the effect of tire design and
construction on rolling resistance of tires. Some discussion was made on the development of tread
materials technology for reducing rolling resistance of tires. The references listed in these reviews
provide additional information about materials development, measurements of rolling resistance,
and the correlation between rolling resistance and fuel economy of motor vehicles.
Other than tire design features, rubber compounds used in different tire components contribute
to the rolling resistance of tires via energy loss from dynamic deformation of the components during
service. The dynamic properties of rubber compounds are influenced by processing parameters as
well as the selection of materials ingredients forming the rubber compounds (Scheme 1).
The major focus of this review is on the development of materials for the improvement of the
rolling resistance performance of tires, hence the fuel economy of motor vehicles. Since, among all
compounds used in tires, tread compounds have the largest contribution to rolling resistance
performance of tires, materials development for tread compounds is the major focus in the review.
However, as rolling resistance targets get more difficult to achieve, exploration and efforts for
solutions beyond the tread component are expected. Different traditional compounding approaches
for reducing hysteresis loss at high temperatures are reviewed, and new materials developments in
elastomers and reinforcing particles are discussed. Discussions on the contribution of other
compounding ingredients to hysteresis of rubber compounds and to rolling resistance of tires, such
as curatives, oils, and resins, can be found in the references cited in this review. New development in
the area of nanoparticles for potential tire applications is briefly reviewed. Since dispersion of
reinforcing particles is very important to achieving the desirable compound performance, such as
rolling resistance, treadwear, and tear, the impact of dispersion of reinforcing particles as well as
technical approaches to achieve good particle dispersion also is discussed.
Rolling resistance loss arises from the deformation of different components of tires and from
the interaction of tires with the road surfaces. From the tire prospective, rolling resistance loss
comes from a combined effect of component material hysteresis, tire structure, inflation pressure,
and tire stiffness.19 Among all tire components, tread compounds make the largest contribution to
the rolling resistance of the tire, accounting for 40%–50% for passenger tires and 35–50% of the
total rolling resistance loss for truck tires, depending on tire aspect ratio and design.20–22 Significant
efforts have therefore been made by tire manufacturers and materials suppliers to develop tread
compounds or tread compound systems (e.g., a cap and base combination) with reduced rolling
resistance that maintain other key performance characteristics of tires.
The level of energy loss from viscoelastic rubber compounds used in the tread under dynamic
deformation depends not only on the viscoelastic properties of the tread compounds, but also on the
mode of deformation. When a viscoelastic material is subjected to a sinusoidal alternating shear
stress r at a frequency of x, the strain c is out of phase by a phase angle of d.
r ¼ ro sinðxt þ dÞ ð1Þ
and
c ¼ co sin xt ð2Þ
where t is time, d is the phase angle between stress and strain, and ro and co are the maximum
amplitude of strain and stress, respectively.
The energy loss from one cycle of deformation DE can be expressed as
Z Z 2px
rdc
DE ¼ rdc ¼ dt ð3Þ
0 dt
In terms of strain amplitudeco,
DE ¼ p c2o G0 tan d ð4Þ

where G 0 is the elastic modulus.
In terms of stress amplitude ro, at temperatures much higher than the glass transition
temperature (Tg) of the rubber compounds,
DE @ x s2o tan d G0 ð5Þ

And in terms of the product of stress and strain amplitudes roco, at temperatures much higher
than the Tg of the rubber compounds,
DE ¼ pro cosin d @ p ro do tan d ð6Þ
To illustrate the dependence of energy loss on the type of deformation process, Futamura23
used two rubber compounds with identical hysteresis loss, tan d, and different dynamic moduli, G 0 ,
as shown in Table 1. Note that energy loss from compound A could be equal to, higher, or lower than
that of compound B, depending on the deformation process to which the rubber compound is
subjected.
TABLE 1
DEPENDENCE OF ENERGY LOSS ON TYPE OF DEFORMATION PROCESSa
Compound
A B
Parameter
Dynamic modulus, MPa 5 10
tan d 0.2 0.2
Type of process Energy loss
Equal strain A,B
Equal energy AþB
Equal stress A.B
a
Reprinted from ref 23.
Deformation of the tire tread compounds can be resolved approximately into two modes:
constant strain from bending and constant stress from compression. Medalia16 suggested that since
the geometric mean of the hysteresis under those two conditions is approximately proportional to
tan d, the energy loss from the tread compounds is, as a first approximation, proportional to tan d.
Futamura23 and Futamura et al.24 proposed to use a deformation index, n, to describe the type of
deformation processes for rubebr compounds, where n¼0, 1, and 2 for a constant strain, a constant
energy process, and a constant stress process, respectively,
DEr G00 =ðG*Þn ð7Þ
where G 0 0 and G* are the the loss and complex modulus of rubber compounds, respectively. When n
¼ 0, 1, and 2, the energy loss of rubber compounds is proportionnal to G 0 0 , tan d, and tan d/G 0 ,
respectively.
Futamura showed through testing of tires having tread compounds with different dynamic
properties that the correlation coefficient of energy loss (rolling resistance) of tires with hysteresis
loss tan d of the tread compound depends on the inflation pressure of tires at a given load. As is
shown in Figure 2, at a low inflation pressure of 207 kPa (30 psi ), the deformation index was 0.5 and
at a high inflation pressure of 758 kPa (110 psi ), the deformation index was 1.1. The inflation
pressure of tires in Futamura’s tire testing program covers what are typically used for passenger tires
(lower pressure end) and truck tires (higher pressure end). Apparently at a low inflation pressure, the
deformation process is dominated by constant strain deformation due to bending of the tread. In
contrast, at a high inflation pressure, the contrbution from the constant stress mode increases due to
compressional deformation at the footprint. As is shown in Figure 3, at an intermediate inflation
pressure of 483 kPa (70 psi ), the rolling resistance of tires correlates very well with the hysterses
loss tan d.
Using a finite element modeling approch, Futamura et al.24 showed that for a radial medium
truck tire tread, the central portion of the tread is primarily under a stress-controlled deformation and
the shoulder area is under an energy-controlled process, whereas the tread of a passeneger tire is
primarily under an energy-controlled deformation. The computed results are more or less in line
with what was observed from the experimental measurement of tires.23 The experimental
observation by Mouri11 that heat buildup of a truck tire tread correlates very well with the
temperature increase of the tread compound when tested under a stress-controlled condition
indicates that the truck tread is mostly under constant stress condition during services. The rolling
resistance performance of truck tires was therefore closely approximated to a constant stress
Fig. 2. — Correlation between rolling resistance and energy loss function with deformation indices, n. Load ¼ 8.9 kN,
inflation pressure at 207 kPa (30 psi), solid line; 483 kPa (70 psi ), dashed-dotted line; and 758 kPa (110 psi ), dashed line.
(Reprinted from ref 23.)
defomation process, with the energy loss from cyclic deformation being proportional to tand and
inversely proportional to elastic modulus of the tread compound (DE a tan d/G 0 ).22
It has been reported that the deformation mode of the tread compound of an electric car tire with
a very high inflation pressure is predominantly compressional (stress controlled). The design of a
low rolling resistance (LLR) tread compound for an electric vehicle will therefore be different from
that of a tread compound for a conventional passenger car.24
Clearly, the energy loss of tires during service is complicated, with the level of enegy loss
during deformation depending on the deformation modes that the tread component experiences.
However, high-temperature hystersis loss, tan d, of rubber compounds at relatively low frequencies
(10–100 Hz) is still commonly used as a lab indictor for rolling resistance in the development of new
materials for tire applications (Figure 4).25 As discussed, since the dominant model of deformation
is a constant energy process for the passenger tread, tan d of the tread compound would be a good
predictor for rolling resistance in passenger tires. Hess et al.7, for example, demonstrated through
tire testing that the rolling resistance of passenger tires correlated very well with the hysteresis losss
Fig. 3. — Correlation between rolling resistance and loss modulus, tan d, and loss compliance. Load ¼ 8.9 kN, Inflation
Pressure ¼ 483 kPa. (Reprinted from ref 23.)
Fig. 4. — Use of hysteresis loss tan d as an indicator for rolling resistance of rubber compounds. (Reprinted from ref 25.)
and rebound at high tempertures of the tread compound. Depending on the type of tires and inflation
pressures, the dynamic modulus, other than hysteresis loss tan, of the tread compounds needs to be
taken into consideration for a bettter assessment of the rolling performance of tread compounds.
II. ORIGINS OF HYSTERESIS LOSS FROM USE OF REINFORCING PARTICLES IN

RUBBER
Conventional rubber used for the manufacture of tires is a viscoelastic material from the cross-
linking of a polymer considered to be in a viscoelastic liquid state initially.26 At temperatures higher
than the Tg, the material exhibits both elastic and viscous responses when subjected to dynamic
deformation. Relative energy storage and loss during the deformation process depend on the
contribution from each component (elastic and viscous). Factors affecting the energy loss of rubber
include the Tg, crystallinity, functionalization, branching, molecular weight, molecular weight
distribution, and the degree of cross-linking. The impact of those factors on the energy loss is
reviewed by Day27 and Sircar et al.,28 and details can be found from the reviews as well as from the
extensive list of references in the reviews.
Pure general purpose elastomers, when properly cured, exhibit very low hysteresis loss at
temperatures significantly higher than the Tg of the elastomers, desirable for LLR for tire
applications. The use of elastomers alone will not provide all needed performance characteristics of
tires. Reinforcing particles (carbon black or silica) are needed to provide reinforcement to rubbers
for improved treadwear, traction, and tear performance of tires. However, as is shown in Figure 5,
the introduction of reinforcing or semi-reinforcing particles into elastomers also leads to increased
hysteresis loss at high temperatures.29 The introduction of reinforcing particles into elastomers not
only results in increased stiffness and hysteresis loss at high temperatures, but also display of
nonlinear behavior, as shown in Figure 6. Such nonlinearity with strain is generally referred to as the
Payne effect, from the early work of Payne and others.29–31 As shown in Figure 7, several factors
contribute to the dynamic properties of rubber compounds, including elastomer network,
hydrodynamic effect from inclusion of hard particles, and particle–elastomer and particle–particle
interactions. The nonlinearity of the dynamic response of reinforcing particle–filled rubber
compounds is generally believed to be due to particle–particle interactions.32,33
Fig. 5. — Impact of introducing carbon black particles on hysteresis loss tan d of rubber compounds at 5% double-strain
amplitude and 10 Hz. (Reprinted from ref 25.)
The mechanisms through which the hysteresis loss of rubber compounds is increased when
reinforcing particles are introduced are not very clearly understood, even though significant efforts
have been made over the decades to develop a mechanistic understanding of the process. In general,
however, it is agreed on that, other than the contribution from the elastomer through the
Fig. 6. — Impact of introducing carbon black particles on (a) elastic modulus of NR-based rubber compounds at 60 8C and
10 Hz and (b) on hysteresis loss tan d of NR-based rubber compounds at 60 8C and 10 Hz. (Unpublished results from Cabot
Corporation, December, 2015.)
Fig. 7. — Schematic representation of the contributing factors to dynamic properties of reinforced rubber compounds
containing carbon black or silica. (Reprinted from ref 39.)
microstructure of the polymer and the degree of cure, the interactions between elastomer and
reinforcing particles and between particles and particles play important roles in determining the
hysteresis loss property as well as the reinforcement characteristics of rubber compounds.25,34–37
A variety of mechanisms, models, and theories have been proposed over the years to interpret
the experimental observations. The proposed mechanisms, models, and theories include the
breakdown and reformation of the particle–particle network; the detachment and reattachment of
polymer molecular chains from and on to the particle surfaces; and the yielding of the particle–
particle bonds formed from glassy polymer bridges.35
When active reinforcing particles, such as carbon black or silica, are introduced into rubber
compounds, due to strong interaction between particles in the uncured viscous elastomer, the
particles tend to agglomerate, forming a particle–particle network. Evidence of reflocculation of
reinforcing particles during storage at elevated temperatures was reported by Boehm and Nguyen.38
The formation of the particle–particle network is clearly evident from the transmission electron
microscopic image of highly filled rubber compounds, as shown in Figure 8.39 The particle–particle
network is considered to be elastic in nature under small strains as indicated from the linearity of the
elastic modulus in Figure 6a and from the very low hysteresis loss in Figure 6b when the strain level
is very low.
Payne29 suggested that the decrease in elastic modulus of particle-reinforced rubber and the
existence of a peak hysteresis loss tan d with increased strain amplitude is due to the breakdown of
the three-dimensional aggregates and agglomerates of carbon black. The breakdown of the
particle–particle network is evidenced from the observation that the changes in electrical
conductivity of rubber compounds with strain amplitude are similar to the change in the dynamic
modulus with strain amplitude.40,41 Another strong support for the mechanism is the dynamic
response of silica-containing compounds with and without using silane coupling agents. It is
generally believed that, due to the existence of hydroxyl groups on the surface of silica and hence
strong particle–particle interaction from hydrogen bonds in a silica rubber compounds, there is a
Fig. 8. —Transmission electron microscopy image of a carbon black network formed in a rubber compound obtained from
an ultra-thin cut of filled rubber samples. (Reprinted from ref 39.)
strong tendency for silica aggregates to form a strong particle-particle network when no silane
coupling agent is used in the formulation. The existence of strong particle–particle network is
clearly evidenced from a large Payne effect and very low hysteresis loss tan d at small strains from
compounds containing no silane coupling agent, as shown in Figure 9a, b. Due to strong interaction
between particles, silica compounds without silane coupling agents exhibited high stiffness at small
deformation; due to the elastic nature of the particle–particle network, the hysteresis loss tan d of the
Fig. 9. — (a) High elastic modulus at small strains from silica compounds without silane coupling agent and (b) low
hysteresis loss tan d at small strains and high hysteresis loss tan d at large strains from silica compounds without silane
coupling agent. Compound formulation: 70/30 phr SSBR/BR, 80 phr silica (Z1165MP), 37.5 phr processing oil, and 6.4 or 0
phr silane coupling agent [bis-(3-(triethoxysilylpropyl)-tetrasulfide]. (Unpublished results from Cabot Corporation,
December 2015.)
Fig. 10. — (a) Schematic drawing showing the structure of particle–particle bonds. The black discs represent parimary
particle aggregate. (Reprinted from ref 48.). (b) Kinetically aggregated particle clusters in a particle-reinforced rubber
compound. ‘‘F’’ is the particle volume fraction in the rubber compounds. (Reprinted from ref 39.)
compounds is very low at such small deformation. However, when the deformation level becomes
large and the particle–particle network starts to break down, the elastic modulus of the compounds
drops significantly, while the hysteresis loss tan d increases dramatically.
Kraus42 developed a mathematical model based on the agglomeration–deagglomeration
mechanisms to interpret the experimental observations. The model was found to describe well the
strain dependence of the elastic modulus of particle-reinforced rubber compounds in different
elastomers, whereas some modifications of the model were needed to better describe the viscous
response of the rubber compounds.43
It has been observed from bound rubber and NMR measurements of rubber compounds that
there is an immobilized layer of rubber with a thickness of on the order of a few nanometers on the
surface of the reinforcing particles.44,45 Flocculation studies of reinforcing particle–filled rubber
compounds demonstrated that there is a relative movement of particles, with the degree of
movement depending on the particle size, molar mass of polymer, and polymer–particle
interaction.39 Based on the experimental observations, Kluppel et al.33,35,39,46–48 proposed a kinetic
cluster–cluster aggregation mechanism (Figure 10a, b). The clusters can be further divided into
rigid and fragile units. It was proposed that under dynamic deformation, the fraction of rigid clusters
decreases with increased pre-strain, leading to pronounced stress softening after the first
deformation cycles. The fraction of already damaged fragile clusters increases with increased pre-
strain. The particle-induced hysteresis loss comes from the cyclic breakdown, and reaggregation of
the residual fraction of more soft and fragile particle clusters with already broken (damaged)
particle–particle bonds.
Fig. 11. — Molecular slippage model of reinforcement and hysteresis loss mechanism. (Reprinted from ref 50.)
Merabia et al.49 suggested that the elastomer matrix in the vicinity of the reinforcing particle is
highly glassy in nature when there is strong interaction between the particle and the elastomer and
proposed that the major source of energy dissipation in a reinforcing particle–filled elastomer is due
to the yielding of the glassy bridges between reinforcing particles.
Dannenberg50 and others have proposed a molecular slippage model to explain the
reinforcement and hysteresis loss in particle-reinforced rubber compounds, as shown in Figure
11. The proposed mechanism assumes that under dynamic stress the surface-adsorbed network
segments move relative to the particle surface. As a consequence of the movement or slippage
process, strain energy is dissipated as frictional heat, resulting in hysteresis loss in the rubber
compounds.
Goritz et al.51 further proposed that polymer chain segments bonded to particle surfaces can be
divided into strong/stabilized and weak/unstable bonds. Only the weak/unstable bonded segments
slide on the particle surface and are therefore responsible for the energy dissipation in reinforcing
particle–filled rubber compounds.
Funt52 suggested that there is an increase in effective cross-link density from entanglements
that are formed between bound rubber and rubber layer in the transition zone between the bound
rubber and the bulk rubber matrix. The hysteresis loss at different strain levels is due to the breaking
and reforming of the entanglements.
The fundamental understanding of the reinforcement and energy loss mechanisms is still an
active area in reinforcing particle–filled rubber compounds, as shown by some more recent
studies.53–55 Clearly, the properties of the elastomer in terms of the microstructure, Tg, and the
Fig. 12. — Impact of elastomer Tg on high temperature hysteresis loss tan d of rubber compounds. Compound formulation:
100 or 60/40 phr SSBR/BR, 50 phr carbon black (N234). (Unpublished results from Cabot Corporation, December 2015.)
degree of cure; the morphology and interaction of the reinforcing particles with the elastomers; and
the particle–particle interaction will affect the reinforcement and hysteresis loss properties of
reinforcing particle–filled rubber compounds. A better understanding of the mechanisms involved
in the hysteresis loss of reinforcing particle–filled rubber compounds will certainly help design new
reinforcing particles to further reduce the rolling resistance of tires.
III. APPROACHES TO REDUCE HYSTERESIS LOSS OF RUBBER COMPOUNDS

A. IMPACT OF ELASTOMERS
Ingredients used in a rubber compound formulation have different degrees of impact on the
hysteresis loss properties of a rubber compound. The major ingredients that affect the hysteresis loss
properties include elastomers, reinforcing particles, and curative packages.7,56,57
A variety of elastomers are used in the tread or subtread components that contribute most
significantly to the energy loss and hence the rolling resistance performance of tires. These
elastomers include NR, BR, and SBR. The microstructure and compositions of the elastomers have
a direct impact on the hysteresis loss properties of rubber compounds at high temperatures. One of
the important characteristics of elastomers that affects the hysteresis loss properties at both low and
high temperatures of rubber compounds is the Tg. Using an elastomer with a low Tg will typically
result in rubber compounds with low hysteresis loss at high temperatures, except for some special
elastomers such as butyl rubber.36,58–60 NR exhibits very low hysteresis at high temperatures
relative to its Tg compared with SBR and BR, whereas very high hysteresis is seen from BR.60
As is shown in Figure 12, the use of low Tg elastomers through blends of solution SBR and BR
leads to rubber compounds with reduced hysteresis loss in the high temperature region, indicative of
low rolling resistance (LRR) for tire tread applications. However, since the wet traction
performance of tires is strongly linked with the Tg of the tread compounds, the use of low Tg
elastomers may lead to a compromise in the wet traction performance, as shown in Figure 13.61
Fig. 13. — Schematic drawing showing compromise between rolling resistance and wet traction performance of tires from
the use of elastomers with different Tg values. (Reprinted from ref 61.)
B. USE OF FUNCTIONALIZED ELASTOMERS WITH REINFORCING PARTICLES
Through the use of elastomers with functional groups that interact with specific reinforcing
particles, the rolling resistance performance of tread compounds can be improved without
compromising the wet traction performance of tires. A variety of such functional groups have been
introduced onto the elastomer chains for different reinforcing particles.
Tin-coupled elastomers and elastomers containing amine functional groups have been found to
interact well with carbon black, leading to a significantly reduced Payne effect and much reduced
hysteresis loss at high temperatures.62–64 The use of tin-coupled solution SBR with carbon black
results in a much reduced Payne effect and a substantial reduction in hysteresis loss at high
temperatures, as shown in Figure 14, and the degree in improvements in the hysteresis loss depends
on the concentration of the tin content and the type of Sn–C bonds at the chain end, as shown in
Figure 15. The reduction of hysteresis loss of rubber compounds through the end modification via
tin coupling is thought to occur via two mechanisms: (1) reduction of the carbon black network due
to strong particle–polymer interaction and (2) reduction of free chain ends.65 The tin end-modified
polymers stabilize individual carbon black aggregates and inhibit their flocculation during storage
and curing. It is generally believed that the free end of the polymer chains does not participate in any
efficient elastically recoverable process; thus, any energy transmitted to this section of the polymer
chains is lost. Tie-up of the free chain ends reduces the contribution of dangling chains to loss
modulus without leading to increased hysteresis.60,65–67 The combination of less carbon black
network formation and less contribution of free chain ends leads to reduced hysteresis loss of rubber
compounds when tin-coupled polymers are used with carbon blacks.
Amine-containing compounds can be introduced during polymerization to end modify the
polymers.68–72 The use of such end-functionalized solution SBR with carbon black leads to rubber
compounds with much improved dynamic performance (much reduced Payne effect and
significantly lowered hysteresis loss at high temperatures). The improved dynamic performance
through the use of amine-functionalized SSBR is explained from the strengthened polymer–particle
interaction and improved dispersion of carbon black in the elastomer matrix.
Fig. 14. — Impact of tin-coupling on hysteresis loss and Payne effect of carbon black–reinforced rubber compounds (100
phr SSBR and 50 phr N330 carbon black). (Reprinted from ref 63.)
In-chain carboxyl-functionalized SSBR has been reported to lead to rubber compounds with
reduced hysteresis at high temperature that is comparable with a silica-based rubber compound
when used in combination with conventional or oxidized carbon black.73–75 The improvement in
the hysteresis property from such a combination is believed to be due to strong interaction between
Fig. 15. — Effects of types of Sn–C bonds and centration of tin on dynamic hysteresis loss properties of carbon black–
reinforced rubber compounds (100 phr SSBR and 50 phr N330 carbon black). (Reprinted from ref 63.)
Fig. 16. — Effect of different functional groups used for the modification of polymers on the hysteresis loss of rubber
compounds. (Reprinted from ref 98.)
carbon blacks and the functional groups through hydrogen bonds to improve the dispersion of the
particles in the rubber and to reduce the particle–particle interaction.
Unlike reinforcing carbon black, due to the existence of hydrophilic groups on the surface, silica
is less compatible with the traditional nonpolar elastomers used for tire applications.32,76 The strong
particle–particle interaction through hydrogen bonding from the hydroxyl groups on the silica
surface forms a strong particle–particle network. Silane coupling agents are needed for silica-based
rubber compounds to enhance the interaction between silica and polymers.77–80 Due to the reactive
nature of the conventional silane coupling agents and the need to complete the silanization process
during mixing, mixing temperature and reaction time need to be well monitored to render the
compound processable for the downstream operations and for achieving good reinforcement.81–85
A variety of functional groups have been introduced into different elastomers either at the chain
end or along the chain to further enhance the interaction of silica with elastomers beyond the use of
silane coupling agents.67,86 Those functional groups include silanol,87–89 alkoxysilane, 67,86,90,91
carboxyl,92–94 epoxide,95 hydroxyl,96 and polyether.97 Figure 16 shows the impact of different end-
chain modifications of polymers on the hysteresis loss of silica-based rubber compounds. Depending
on the type of functional groups used, the hysteresis loss of rubber compounds can be significantly
reduced compared with unfunctionalized solution SBR.98 To further improve the dynamic
performance of rubber compounds, multifunctionalized solution SBRs have been developed
through functionalized initiators or copolymerization of functionalized monomers.98–100
Many mechanisms may be involved in the reduction of the hysteresis loss of rubber
compounds when functionalized polymers are used in combination with silica and silane coupling
agents. It is generally believed that improved dispersion of silica through better interaction of silica
with elastomer and less free chain ends are the primary reasons for the improved dynamic
performance of functionalized rubber compounds containing silica and silane coupling agents.98
C. PARTICLE MORPHOLOGY AND FORMULAION APPROACHES
Other than the choice of elastomers as discussed in the previous section, various approaches
using particle parameters have been taken for developing rubber compounds with reduced
hysteresis at high temperatures. These particle parameters include surface area, structure, and
surface activities.25
The surface area of reinforcing particles has a significant impact on the hysteresis loss of rubber
compounds. At constant loading, as shown in Figure 17, increasing the surface area of the carbon
black will significantly increase the hysteresis loss of rubber compounds under conditions of
Fig. 17. — Loss tangents of vulcanizates as a function of the surface area of carbon blacks (SBR1500 and 50 phr carbon
black). (Reprinted from ref 7.)
constant strain or energy. However, due to changes in stiffness (modulus) of rubber compounds, the
effect of the surface area of particles on the hysteresis loss of rubber compounds is less pronounced
at constant stress.7,101 Still, carbon blacks with low surface areas are sometimes used to develop
rubber compounds with very low hysteresis for LRR in passenger tires. However, other tire
performances such as treadwear and handling characteristics could be negatively affected from the
use of low surface area carbon blacks in tread compounds. As is shown in Figure 18, the abrasion
resistance of rubber compounds is reduced when a low-surface-area carbon black is used.102
It is well known that hysteresis loss is a strong function of the carbon black loading in rubber
compounds. To reduce the hysteresis loss under constant strain and constant energy processes, the
loading of carbon black in the rubber compounds can be reduced. As shown in Figure 19, the use of
low carbon black loading leads to rubber compounds with reduced hysteresis loss at high
temperatures. However, the dynamic stiffness of rubber compounds is also negatively affected
when the loading of carbon black in the rubber compound is reduced. Lower dynamic stiffness of
the tread compounds not only negatively affects the vehicle handling, but also performance and the
treadwear performance of the tire might not be optimized.103
Clearly, both the surface area and loading of carbon black have a significant impact on the
hysteresis loss properties of rubber compounds.104 The hysteresis loss factor of rubber compounds
is proportional to the surface area of conventional carbon blacks and to the square of carbon black
loading, as shown in Eq. 8 below.105

carbon black ðphrÞ 2
Hysteresis loss factor ¼ K 3 surface area ð8Þ
Total compound ðphrÞ
Or alternatively, the hysteresis loss tan d has been shown to closely relate to a simple combined
function of carbon black surface area and loading, or loading-interfacial area parameter in the
rubber compound, UW.
Hystersis loss tand ¼ KUW ¼ qSU2 ð9Þ
where U is the volume fraction of carbon black and W is the interfacial area qSU, wherein q and S
are the density and surface area of carbon black, respectively.104,106–108 As is shown in Figure 20,
Fig. 18. — Abrasion resistances of rubber compounds as measured by Cabot abrader, a Lambourn-type abrasion tester, vs. surface
areas for a variety of carbon blacks in truck tire compounds (NR 100 phr and carbon black 50 phr). (Reprinted from ref 102.)
Fig. 19. — Effect of carbon black loading on hysteresis loss and elastic modulus of truck tire compounds (NR 100 phr and
carbon black loading ranging from 40 to 60 phr). (Unpublished results from Cabot Corporation, December 2015.)
Fig. 20. — Loss tan d correlation with loading-interfacial area parameters for NR vulcanizates. Medium-color furnace
black; N110; N234; N219; N375; þ N351; Y N660. (Reprinted from ref 107.)
the hysteresis loss tan d of rubber compounds correlates well with the UW in conventional carbon
black–based compounds.
Based on such an experimental observation, a ‘‘radical compounding’’ approach has been
proposed for achieving lowered hysteresis loss through reduced loading of highly reinforced
carbon blacks with very high surface areas while still enhancing the treadwear performance of
rubber compounds, as shown in Table 2.105
The impact of the structure of particles on the hysteresis loss of rubber compounds is
complicated. It has been observed that the structure of carbon black is partially broken during
mixing.25 It is believed that reactive surfaces area created can potentially interact with rubber,
leading to strong polymer–particle interaction in the rubber compound. It is therefore expected that
high structure carbon black would lead to less particle–particle network formation from polymer–
particle interaction point of view.25,109,110 It is generally observed that increased carbon black
structure (compressed oil absorption number) raises compound hysteresis at constant strain, but has
little or no effect at constant energy input. At constant stress, the use of higher structure carbon black
TABLE 2
RADICAL COMPOUNDING IN ESBR/BR SYSTEM FOR ENHANCED
TREADWEAR AND REDUCED HYSTERESISa
Tire Tan d at
wear 60 8C
N220, 65 phr black/35 phr oil 100 100

EXP1b, 65/35 116 137c
EXP 1, 58/23 114 138
EXP 1, 50/14 120 116
EXP 1, 40/5 129 89
a
Reprinted from ref 105.
b
150 m2/g product not ordinarily thought of as having the potential to use in a
low-hysteresis application.
c
xxxx.
tends to lower hysteresis loss of rubber compounds.7 As discussed previously, the use of high-
structure carbon blacks would be expected to have a positive impact on the rolling resistance
performance of truck tread compounds where the deformation mode is considered to be stress
controlled.
The increased occluded rubber from the use of carbon blacks with a very high structure leads to
high effective loading volume of carbon black. The compound stiffness is therefore increased at
constant loading of carbon blacks compared with carbon blacks with normal structure.76 Like the
case with carbon blacks with very high surface areas, the radical compounding approach can also be
used for reduced hysteresis loss tan d of rubber compounds when working with carbon black with
very high structure by reducing the loading of the carbon black in the rubber compound while still
maintaining treadwear performance.105,111–115
In general the conventional compounding approaches for reduced hysteresis loss at high
temperatures often lead to compromises in other desirable compound properties or performances
such as dynamic stiffness and abrasion resistance, making it difficult to use such rubber compounds
for LRR tread applications without affecting other tire performances.22 The development of new
materials including elastomers and reinforcing particles is therefore needed to improve the rolling
resistance performance of tread compounds without significantly affecting other critical tire
performance attributes.
D. IMPACT OF PARTICLE DISPERSION ON COMPOUND HYSTERESIS
It is well recognized that dispersion of reinforcing particles in a rubber compound has a

significant impact on the dynamic properties (modulus and hysteresis loss tan d) of the rubber
compound. The early work by Payne116 and Boonstra and Medalia117 clearly demonstrated that, in
general, with improved dispersion of reinforcing particles, the hysteresis loss of rubber compounds
is reduced, resulting in less heat buildup and reduced rolling resistance for tire applications. Hess118
summarized the impact of dispersion on the hysteresis loss properties of rubber compounds and
showed that rebound tends to increase gradually with improved dispersion initially and increases
sharply when the dispersion index is from 95 to 99%, suggesting that the improved microdispersion
(reduction in particle–particle networking) is the major effect. Such results clearly suggested that to
get a maximum benefit for reduced hysteresis from dispersion, nonconventional mixing approaches
need to be developed to achieve very good dispersion of reinforcing particles, especially those
particles that are very difficult to disperse, in rubber compounds. In contrast, it was observed in early
work that rubber compounds with very poor dispersion of reinforcing particles would also exhibit
low hysteresis loss, since undispersed agglomerates act as coarse particles with increased
interparticle distances.117,118
The dispersion of reinforcing particles that are more difficult to disperse in rubber compounds
can be improved through multistage mixing protocols using a conventional mixer such as a
Banbury. An intermeshing mixer that creates a high shear environment can be used to further
improve the dispersion of such reinforcing particles in rubber compounds.119 However, some
caution needs to be exercised when mixing NR-based rubber compounds, since overmixing such
compounds may lead to degradation of the molecular weight of NR, leading to poor compound
properties, even though the dispersion of the reinforcing particles is improved.
Liquid mixing technology can also be used to improve the dispersion of reinforcing particles in
rubber compounds. The dispersion of carbon black, for example, can be significantly improved
through the use of a liquid mixing process technology such as Cabot Corporation’s elastomer
composite (CEC) technology, as shown in Figure 21.120–123 Other than an improvement in tear,
tensile strengths, and flex fatigue life of NR-based rubber compounds (Figure 22), the enhanced
dispersion also leads to close to 15% reduction in hysteresis loss tan d and much reduced Payne
Fig. 21. — Dispersion of carbon black N134 in CEC and dry-mixed compounds. (Reprinted from ref 123.)
effect at high temperatures (Figure 23), desirable for truck tread (on or off the road) applications for
enhanced fuel economy, improved treadwear and cutting, and chipping and chucking
performances.124–126
Other liquid mixing approaches involving water and organic solvents can also be used to
improve the dispersion of reinforcing particles in different elastomeric matrices and to enhance the
silanization reaction of silica-containing rubber compounds, thereby further lowering the hysteresis
loss of rubber compounds at high temperatures.127–134
Fig. 22. — Comparison of properties of NR vulcanizates between CEC and dry-mixed compounds. (Reprinted from ref
123.)
Fig. 23. — Lowered hysteresis loss and reduced Payne effect from CEC compared with dry-mixed compounds, indicating
improved microdispersion and reduced particle–particle networking. (Unpublished results from Cabot Corporation,
December 2015.)
High temperature mixing has been demonstrated to lead to rubber compounds with
significantly reduced flocculation of the reinforcing particles and reduced particle–particle network
formation, resulting in significantly lowered hysteresis loss at high temperatures and reduced heat
buildup of rubber compounds.50,135,136
IV. RECENT DEVELOPMENT OF REINFORCING PARTICLES FOR REDUCED

HYSTERESIS
A variety of reinforcing particles have been developed to reduce the hysteresis of rubber
compounds for LRR tire applications. These materials can be generally classified to rely on various
strategies: morphology control, surface control, and composition control. Some reinforcing
materials from more recent developments are reviewed in this section.
A. ADVANCED MORPHOLOGY CONTROL: AGGREGATE SIZE DISTRIBUTION
At equivalent surface area, carbon blacks with a broad aggregate size distribution produce a
marked reduction in hysteresis of rubber compounds.7 As an example, Cabot Corporation’s new
PROPELTM E series reinforcing carbon black E6 exhibits a broad aggregate size distribution
compared with conventional reinforcing carbon blacks. Associated with the broad aggregate size
distribution are a much reduced Payne effect and much reduced hysteresis when such carbon black
is incorporated into rubber compounds. The use of this type of carbon black in tread applications is
expected to lead to lower rolling resistance of tires, while maintaining the treadwear performance
from good interaction of the carbon black with elastomer as indicated by high bound rubber content
and high surface energy of the carbon black.137
Hess and Chirico138 and McDonald and Hess139 explained the reduced hysteresis from the use
of particles with a broad aggregate size distribution in terms of reduced network formation through a
packing mechanism, that is, the smaller aggregates fit into the spaces between the larger aggregates,
reducing the effective packing volume. Using a simplified model consisting of two particles with
different sizes, Wang et al.76 demonstrated that the distance between two particles is increased when
the two particles are of difference sizes compared with the case when the two particles are of the
same size. The reduced hysteresis loss from the use of reinforcing carbon blacks with a broad
aggregate size distribution is therefore explained in terms of increased particle–particle distance,
hence reduced particle–particle interaction and a reduced tendency to form particle–particle
network in the rubber compound.25
It has been shown that carbon blacks with a very broad aggregate size distribution may lead to
lower treadwear performance.7 Carbon blacks with tailor-made aggregate size distributions are
needed to achieve reduced rolling resistance without affecting treadwear performance of
tires.137,140
B. COMPOSITION CONTROL
Via a cofuming process in the carbon black manufacturing unit, silica can be introduced into
the carbon black aggregates to form a composite particle called a carbon-silica dual phase filler
particle (CSDPF), marketed under ECOBLACKTM series carbon black products.141–143
Depending on the equipment setup and the operational conditions used during the manufacturing
process, the silica phase can be distributed throughout the aggregates or located primarily at the
surface of the carbon black aggregates, as shown schematically in Figure 24.144,145 It has been
demonstrated that the surface of such carbon black is highly active and that there is a high
concentration of the silanol groups on the silica part of the particle surface. A low level of silane
coupling agent is therefore suggested to maximize the properties and performance of rubber
compounds containing such particles.102,145 It is therefore expected that there is strong interaction
of the carbon-silica dual phase particles with polymer through physical as well as chemical
interaction via the use of silane coupling agents.
Fig. 24. — Different silica phase distributions, throughout carbon black aggregates or located primarily at surfaces of
aggregates, depending on unit setup and operational conditions during manufacturing process. (Reprinted from ref 144.)
As is shown in Figure 25, the use of CSDPF 2124 and CSDPF 4210 carbon blacks in NR and
solution SBR/BR leads to rubber compounds with much reduced Payne effect compared with
conventional carbon blacks such as N134 and N234, indicative of less particle–particle networking
and strong particle–polymer interaction. The hysteresis loss at high temperatures is also
significantly reduced when such carbon blacks are used in combination with solution SBR/BR
and NR (Figure 26). Based on the performance requirements for passenger and truck tires, the lab
results suggest that the CRXTM 2000 series carbon black is a good reinforcing particle for truck
tread applications due to its much reduced hysteresis loss at high temperatures and enhanced
reinforcement property,102 whereas the CRX TM 4000 series carbon black is considered to be a good
candidate reinforcing particle for passenger tread applications owning to its lower hysteresis loss at
Fig. 25. — Strain dependence of elastic modulus of SSBR/BR and NR compounds filled with different reinforcing particles
showing much reduced Payne effect of compounds containing CRX2000 and CRX4000 series carbon blacks. (Reprinted
from ref 144.)
Fig. 26. — Temperature dependence of hysteresis loss of SSBR/BR and NR compounds filled with different reinforcing
particles showing much reduced hysteresis loss of compounds containing CRX2000 and CRX4000 series carbon blacks.
high temperatures and enhanced wet skid resistance compared with conventional carbon
blacks.146–148
C. MANUPULATION OF PARTICLE SURFACES
Through controlling the combustion in the reactor and via process variations, carbon blacks
with high surface roughness on a microscopic scale can be produced.111,149,150 As schematically
shown in Figure 27, the carbon blacks are believed to have smaller and more disordered crystallites
and an increased number of active sites on the carbon black surface, leading to stronger interaction
of the carbon black particles with polymers, a weak particle–particle network, and consequently
reduced hysteresis loss, as shown in Figure 28. Based on the improved hysteresis property
observed, the application of such carbon blacks in tread compounds is expected to lead to tires with
reduced rolling resistance, hence improving vehicle fuel economy.149
Carbon black reinforcing particles with 2–10 nm microprotrusions formed on the surface of the
primary particles were found to lead to reduced hysteresis loss at high temperatures without
affecting the abrasion resistance of rubber compounds.151,152
The surface of carbon blacks and other reinforcing particles can be modified using a variety of
chemicals to enhance the interaction between particles and polymers and to reduce the tendency of
the particles to form a network in the rubber compound for improved hysteretic properties of the
compounds.36
Ozone, peroxide, and amine can be used to treat carbon black in a carbon black post-
manufacturing process to introduce different functional groups on the surface of the carbon black.
Fig. 27. — Schematic drawing showing smaller and disordered crystallites from high surface active carbon black compared
with conventional carbon blacks. (Reprinted from ref 111.)
Fig. 28. — Reduction of hysteresis loss tan d at high temperatures from use of high surface active carbon black compared
with conventional carbon blacks. (Reprinted from ref 111.)
The treated carbon black can be used in combination with functionalized solution SBR to enhance
the interaction between carbon black particles and the functional groups on the polymer for reduced
Payne effect and lowered hysteresis loss at high temperatures.73.74
Polysulfide compounds can be used to treat carbon blacks to decrease filler–filler interaction
and to increase filler–polymer interaction for reduced hysteresis.153,154 As is shown in Figure 29,
compared with an untreated carbon black N234 with a slightly higher surface area and a similar
structure, the polysulfide-treated carbon black ES200 gives rise to about 15%–18% reduction of
hysteresis loss tan d at 60 8C when used in NR or in a blend of NR and polybutadiene rubber.155
Heterocyclic compounds including triazole, pyrazole, and imidazole having a sulfur-
containing substituent can also be used to modify the surface of carbon black and other particles to
enhance the interaction of particles with polymer.137,156,157 The application of such modified
carbon blacks (LRR truck) in NR or in a blend of NR and polybutadiene leads to about 30%
reduction in hysteresis loss tan d at high temperatures without affecting other compound properties
that are critical for truck tread applications such as tensile and tear strength, as shown in Figure
30.137
D. DEVELOPMENT OF NANOPARTICLES
Significant efforts have been made in developing nanofillers and in exploring potential
applications of such reinforcing particles for different applications in tires.158,159 Three main
families of nanofillers have attracted most attention for their potential applications for enhanced tire
performance: (1) nanoclay and organoclays, (2) graphene or graphenic nanofillers, and (3) carbon
nanotubes. Other than the expected enhancement of the reinforcement properties of rubber
compounds, nanofillers are explored for applications in different components of the tires such as
tread, inner liner, and other inner components by making use of their unique characteristics in air
impermeability160,161 and thermal and electrical conductivity.162–168 Due to their intrinsic small
sizes, when well-dispersed in rubber compounds, nanofillers, especially with functionalization, are
expected to provide good reinforcement to rubber compounds, hence enhancing the performance of
tires.168–171
Fig. 29. — Reduced hysteresis loss tan d at high temperatures from ES200 in NR, NR/BR blend compared with untreated
reinforcing carbon blacks. (Reprinted from ref 155.)
Nanoclays have been used in combination of functionalized elastomers through a

masterbatching process to achieve good dispersion and to promote strong interaction between
nanoclay particles and polymers for enhanced mechanical properties of rubber compounds.172,173
The inclusion of 7.5 and 10 phr clay particles in such polymer systems results in rubber compounds
with Shore A hardness similar to that of a rubber composition containing 50 phr reinforcing carbon
black and with a 50 and 20% reduction of hysteresis loss tan d at 100 8C, respectively.
Low loading of organoclay has been used in combination with conventional carbon blacks for
reduced hysteresis loss for tire applications while maintaining good reinforcement characteristics of
rubber compounds.174
When well dispersed, graphene particles can also provide superior reinforcement in rubber
compounds at an extremely low loading level.175,176 As shown in Figure 31, the use of only 2.5 and
5 phr graphene leads to a significant enhanced modulus of NR compounds compared with rubber
compounds containing 30 and 50 phr N134, respectively. As shown in Figure 32, extremely low
Payne effect and low hysteresis loss tan d at high temperatures were achieved from the graphene-
Fig. 30. — Use of modified carbon blacks (LRR truck) in NR and in NR/BR blend leads to about 30% reduction in
hysteresis loss tan d at high temperatures without affecting other compound properties critical for truck tread applications.
containing rubber compounds. However, as shown in Figure 31, the reinforcement characteristics
of rubber compounds containing low loading of graphene is not entirely satisfactory for practical
tread applications in tires due to the extremely short elongation at break and very low tensile
strength.
Fig. 31. — Use of only 2.5 and 5 phr graphene leads to significant enhanced modulus of NR compounds comparable with
rubber compounds containing 30 and 50 phr N134, 100 phr NR, 30/50 phr N134, or 2.5/5.0 phr graphene. (Unpublished
results from Cabot Corporation, December 2015.)
Fig. 32. — Extremely low Payne effect and low hysteresis loss tan d from the use of only 2.5 and 5 phr graphene in NR. 100
phr NR, 30/50 phr N134, or 2.5/5.0 phr graphene. (Unpublished results from Cabot Corporation, December 2015.)
The length of a carbon nanotube is of the order of a few micrometers to millimeters, with a
diameter of the order of nanometers. A single nanotube is a hundred times stronger and six times
lighter than steel and exhibits good electrical and thermal conductivity. The material therefore
shows potential applications in improving the electrical and thermal conductivity and in enhancing
the reinforcement of rubber compounds. As in the case of graphene, the need to use a very small
loading level of carbon nanotubes is also expected to provide rubber compounds with reduced
hysteresis loss tan d at high temperatures. However, a combination of low loading of carbon
nanotubes and conventional reinforcing particles such as carbon black seems to give rise to rubber
compounds with better overall performance from the synergetic effect of the hybrid
system.167,168,177,178
V. CHALLENGES IN ADOPTING NEW MATERIALS FOR REDUCED ROLLING

RESISTANCE IN THE TIRE INDUSTRY
It typically take a long time for the tire industry to adopt a new material for applications in
different parts of tires. There are multiple reasons for the slow pace of adoption of new materials by
tire companies. Some of the reasons include the following:
1. Saving fuel for cost savings is important. However, the ability to stop the vehicle under, for
example, wet conditions (wet grip/traction) and to maneuver the vehicle under emergency
situations (handling) will take priority in materials design for tires.
2. Needs to expand and improve materials storage and handling capabilities at the tire plants
for new materials.
3. Tedious testing, both at a lab and large plant scales, to ensure the safety and performance of
tire products.
4. Changes and adjustments in the compound formulations, mixing conditions, and
downstream operations in working with new materials.
5. Higher costs of new materials with improved performance in the early stages of the
materials development and adoption.
6. Need for major capital investments for the materials suppliers to produce new materials.
7. Mismatch of properties and performance of materials prepared from a small-scale

laboratory bench and produced from a large-scale plant operation.
8. Mismatch of performance expectations during early stages of new materials development
due to lack of good communications between materials developers and the tire customers
for the desirable performance to be achieved.
Besides rolling resistance, there are other performance requirements for passenger tires such as
wet and dry grip/traction and handling performances, essential critical to qualities (CTQs) for the
safety of the operators of the motor vehicle.179 The development of new materials for tire treads with
reduced rolling resistance without significantly compromising those performance requirements
will facilitate the adoption of the new materials for tire applications.
Reinforcing particles such as carbon blacks are typically stored in a limited number of silos in
conventional tire plants. The introduction of a new grade of reinforcing materials into the tire plant
requires the installation of new silos or the removal of a grade of existing reinforcing particles at the
tire plant. The use of intermediate bulk containers (IBCs) or supersacks for materials packaging
may help accelerate the process of adopting new reinforcing particles when the plant facility is
equipped with the IBC handling capability.
The ready-to-use elastomer/reinforcing particle composites such as CEC products that
eliminate the need for handling and storage of power materials, together with less impact on the
plant environment and reduced complexity of the mixing operation, can make the adoption of new
materials less painful at the plant level. A reinforcing particle that can provide the function and
performance of several grades of reinforcing particles may make the adoption of the new material a
bit easier.
The correlation between lab-tested dynamic property and tire rolling resistance is more
established than other tire performances such as treadwear and wet grip performance. To assess the
treadwear performance of tread compounds with improved rolling resistance, significant time is
needed to conduct indoor and outdoor road treadwear tests. This is especially true for truck tires
where the treadwear testing could last for months to years.
When exploring other tire components for reduced tire rolling resistance of tires beyond tread
compounds, such as belt compounds and carcass compounds, the adhesion of the compounds with
steel and textile cords under different aging conditions is a vital CTQ from the safety point of view.
Tedious testing will therefore need to be conducted to assess the performance of new rubber
compounds ensure the safe operation of tires. The experimentation cycle of adopting new materials
for those applications tends to be very long.
The positive contribution of silica/silane systems to tire wet traction was well recognized even
in the 1970s, and with proper adjustments of curative packages and use of silane coupling agents,
heat buildup of silica-based compounds could be significantly reduced.180 However, a significant
loss in treadwear from the silica-containing tread compounds prevented the adoption of the
technology for passenger tire applications. The adoption of silica compounds for tire tread
applications in a significant way only occurred in the 1990s when new solution SBR and silane
coupling agents were combined with new mixing technology to achieve reduced rolling resistance
and enhanced wet traction while maintaining the treadwear performance of passenger tires.80
Adoption of silica/silane systems for tire applications was a truly challenging task for the tire
industry. The compound formulation needs to be adjusted when using silica and silane coupling
agents due to different cure behavior of the silica compounds compared with conventional carbon
black–based rubber compounds. The cost of raw materials, both from highly dispersible silica and
silane coupling agents, was very high in the early stage of adoption of the silica/silane technology.
On top of the high materials cost were additional costs associated with extended mixing cycles and
needs for multistage mixing and slower extrusion rates that affected productivity at the tire plant. In
mixing silica compounds, the internal mixer needs to be treated as a reactor rather than simply a
blender to mix all ingredients together—more careful control of mixing times and temperatures
need to be exercised to ensure that good silanization reaction is completed and that no scorching
occurs during mixing to obtain quality tread compounds. Even though fairly commonly used in
passenger tread compounds, silica and silane coupling agents are still not widely used at high
loading levels in truck tread compounds due to poor treadwear performance of the silica-containing
formulation. Significant efforts are still being made in developing silane coupling agents that
improve the interaction of silica with NR.181,182
Similar to silica, many newly developed reinforcing particles that enhance the hysteresis
properties of rubber compounds will not simply be a ‘‘drop-in’’ replacement for existing reinforcing
particles that are used in the tire plant, due to their impact on processing and curing behavior of
rubber compounds. Silica-modified carbon blacks, for example, require the use of a low level of
silane coupling agents to maximize the compound properties and performance.102 Some good
control in mixing time and temperature would be needed to achieve compounds with desirable
performance even though the requirement for time and temperature control is not stringent as in the
case of silica-based compounds. The curative package for compounds containing such reinforcing
particles also needs to be modified to ensure a desirable degree of cure. Similarly, depending on the
types of chemicals used as treatment agents, the use of chemically modified carbon blacks such as
LRR products developed by Cabot Corporation can also lead to different cure behavior of rubber
compounds.156,157 Adjustments of curatives or sometimes anti-reversion agents are needed to
achieve a desirable cure behavior for improved dynamic properties of compounds containing such
modified carbon blacks. Protocols for mixing chemically modified carbon blacks with other
ingredients of rubber compounds might need to be modified to prevent pre-scorching due to the
sensitivity of the treatment agents to high temperatures during mixing.
Like modified carbon black particles, some attention needs to be exercised in mixing
functionalized polymers. Depending on the types of functional groups introduced onto the polymer
chains, mixing at very high temperature and for an extended time may lead to compounds with poor
processability in the downstream operations.
Radial tires, other than other tire performance enhancements such as precise steering/cornering
and improved treadwear, provide better rolling resistance and heat buildup performance than
conventional bias ply-based tires.7,179,183 Interestingly, even though the concept was invented in
the 1940s, radializaion approached 100% in France, only 70% in Western Europe, and as little as
5%–7% in the United States by 1971. Only in the late 1980s did radial tires account for almost 100%
of original equipment passenger tire shipments in the United States and 9 out of 10 replacements.
The historical account for the development of the radial tires and the adoption of the concept
through a long period provide an excellent example of the significant time and effort that is needed
to convert an idea into the reality of a performing tire through materials development, tire design/
test, design and build of a totally different production process, manufacture, marketing, and
adoption of a new tire.183 The following quote from Massoubre outlines well the challenge in
reducing an idea into a reality:
‘‘Here resides the mystery of invention: converging ideas, old concerns, exacting
rationality, a rich experience, a fertile and attentive imagination pave the way. But there is
moment which cannot be planned, when the discoverer deduces, sees and understands at the
same what is at stake. This unique moment is the most beautiful tributes to the freedom of the
Spirit, to the independence of research.’’183
The development and commercialization of the CEC technology provide additional accounts
for fairly significant time and efforts that are needed to produce reinforcing composites to meet the
needs of the tire customers. The development work for the mixing technology was conducted in
mid-1990s, demonstrating improved dispersion of reinforcing particles in NR and enhanced
compound performance.120 However, the technology was not commercialized until much later. It
can be imagined that, due to a significant deviation from the conventional masterbatching process, a
significant amount of effort was needed to develop a process that could be scaled up for making
composites for commercialization and many hurdles needed to be crossed to make the composites
fit for tire applications. One such hurdle was the poor processing characteristics of the early version
of CEC products from the generation of a spike in torque when the reinforced composite material
was introduced into a Banbury or an intermeshing mixer. An innovative packaging method for the
product in the form of loose bale was developed to resolve the issue.122
To accelerate the process for the development and adoption of new materials for reduced
rolling resistance of tires, a close collaboration is required between the materials developer and the
tire company so that the needs and concerns of the tire manufacturer are well understood by the
materials supplier. Focused research and demonstration efforts can then be made through materials
development programs that can generate materials to meet the need of the tire manufacturer. A close
collaboration can also ensure a fast feedback from the tire manufacturer about the performance of
materials so that the materials developer can respond promptly to reduce the development cycle
time.
Advances in multiscale computer modeling and better laboratory test methods to predict on-
road tire performance will play a big role in identification of new material solutions and reduce the
cycle time and costs associated with new materials screening.
VI. SUMMARY
The concerns about the environment impact of greenhouse gas emissions and the fuel
efficiency of motor vehicles put a significant demand for the development of rubber compounds
with low hysteresis loss at high temperatures to reduce the rolling resistance of tires. A variety of
conventional compounding approaches, such as reducing the loading level of reinforcing particles
and using reinforcing particles with lower surface areas, can be used to improve the hysteretic
properties of rubber compounds. However, the treadwear, traction, and handling performance of
tires can be negatively affected from these conventional compounding approaches.
Low Tg elastomers provide the compound designers with an approach to reduce the hysteresis
of rubber compounds at high temperatures at the expense of wet grip performance. The use of
functionalized polymers gives the compounders the flexibility of enhancing the rolling resistance
performance of tires without compromising other critical tire performances such as wet and dry
traction.
Different reinforcing particles using a variety of methods have been developed specifically to
provide the compounding engineers and scientists with new tools to improve the dynamic
properties of rubber compounds. Those new reinforcing particles can enhance the rolling resistance
performance of tires without compromising, or even by improving, other performances of tires.
With the advancement of the nanoparticle technology, materials scientists and engineers will have
additional new tools to further improve the fuel economy and enhance other performances while
reducing the weight of tires.
VII. ACKNOWLEDGEMENTS
The authors thank Cabot Corporation for support and for permission to publish this review.
Discussions with R. Dickinson, A. Kyrlidis, L. M. Chen, J. Choi, S. List, and F. Rumpf and support
from the Cabot Application Service Lab are greatly appreciated.
VIII. REFERENCES
1
European Union Regulation No. 1222/2009 of the European Parliament and of the Council of 25 November 2009 on the
Labelling of Tyres with Respect to Fuel Efficiency and Other Essential Parameters. Official Journal of the European Union
(2009).
2
National Highway Traffic Safety Administration, Factors and Considerations for Establishing a Fuel Efficiency
Regulatory Program for Commercial Medium- and Heavy-Duty Vehicles, Department of Transportation (2010).
3
Environmental Protection Agency and National Highway Traffic Safety Administration, Fuel Efficiency and Greenhouse
Gas Emission Standards and Fuel Efficiency Standards for Medium- and Heavy-Duty Engines and Vehicles – Regulatory
Impact Analysis (2011).
4
EPA, ‘‘SmartWay Technology: About the SmartWay Technology Program,’’ http://www3.epa.gov/smartway/
forpartners/technology.htm. Accessed date December 3, 2015.
5
National Petroleum Council, Advancing Technology for America’s Transportation Future: Fuel and Vehicle System
Analysis, Heavy Duty Engines and Vehicle Analysis (2012).
6
Department of Energy, Research and Development Opportunities for Heavy Duty Trucks, U.S. Department of Energy
Report (2009).
7
W. M. Hess and W. K. Klamp, RUBBER CHEM. TECHNOL. 56, 390 (1983).
8
D. Hall and J. C. Moreland, RUBBER CHEM. TECHNOL. 74, 525 (2001).
9
Argonne National Lab, Evaluation of Fuel Consumption Potential of Medium and Heavy Duty Vehicles through
Modeling and Simulation, Report to National Academy of Sciences, Contract DEPS-BEES-001 (2009).
10
Michelin, The Tyre Rolling Resistance and Fuel Savings, Societe de Technologie Michelin (2003).
11
H. Mouri, Rubber World September, 24 (1996).
12
J. M. Baldwin and D. R. Bauer, RUBBER CHEM. TECHNOL. 81, 338 (2008).
13
S. Laube, J. Shell, and P. Zhang, Paper 2, presented at a Meeting of the Rubber Division, American Chemical Society,
Savannah, April 29–May 1, 2002.
14
D. C. Novakoski, J. A. Shell, and P. Zhang, Paper 47, presented at a Meeting of the Rubber Division, American Chemical
Society, San Francisco, April 28–30, 2003.
15
M. J. Wang, P. Zhang, K. Mahmud, T. Lanoye, and V. Vejins, Tire Technol. Int. (2002).
16
A. I. Medalia, RUBBER CHEM. TECHNOL. 64, 481 (1991).
17
D. J. Schuring and S. Futamura, RUBBER CHEM. TECHNOL. 63, 315 (1990).
18
D. J. Schuring, RUBBER CHEM. TECHNOL. 53, 600 (1980).
19
P. S. Pillai and G. S. Fielding-Russell, RUBBER CHEM. TECHNOL. 65, 444 (1993).
20
S. Ghosh, R. A. Sengupta, M. Kaliske, RUBBER CHEM. TECHNOL. 87, 276 (2014).
21
Bridgestone, Tire and Truck Fuel Efficiency, A New Perspective, Bridgestone/Firestone North America Tire LLC,
Special Edition Four, 2008.
22
H. Mouri and J. E. Hall, Paper 56, presented at the 146th ACS Rubber Division Meeting, Pittsburgh, 1994.
23
S. Futamura, RUBBER CHEM. TECHNOL. 64, 57 (1991).
24
S. Futamura, T. G. Ebbott, A. A. Goldstein, L. R. Hohman, presented at 17th Annual Meeting and Conference on Tire
Scienc and Technolology, Akron, April 28–29, 1998.
25
M. J. Wang, RUBBER CHEM. TECHNOL. 71, 520 (1998).
26
K. L. Ngai and D. J. Plazek, RUBBER CHEM. TECHNOL. 68, 376 (1995).
27
G. Day, ‘‘General Purpose Elastomers and Blends’’ in Rubber Technology Compounding and Testing for Performance, J.
S. Dick, Ed., Hanser, Munich, 2001.
28
A. K. Sircar, M. L. Galaska. S. Rodrigues, and R. P. Chartoff, RUBBER CHEM. TECHNOL. 72, 513 (1999).
29
A. R. Payne and R. E. Whittaker, RUBBER CHEM. TECHNOL. 44, 440 (1971).
30
A. R. Payne, J. Appl. Polym. Sci. 8, 2661 (1965).
31
A. M. Gessler and A. R. Payne, J. Appl. Polym. Sci. 7, 1815 (1963).
32
J. B. Donnet, RUBBER CHEM. TECHNOL. 71, 323 (1998).
33
M. Kluppel, R. H. Schuster, and G. Heinrich, RUBBER CHEM. TECHNOL. 70, 243 (1997).
34
B. B. Boonstra, Polymer 20, 691 (1979).
35
G. Heinrich and M. Kluppel, Adv. Polym. Sci. 160, 1(2002).
36
A. Scurati and C. J. Lin, RUBBER CHEM. TECHNOL. 79, 170 (2006).
37
K. W. Stöckelhuber, A. S. Svistkov, A. G. Pelevin, and G. Heinrich, Macromolecules 44, 4366 (2011).
38
G. Boehm and M. N. Nguyen, J. Appl. Polym. Sci. 55, 1041 (1995).
39
M. Kluppel and G. Heinrich, Kaut. Gummi Kunst. 58, 217 (2005).
40
41
A. Voet and F. R. Cook, RUBBER CHEM. TECHNOL. 41, 1207 (1968).
42
G. Kraus, J. Appl. Polym. Sci. Appl. Polym. Symp. 39, 75 (1984).
43
J. D. Ulmer, RUBBER CHEM. TECHNOL. 69, 15 (1996).
44
P. Bluemler and B. Bluemich, RUBBER CHEM. TECHNOL. 70, 468 (1997).
45
H. Luchow, E. B. Reler, and W. Gronski, RUBBER CHEM. TECHNOL. 70, 747 (1997).
46
H. Lorenz, M. Kluppel, and G. Heinrich, Paper 39, presented at the Fall 178th Technical Meeting of the Rubber Division
of the American Chemical Society, Milwaukee, October 12–14, 2010.
47
J. G. Meier and M. Kluppel, Macromol. Mater. Eng. 293, 12 (2008).
48
G. Heinrich and M. Kluppel, Kaut. Gummi Kunstst. 57, 452 (2004).
49
S. Merabia, P. Sotta, and D. R. Long, Macromolecules 41, 8252 (2008).
50
E. M. Dannenberg, RUBBER CHEM. TECHNOL. 48, 410 (1975).
51
J. G. Maier and D. Goritz, Kaut. Gummi Kunstst. 49, 18 (1996).
52
J. M. Funt, RUBBER CHEM. TECHNOL. 61, 842 (1988).
53
C. Sun, P. Zhang, C. Wrana, R. Schuster, and S. H. Zhao, RUBBER CHEM. TECHNOL. 87, 647 (2014).
54
L. B. Tunnicliffe, A. G. Thomas, K. E. Young, J. A. Stuart, and J. C. Busfield, Paper 68, presented at the Fall 182nd
Technical Meeting of the Rubber Division of the American Chemical Society, Inc., Cincinnati, October 9–11, 2012.
55
A. Bhattacharya, G. Medvedev, and J. M. Caruthers, RUBBER CHEM. TECHNOL. 64, 296 (2011).
56
N. Vleugels, W. Pille-Wolf, W. K. Dierkes, and J. W. M. Noordermeer, RUBBER CHEM. TECHNOL. 88, 65 (2015).
57
S. Futamura and K. C. Hua, Rubber World September, 17 (2010).
58
G. Heinrich and H. B. Dumler, RUBBER CHEM. TECHNOL. 71, 53 (1998).
59
K. A. Grosch, RUBBER CHEM. TECHNOL. 69, 495 (1996).
60
S. L. Aggarwal, I. G. Hargis, R. A. Livibni, R. J. Fabris, and L. F. Marker, ‘‘Structure and Properties of Tire Rubber
Prepared by Anionic Polymerization,’’ in Advances in Elastomers and Rubber Elasticity, J. Lal and J. E. Mark, Eds.,
Plenum Press, New York, 1986.
61
H. D. Brandt, W. Nentwig, N. Rooney, R. T. LaFalair, U. U. Wolf, J. Dueffy, J. E. Puskas, G. Kaszas, M. Drewitt, and S.
Glander, ‘‘Solution Rubber,’’ in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim, 2012.
62
V. R. S. Quiteria, C. A. Serra, J. M. Gomez-Fatou, C. Galan, and L. M. Frga, Angew. Makromol. Chem., 246, 85 (1997).
63
F. Tsutsumi, M. Sakakibara, and N. Oshima, RUBBER CHEM. TECHNOL. 63, 7 (1990).
64
E. J. Blok, P. H. Sandstrom, W. L. Hsu, and A. F. Halasa, U.S. Patent 5,994,448 (to Goodyear), November 30, 1999.
65
J. D. Ulmer, W. L. Hergenrother, and D. F. Lawson, RUBBER CHEM. TECHNOL. 71, 637 (1998).
66
H. D. Feng, X. Y. Zhang, and S. H. Zhao, J. Appl. Polym. Sci. 111, 602 (2009).
67
S. Thiele and S. Rulhoff, U.S. Patent 8,895,684 (to Styron), November 25, 2014.
68
N. Nagata, T. Kobatake, H. Watanabe, A. Ueda, and A. Yoshioka, RUBBER CHEM. TECHNOL. 60, 837 (1987).
69
S. Cambon and D. Thomasson, U.S. Patent Application 20130245186 (to Michelin), September 19, 2013.
70
J. Matsushita and Y. Ozawa, U.S. Patent 8,729,184 (to Bridgestone), May 20, 2014.
71
E. Suzuki and T. E. Hogan, U.S. Patent 8,729,204 (to Bridgestone), May 20, 2014.
72
Y. Y. Yan, U.S. Patent 8,642,706 (to Bridgestone), February 4, 2014.
73
J. Douglas, S. Crossley, J. Hallett, J. Curtis, D. Hardy, T. Gross, N. Steinhauser, A. Lucassen, and H. Kloppenburg, Paper
38, presented at the 180th Technical Meeting of the Rubber Division of the American Chemical Society, Inc., Cleveland,
October 11–13, 2011.
74
C. Herd, C. Edwards, J. Curtis, S. Crossley, K. C. Schomberg, T. Gross, N. Steinhauser, H. L. Kloppenberg, D. Hardy, and
A. Lucassen, U.S. Patent Application 20130046064 (to Columbian and Lanxess), February 21, 2013.
75
N. Steinhauzer, D. Hardy, and T. Gross, U.S. Patent Application 20110021660 (to Lanxess), January 27, 2011.
76
M. J. Wang, S. Wolff, and E. H. Tan, RUBBER CHEM. TECHNOL. 66, 178 (1993).
77
T. A. Okel, S. D. Patkar, and J. E. Bice, Rubber Plastics Technol. 15, 1 (1999).
78
J. T. Byers, Rubber World September, 38 (1998).
79
U. Goerl, A. Hunsche, A. Mueller, and H. G. Koban, RUBBER CHEM. TECHNOL. 70, 608 (1997).
80
R. Pauline, U.S. Patent 5,227,425 (to Michelin), July 13, 1993.
81
W. Dierkes and J. Noordermeer, ‘‘Rubber-Silica Mixing,’’ in Current Topics in Elastomers Research, A. K. Bhowmick,
Ed., CRC Press, Boca Raton, 2008.
82
L. Guy, Y. Bomal, and Ph. Cohet, Kaut. Gummi Kunst. 58, 43 (2005).
83
J. W. Brinke, P. J. van Swaaij, L. A. E. M. Reuvekamp, and J. W. M. Noordermeer, RUBBER CHEM. TECHNOL. 75, 12
(2003).
84
L. A. E. M. Reuvekamp, J. W. ten Brinke, P. J. van Swaaij, and J. W. M. Noordermeer, Kaut. Gummi Kunstst. 55, 41
(2002).
85
S. Wolff, RUBBER CHEM. TECHNOL. 55, 967 (1982).
86
T. E. Hogan, A. Randall, W. L. Hergenrother, and C. J. Lin, Rubber World September, 38 (2010).
87
J. M. Marechal, P. Chaboche, and J. M. Favrot, U.S. Patent 8,344,063 (to Michelin), January 1, 2013.
88
J. L. Cabioch and G. Labauze, U.S. Patent 6,013,718 (to Michelin), January 11, 2000.
89
G. Labauze, U.S. Patent 5,811,479 (to Michelin), September 22, 1998.
90
G. Labauze, U.S. Patent 5,977,238 (to Michelin), November 2, 1999.
91
T. Hamada, H. Fukuoka, H. Komatsu, and T. Fujimaki, U.S. Patent 5,066,721 (to Bridgestone), November 19, 1991.
92
P. Robert and S. Mathreen, U.S. Patent 7,649,042 (to Michelin), January 19, 2010.
93
P. Robert, J. M. Favrot, and C. Frandin-Cohas, U.S. Patent 6,815,473 (to Michelin), November 9, 2004.
94
S. Gandon-Pain, U.S. Patent 7,312,264 (to Michelin), December 25, 2007.
95
G. Lopitaux, D. Vasseur, and F. Varagniat, U.S. Patent Application 20120259043 (to Michelin), October 11, 2012.
96
G. Thielen and F. Schmitz, U.S. Patent 7,671,128 (to Goodyear), March 2, 2010.
97
P. Robert, F. Barbotin, J. M. Favrot, and P. Chaboche, U.S. Patent 8,455,584 (to Michelin), June 4, 2013.
98
T. Kawai, Paper 18, presented at the 182nd Technical Meeting of the ACS Rubber Division, Cincinnati, October 9–11,
2012.
99
K. Tsukimawashi, N. Kobayashi, T. Toyoshima, T. Tadaki, and K. Trigichi, U.S. Patent 7,342,070 (to JSR), March 11,
2008.
100
G. G. Bohn, W. L. Hergenrother, and C. M. Rodemacher, U.S. Patent 7,250,476 (to Bridgestone), July 31, 2007.
101
G. Kraus, RUBBER CHEM. TECHNOL. 51, 297 (1978).
102
M. J. Wang, P. Zhang, and K. Mahmud, RUBBER CHEM. TECHNOL. 74, 124 (2001).
103
N. Tokita, C. H. Shieh, G. B. Ouyang, and W. J. Patterson, Kaut. Gummi Kunst. 47, 416 (1994).
104
A. I. Medalia and S. G. Laube, RUBBER CHEM. TECHNOL. 51, 89 (1978).
105
S. Laube, S. Monthey, and M. J. Wang, ‘‘Compounding with Carbon Black and Oil,’’ in Rubber Technology
Compounding and Testing for Performance, J. S. Dick, Ed., Hanser, Munich, 2001.
106
A. I. Medalia, RUBBER CHEM. TECHNOL. 51, 438 (1978).
107
J. M. Caruthers, R. E. Cohen, and A. I. Medalia, RUBBER CHEM. TECHNOL. 49, 1076 (1976).
108
E. H. Tan and M. J. Wang, ‘‘A New Approach for Studying the Effect of Fills on Dynamic Properties in Natural Rubber,’’
Proceedings of the International Rubber Technology Conference: Current Developments in Product Manufacture and
Applications, Kuala Lumpur, Malaysia, June 16, 1993.
109
S. S. Choi, J. Polym. Sci. 93, 1001 (2004).
110
S. Wolff, M. J. Wang, and E. H. Tan, RUBBER CHEM. TECHNOL. 66, 163 (1993).
111
M. Heinz, R. Friehmelt, and M. Borm, Kaut. Gummi Kunst. 65, 37 (2012).
112
C. H. Shieh, W. A Farr, T. E. McElwain, R. W. Taylor, W. J. Patterson, G. E. Denstaedt, R. R. Juengel, and S. G. Laube,
U.S. Patent 5,393,821 (to Cabot), February 28, 1995.
113
N. Endter and E. C. Mizner, U.S. Patent 5,132,357 (to Goodyear), July 21, 1992.
114
R. A. Swor, W. Hess, and E. Micek. Elastomerics 3, 18 (1991).
115
R. A. Swor, W. Hess, and E. Micek. Elastomerics 4, 30 (1991).
116
117
B. B. Boonstra and A. I. Medalia, Rubber Age 92, 892 (1963).
118
W. M. Hess, RUBBER CHEM. TECHNOL. 64, 386 (1991).
119
F. J. Borzenski and Q. Hartley, Rubber World July, 18 (2013).
120
M. A. Mahry, F. H. Rumpf, I. Z. Podobnik, S. A. Westveer, A. C. Morgan, B. Chung, and M. J. Andrews, U.S. Patent
6,040,364 (to Cabot), March 21, 2000.
121
M. A. Mahry, F. H. Rumpf, I. Z. Podobnik, S. A. Westveer, A. C. Morgan, B. Chung, and M. J. Andrews, U.S. Patent
6,413,478 (to Cabot), July 2, 2002.
122
T. Wang, G. A. McConnell, and M. J. Wang, U.S. Patent 7,341,142 (to) , March 11, 2008.
123
M. J. Wang, Kaut. Gummi Kunst., Dec., 626 (2005).
124
T. Wang, M. J. Wang, J. Shell, Y. L. Wong, and V. Vejins, Paper 24, presented at a Meeting of the Rubber Division,
American Chemical Society, Cleveland, October 14–17, 2003.
125
M. J. Wang, T. Wang, Y. L. Wong, J. Shell, and K. Mahmud, Kaut. Gummi Kunst. 55, 7 (2002).
126
T. Wang, M. J. Wang, J. Shell, and N. Tokita, Kaut. Gummi Kunst. 53, 497 (2002).
127
P. J. Wallen, G. C. Bowman, H. A. Colvin, C. J. Hardiman, and J. E. R. Reyna, U.S. Patent 8,357,733 (to Negromex and
Cooper), January 22, 2013.
128
P. Zhang and S. L. Chen, U.S. Patent 7,307,121 (to Goodyear), December 11, 2007.
129
S. L. Chen and H. A. Colvin, U.S. Patent 7,101,922 (to Goodyear), September 5, 2006.
130
U. Goerl, R. Stober, and M. Schmitt, U.S. Patent 6,878,759 (to Degussa), April 12, 2005.
131
U. Goerl and M. Schmitt, Kaut. Gummi Kunst. 55, 23 (2002).
132
U. Goerl and M. Schmitt, Kaut. Gummi Kunst. 55, 502 (2002).
133
J. W. Lightsey, D. J. Kneilling, and J. M. Long, Rubber World June, 35 (1998).
134
J. W. Lightsey, D. J. Kneilling, and J. M. Long, U.S. Patent 5,763,388 (to DSM Copolymer), June 9, 1998.
135
J. M. Loubaresse, M. Eloy, F. Voishin, G. Huguenot, and J. Loyau, U.S. Patent Application 20140200307 (to Michelin),
July 17, 2014.
136
R. H. Gerke, G. H. Ganzhorn, and L. H. Howland, U.S. Patent 2,118,001 (to US Rubber Products), May 24, 1938.
137
P. Zhang, ‘‘Particle Technologies for Lowering Hysteresis Loss of Rubber Compounds,’’ Paper , presented at IRC2014,
Beijing, September 16–18, 2014.
138
W. M. Hess and V. E. Chirico, RUBBER CHEM. TECHNOL. 50, 301 (1977).
139
G. C. McDonald and W. M. Hess, RUBBER CHEM. TECHNOL. 50, 301 (1977).
140
B. Schwaiger, F. Diehl, W. Niedermeier, and L. Bradley, Paper 41, presented at the Fall 187th Technical Meeting of
Rubber Division, ACS, Cleveland, October 13–15, 2015.
141
K. Mahmud, M. J. Wang, and Y. Kutsovsky, U.S. Patent 6,364,944 (to Cabot), April 2, 2002.
142
K. Mahmud, M. J. Wang, R. A. Francis, and J. Belmont, U.S. Patent 6,028,137 (to Cabot), February 22, 2000.
143
K. Mahmud, M. J. Wang, and R. A. Francis, U.S. Patent 5,948,835 (to Cabot), September 7, 1999.
144
M. J. Wang, Y. Kutsovsky, P. Zhang, G. Mehos, L. J. Murphy, and K. Mahmud, Kaut. Gummi Kunst. 55, 33 (2002).
145
M. J. Wang, Y. Kutsovsky, P. Zhang, L. J. Murphy, S. Laube, and K. Mahmud, RUBBER CHEM. TECHNOL. 75, 247 (2002).
146
M. J. Wang and Y. Kutsovsky, RUBBER CHEM. TECHNOL. 81, 576 (2008).
147
M. J. Wang and Y. Kutsovsky, RUBBER CHEM. TECHNOL. 81, 552 (2008).
148
P. Zhang, M. J. Wang, Y. Kutsovsky, S. Laube, and K. Mahmud, Rubber World April, 43 (2002).
149
H. D. Luginsland and W. Niedermeier, Rubber World September, 34 (2003).
150
C. Vogler, U.S. Patent 6,251,983 (to Degussa), June 26, 2001.
151
Harada and T. Abahane, U.S. Patent 9,145,482 (to Tokai Carbon), January 31, 2015.
152
F. Visel, U. E. Frank, R. J. Zimmer, T. F. E. Materne, and G. Agostini, U.S. Patent 6,121,346 (to Goodyear), September 19,
2000.
153
W. Wampler, B. M. Jacobsson, L. Nikiel, P. D. Cameron, and J. Neilsen, U.S. Patent 9,005,359 (to Sid Richardson), April
14, 2015.
154
M. Jacobsson, P. Cameron, J. Neilsen, L. Nikiel, and W. Wampler, Rubber World February, 22 (2013).
155
M. Jacobsson, P. Cameron, J. Neilsen, L. Nikiel, and W. Wampler, Paper 45, presented at the 182nd Technical Meeting of
the ACS Rubber Division, Cincinnati, October 9–11, 2012.
156
J. A. Belmont and V. R. Tirumala, U.S. Patent 8,975,316 (to Cabot), March 10, 2015.
157
J. A. Belmont, V. R. Tirumala, and P. Zhang, U.S. Patent Application 20150183962 (to Cabot), July 2, 2015.
158
M. Galimberti, V. Cipolletti, S. Musto, S. Cioppa, G. Peli, M. Mauro, G. Gaetano, S. Agnelli, R. Theoni, and V. Kumar,
RUBBER CHEM. TECHNOL. 87, 417 (2014).
159
M. Maiti, M. Bhattacharya, and A. K. Bhowmick, RUBBER CHEM. TECHNOL. 81, 384 (2008).
160
A. Joseph and A. Riou, U.S. Patent 8,304,471 (to Michelin), November 6, 2012.
161
D. Lavialle and J. Besson, U.S. Patent Application 20120175633 (to Michelin), July 12, 2012.
162
L. Du, X. P. Yang, and C. T. Pulford, U.S. Patent Application 20140155544A1 (to Goodyear), June 5, 2014.
163
J. R. Potts, O. Shankar, L. Du, and R. S. Ruoff, Macromolecules 45, 6045 (2012).
164
J. Martin, N. R. Vanier, B. K. Rearick, R. G. Kohlah, T. A. Okel, D. Asay, C. F. Kahle, and C. H. Hung, U.S. Patent
Application 20130296479A1 (to PPG), November 7, 2013.
165
R. Prud’homme and I. A. Aksay, U.S. Patent 8,047,248 (to Princeton University), November 1, 2011.
166
R. Prud’homme, B. Ozbas, I. A. Aksay, R. Register, and D. Adamson, U.S. Patent 7,745,528 (to Princeton University),
June 29, 2010.
167
H. Lorenz, J. Fritzsche, A. Das, K. W. Stockelhuber, R. Jurk, G. Heinrich, and M. Kluppel, Composites Sci. Technol. 69,
2135 (2009).
168
A. Das, K. W. Stockelhuber, R. Jurk, M. Saphiannikova, J. Fritzsche, H. Lorenz, M. Kluppel, and G. Heinrich, Polymer
49, 5176 (2008).
169
M. N. Nanni, L. Giannini, and A. Losttritto, U.S. Patent Application 20140196825A1 (to Pirelli ), July 17, 2014.
170
Z. H. Tang, L. Q. Zhang, W. J. Feng, B. C. Guo. F. Liu, and D. M. Jia, Macromolecules 47, 8663 (2014).
171
B. Ozbas, C. D. O’Neil, R. A. Register, I. A. Aksay, R. K. Peud’homme, and D. H. Adamson, J. Polym. Sci. B. Polym.
Phys. 50, 910 (2012).
172
X. P. Yang, J. J. Kulig, and D. K. Parker, U.S. Patent 7,750,070 (to Goodyear), July 6, 2010.
173
P. H. Sandstrom, P. Zhang, X. P. Yang, J. J. Kulig, A. S. Puhala, and R. L. Dando, U.S. Patent Application 20100078110
(to Goodyear), April 1, 2010.
174
J. A. Gopi, S. K Patel, A. K. Chandra, and D. K. Tripathy, J. Polym. Res. 18, 1625 (2011).
175
J. Yang, M. Tian, Q. X. Jia, J. H. Shi, L. Q. Zhang, S. H. Lim, Z. Z. Yu, and Y. W. Mai, Acta Mater. 55, 6372 (2007).
176
A. Kyrlidis, ‘‘Commercializing Graphene Solutions for Composites and Batteries,’’ presented at Graphene USA, Santa
Clara, November 18–19, 2015.
177
M. Galimberti, M. Coombs, V. Cipolletti, L. Giannini, T. Ricco, S. Pandini, L. Conzatti, M. Mauro, and G. Guerra, Paper,
presented at the 181th Technical Meeting of the Rubber Division of the American Chemical Society, Inc., San Antonio,
April 22–25, 2012.
178
L. Bokobza, M. Rahmani, C. Belin, J. L. Bruneel, and N. E. El Bounia, J. Polym. Sci. 46, 1939 (2008).
179
B. E. Lindemuth, ‘‘An Overview of Tire Technology,’’ in Pneumatic Tire, A. N. Gent and J. D. Walter, Eds., DOT HS 810
561, U.S. Department of Transportation, National Highway Traffic Safety Administration, February, 2006.
180
M. P. Wagner, RUBBER CHEM. TECHNOL. 49, 703 (1976).
181
J. C. A Da Silva, K. Lonchambon, S. Sterin, and A. Vayland, U.S. Patent 9,010,393 (to Michelin), April 21, 2015.
182
L. Guy, M. Fernandez, and S. Sterin, U.S. Patent 8,524,823 (to Rhodia), September 3, 2013.
183
J. M. Massoubre, RUBBER CHEM. TECHNOL. 62, G83 (1989).
[Received January 2016]

Zhang 2016

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Materials Development for Lowering Rolling Resistance of Tires

PING ZHANG,* MICHAEL MORRIS, DHAVAL DOSHI

I. TIRE ROLLING RESISTANCE AND COMPOUND HYSTERESIS

*Corresponding author. Ph: ; email: ping.zhang@cabotcorp.com

DE ¼ p c2o G0 tan d ð4Þ

DE @ x s2o tan d G0 ð5Þ

II. ORIGINS OF HYSTERESIS LOSS FROM USE OF REINFORCING PARTICLES IN

III. APPROACHES TO REDUCE HYSTERESIS LOSS OF RUBBER COMPOUNDS

B. USE OF FUNCTIONALIZED ELASTOMERS WITH REINFORCING PARTICLES

C. PARTICLE MORPHOLOGY AND FORMULAION APPROACHES

N220, 65 phr black/35 phr oil 100 100

D. IMPACT OF PARTICLE DISPERSION ON COMPOUND HYSTERESIS

It is well recognized that dispersion of reinforcing particles in a rubber compound has a

IV. RECENT DEVELOPMENT OF REINFORCING PARTICLES FOR REDUCED

A. ADVANCED MORPHOLOGY CONTROL: AGGREGATE SIZE DISTRIBUTION

C. MANUPULATION OF PARTICLE SURFACES

Nanoclays have been used in combination of functionalized elastomers through a

V. CHALLENGES IN ADOPTING NEW MATERIALS FOR REDUCED ROLLING

7. Mismatch of properties and performance of materials prepared from a small-scale

[Received January 2016]

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