SILICA-REINFORCED EPOXIDIZED NATURAL RUBBER TIRE TREADS —

PERFORMANCE AND DURABILITY

PAMELA J. MARTIN,* PAUL BROWN, ANDREW V. CHAPMAN, STUART COOK

TUN ABDUL RAZAK RESEARCH CENTRE (TARRC), MALAYSIAN RUBBER BOARD,
BRICKENDONBURY, HERTFORD, SG13 8NL, UK

RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

ABSTRACT
Concerns regarding climate change and public health have compelled governments to reduce the environmental
impact of transport. Many countries are introducing tire labeling and legislation targeting rolling resistance, wet grip, and
noise. The proposed U.S. tire label also includes wear performance. Implementation of tire labeling is enabling buyers to
choose better tires. The tire industry is responding to these demands and is developing the next generation of green tires.
Current passenger tire tread technology is primarily petroleum based; however, the long-term availability of fossil-fuel
supplies is limited. Thus a further step to minimize the environmental impact and carbon footprint of tires over their life
cycle is to use sustainable materials not derived from fossil-fuels. Sumitomo Rubber Industries used epoxidized natural
rubber (ENR) reinforced with silica in their route to a greener fossil-fuel free tire (the ENASAVE 100). At 25 mol%
epoxidation, ENR has a glass transition temperature (Tg) most suitable for tread applications. Silica-filled ENR-25 tread
compounds deliver lower rolling resistance, hence reduced fuel consumption, and enhanced wet and ice traction compared
with benchmark premium passenger or truck treads. Optimization of wear performance to extend product durability is a
current focus of research. However, correlation between laboratory abrasion and on-the-road tire wear is notoriously poor.
The Tun Abdul Razak Research Centre (TARRC) have used light microscopy and transmission electron microscopy
(TEM) to ascertain a mechanistic insight into tread wear, using results from wear studies on-the-road and laboratory
abrasion. The results indicate that the mechanism of on-the-road tire wear differs from that of in-laboratory Akron abrasion
tests. [doi:10.5254/rct.15.85940]

INTRODUCTION
The tire is a prerequisite for modern day road transportation. However, most people give tires
little thought, unless they need a replacement. Yet, the unassuming tire is in fact a highly engineered
piece of equipment that, despite years of research, is even today not fully understood. Society is
heavily reliant on tires and the design and technology that has gone into developing them. Tires are
composed of complex multi-component structures, comprising polymeric matrix and reinforce-
ment layers, but the only part of the tire in direct contact with the road is the tread, through an area
known as the contact patch or footprint. It is the contact patch that is largely responsible for motion
and safety.
Increased environmental awareness and concerns regarding climate change and public health
have compelled governments to reduce the environmental impact of transport. Many countries
(Japan, Europe, Turkey, the United States, Brazil, Israel, and Korea) have already introduced, or
propose to introduce, compulsory or voluntary tire labeling and legislation targeting rolling
resistance, wet grip, and noise, which is expected to spread to other countries and thus have a global
impact. Implementation of tire labeling is enabling buyers to choose better tires. The tire industry is
looking for ‘‘greener’’ solutions.
The tread is a major contributor both to rolling resistance and to wet traction.1,2 The tread
compound must be engineered to achieve an optimized balance between rolling resistance, wet
grip, and abrasion resistance properties in tires, often referred to as the ‘‘magic triangle.’’ Since 1992
and the advent of so-called ‘‘green’’ or ‘‘energy tires,’’ silica has become one of the most extensively
used fillers in passenger tire tread compounds.3,4 Replacing carbon-black reinforcement, it provides

*Corresponding author. Email: pmartin@tarrc.co.uk

390
 SILICA-REINFORCED ENR TIRE TREADS 391

a significant reduction in rolling resistance and improvement in wet grip (without significant loss in
wear performance). However, silica-filled compounds, based on non-polar s-SBR and BR, require
the use of a coupling agent (e.g., bis(3-triethoxysilylpropyl)-tetrasulfide (TESPT)) to provide
reinforcement and improve processing and filler dispersion.
During mixing, at temperatures of approximately 145 8C, the coupling agent reacts with
silanol groups on the surface of the silica and generates an alcohol (usually ethanol); this reduces
silica–silica interactions and increases the compatibility of the silica with the rubber. When using
coupling silanes, such as TESPT, covalent chemical bonds between silica and rubber via the
silane are formed during vulcanization, although some coupling may occur during mixing,
especially where temperatures above the recommended boundary of reactive mixing conditions
are allowed, or a more reactive silane coupling agent is used.5 This technology is only now being
applied to bus and truck tires. Natural rubber (NR), a renewable resource, is traditionally the
major constituent in the formulation used for the tread on truck tires, which also includes BR and
carbon black as the reinforcing filler. However, the use of silica filler in truck tread compounds
has not been taken up by the market.6,7 Wolff investigated silane-coupled silica-filled NR in truck
tread tire compounds, finding a significant improvement in rolling resistance while maintaining
the other tire properties.8 Bennett and Brown found a 10% improvement in rolling resistance
when replacing 20% of carbon black with silane-coupled silica in an NR/BR truck tread
compound, while maintaining comparable wear performance.9 The coupling of silica to NR using
conventional silane coupling agents has been claimed to be ineffective, although the reasons are
not well understood. One possible source of the poor coupling may stem from a reduced ability of
the silanes to form covalent bonds with NR during cure.10,11 NR contains non-rubbers, proteins,
fatty acids, phospholipids, and other ester-like substances, which are responsible for its
outstanding properties, but these and/or emulsifiers may also be culpable for competing side
reactions of coupling agents for reaction with silica during mixing and thus affect the final
properties of the compound.12,13 Non-rubbers are also easily absorbed onto the silica surface.14
Recently, new silane products have been emerging on the market specifically targeted at use of
silica as filler in NR.15
In recent years interest has grown in the use of alternative rubbers, in particular the modified
natural rubber, epoxidized natural rubber (ENR), because it is derived from natural rubber and
boasts a negative carbon footprint. Rubber trees sequester 17.5 kg of CO2 per kilogram of rubber
produced, the process of epoxidizing NR uses 7.7 kg of CO2 per kilogram of rubber produced, so
overall there is a net sequestration of 9.8 kg of CO2 per kilogram of ENR-25 produced.16 A suitable
partial or entire replacement for synthetic rubbers is 25 mole percent epoxidized natural rubber
(ENR-25, trade name Ekoprena-25e), which has a similar Tg to that of modern day s-SBR
polymers used in tire treads. ENR tire tread compounds were first developed in these laboratories in
the 1980s, and at that time ENR-25 compounds containing silica or silica/black without use of
coupling silane were shown to give the best performance in terms wet grip and rolling resistance,
when compared with other epoxidation levels and NR or emulsion-SBR.17 In 2013 Sumitomo
Rubber Industries (SRI) launched the ENASAVE 100 as the first completely fossil resource
(petroleum and coal) free tire.18 This tire uses both NR and ENR, with the ENR in the tread,
sidewall, and liner components and silica reinforcement.
Owing to its polarity, ENR develops a significant interaction with silica filler during mixing in
the absence of a silane coupling agent, demonstrated by high bound rubber content and properties
associated with low hysteresis.19–21 Much of the interaction is believed to be a result of hydrogen-
bonding22 between the rubber and silica-filler, and it is sufficiently strong that in passenger tire
treads a coupling agent is not required,19,23 in contrast to standard hydrocarbon rubbers.
Both passenger and truck tread compounds based on silica-filled ENR-25 have been developed
at TARRC with both low rolling resistance and very good wet grip when compared with a
392 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

benchmark commercial low rolling resistance passenger tire that has a silane-coupled silica-
reinforced solution styrene-butadiene rubber/butadiene rubber (s-SBR/BR) tread24,25 or a
conventional black-filled NR/BR truck tread.26 Thus, ENR-silica treads meet the challenges
raised by the tire labeling and legislation, focusing on tire rolling resistance and wet grip.
The proposed U.S. tire label also includes wear performance. Several well-established
laboratory test standards are available to measure abrasion resistance, for example Deutsches
Institut für Normung and Akron tests; however, it is not possible to rely on laboratory testing of
tread compounds alone to predict tire wear rate, since poor correlation with on-road testing is well-
known among tire technologists.27 The wear phenomenon has been extensively studied, and there
are a number of reviews and book chapters dedicated to this complicated and poorly understood
topic.28–33 Wear rates of different tread compounds can rank one way in laboratory tests, only to be
reversed in on-the-road trials. Many diverse parameters constantly change throughout the life of the
tire and influence the rate of wear. These include, but are not limited to, climatic conditions, which
change with the weather and season; speed; load; tire inflation and contact patch area; driving style;
the journey route; road surface texture and material; tire slip angle in relation to the direction of
travel from steering input; acceleration; and breaking. Additionally, the physical properties of the
tire tread compound can change with age, exposure to oxygen and ozone in the air, UV from
sunlight, heat, mechanical work, hysteresis, and tread depth. The stress–strain behavior of the virgin
material in a conventional tensile test may not correspond to that which would be obtained after a
period of deformation during tire usage. Localized strain hardening of an otherwise soft material
may also enable it to resist wearing. Categories of wear are abrasive, adhesive, and erosive, and the
process is thought to involve mechanical failure (fatigue and tearing) and mechano-chemical and
thermo-chemical processes. Generally, the process is known to involve the detachment and
removal of small particles of rubber, 0.6–5 lm in size, probably constituting the basic abrasion
process, and larger pieces 50–100 lm in size torn away from the surface.34–39 Unfortunately, to
date, this phenomenon is not fully understood, and therefore this is considered a primary topic for
discussion.
This paper will discuss the results of the examination of some laboratory Akron abrasion
samples and on-the-road tire wear for two different tire tread compounds, a silica-filled ENR-25
truck tread and a conventional black-filled NR/BR compound. Light microscopy and
transmission electron microscopy (TEM) have been used to view the deteriorated tire tread
rubber and compare the two different wear methods and the two compounds, to try to ascertain a
mechanistic insight into the modes of tread removal. It is hoped this will ultimately assist in
developing a laboratory method (either a physical test or a computer model) for predicting tire
wear more accurately during tire compound development and thus reduce the need for costly and
time consuming road trials.

EXPERIMENTAL
MATERIALS

The following rubber types were used: natural rubber (NR, SMR-10) and 25 mol%
epoxidized natural rubber (Ekoprena, ENR-25), as supplied by the Malaysian Rubber Board, and
cis-1,4 polybutadiene rubber (BR, Europrene Neo cis-BR-40, supplied by Polymeri Europa, now
renamed Versalis). Precipitated silica filler (Zeosil 1165 MP) was used as supplied by Rhodia SA,
now renamed Solvay. This filler is a highly dispersible grade with a Brunauer–Emmett–Teller
surface of 160 m 2 /g and a cetyltrimethylammonium bromide surface of 155 m 2 /g.
Bis(triethoxysilylpropyl) tetrasulfide (TESPT) (Si69) was provided by Evonik AG. The carbon
black, N234 grade (Vulcan 7H), was from Cabot and is a grade suited for tire treads that require
 SILICA-REINFORCED ENR TIRE TREADS 393

TABLE I
COMPOUND FORMULATIONS (PHR)

Compound NR/BR ENR-25

First stage
ENR-25 — 100
SMR-10 70 —
cis-BR 30 —
Silica (Zeosil 1165 MP) — 55
Carbon black (N234) 53 3
Wax 1 1
6PPDa 2.5 1
TMQb 1 1
Zinc oxide 3.5 3
Stearic acid 2.5 3
Calcium stearate — 2
X50Sc — 4.4
Final stage
Sulfur 1.2 0.7
TBBSd 1 1.5
TBzTDe — 0.25
TESPT — 1
a
N-1,3-dimethylbutyl-N 0 -phenyl-p-phenylenediamine.
b
Polymerized 1,2-dihydro-2,2,4-trimethylquinoline.
c
1:1 wt:wt ratio blend of N330 carbon black and bis(triethoxysilylpropyl)-
tetrasulfide.
d
N-tert-butylbenzothiazole-2-sulfenamide.
e
Tetrabenzylthiuram disulfide.

excellent wear resistance.40 X50S is a blend of TESPT and an N330 carbon black (ratio 1:1 by
weight) supplied by Evonik AG. The sulfur, rubber accelerators and antioxidants, zinc oxide,
stearic acid, wax, and calcium stearate were commercial rubber chemicals.

RUBBER COMPOUNDS AND MIXING

The formulations for the truck tread compounds studied are given in Table I. The ENR-25 bus/
truck tire tread formulation is based on 55 phr silica filler with a small amount of N234 black for
color and UV protection and has a low level of silane coupling agent (X50S). For comparison, a
premium retread formulation, N234 black-filled (53 phr) NR/BR (70/30), compound was used. For
both formulations a semi-efficient vulcanization (EV) cure system was used.20 In the case of the
ENR formulation this appears to be rather more efficient, but the TESPT added with the curatives is
acting as a sulfur donor, and while additional accelerator is used, some is consumed in reaction with
epoxide41 and silica.42
Compounds for retreading tires were mixed in a K2A intermix (44 L capacity) with
intermeshing rotors using a three stage mixing procedure with the last stage for adding curatives.
For producing laboratory scale measurements (Akron discs, wet skid test pieces, 1 mm and 2 mm
thick sheets, and hardness buttons), compounds were mixed in a Brabender Polylab (390 ml
394 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

TABLE II
FIRST STAGE MIX CYCLE OF NR/BR BUS/TRUCK TIRE TREAD COMPOUNDS

Time, s Addition

0 Rubber and half black

45 half black
90 Powders
135 Sweep
180 Dump

capacity) internal mixer fitted with a 350S mixing head (Banbury tangential rotors), using a three
stage mixing procedure, with the last stage for adding curatives.
When using a silane coupling agent, it is important that during the first and second stages of
mixing silanization occurs; reaction of silica and silane was achieved by maintaining the batch
temperature at approximately 150 8C for 3 min during mixing. This temperature control was
achieved by adjusting the rotor speed appropriately. For the ENR-based bus/truck tread compounds
it is necessary to use a small amount of silane coupling agent (2.2 phr), because of the higher service
temperatures experienced by bus/truck treads. The operating temperatures of bus/truck treads are
70–90 8C in temperate ambient conditions, which is higher than for passenger tires (approximately
40 8C). This level of silane coupling agent was chosen at TARRC for the formulation, since it was
shown to give satisfactory heat build-up (HBU) for ENR-25 truck tread applications.26
Subsequently, Kaewsakul et al.43 discussed the use of TESPT in silica-filled compounds using
their ‘‘in-house’’ synthesized ENR to reduce filler–filler interaction and improve vulcanization rate
(diphenyl guanidine/N-cyclohexylbenz-thiazylsulfenamide/sulfur cure system) and vulcanizate
properties. They concluded that, for an epoxide content in the range 20–30 mol%, 2–4 wt% of
TESPT relative to the silica content was optimal for laboratory dynamic measurements, which were
used to predict rolling resistance.
Table I also specifies which ingredients were added in each stage. The first stage mix cycles are
given in Tables II and III. In the case of the ENR compound, a longer first mix cycle was followed to
enable the silane to react with the silica. In laboratory scale mixes the temperature was set at 50 8C,
rotor speed at 80 rpm, and fill factor 0.75. The rotor speed was reduced during the mix cycle to 60
rpm to maintain a mix temperature of about 150 8C, and the compound was dumped after 3 minutes
at this temperature. For tire production, compounds were mixed in the K2A, the fill factor was 0.63,
the cooling water was on, and the initial rotor speed was 50 rpm, which was reduced to 25 rpm once
the temperature reached the reactive window.

TABLE III
FIRST STAGE MIX CYCLE OF ENR BUS/TRUCK TIRE TREAD COMPOUNDS

Time, s Addition

0 Rubber and powders

45 5
=
8 (silica and X50S)

90 3
=
8 (silica and X50S)

150 Sweep
Dump after 3 min above 140 8C.
 SILICA-REINFORCED ENR TIRE TREADS 395

The compounds were remilled and batches cross-blended in the internal mixer for 2 min, with
the temperature set at 50 8C, rotor speed at 80 rpm, and fill factor 0.75. For K2A mixes the fill factor
was 0.61 and compounds were remilled for 90 s, obtaining a dump temperature close to 150 8C.
The compounds were finalized with the sulfur cure system in a third mixing stage, where a
batch temperature of no more than 110 8C was allowed to prevent premature curing or scorch of the
compound. A standard semi-EV sulfur/N-t-butyl-2-benzothiazole sulfenamide (TBBS) cure
system was used for black-filled NR/BR and, in the case of ENR-25, a more efficient cure system
including tetrabenzylthiuram disulfide (TBzTD) was used, since some accelerator is lost through
reaction of 2-mercaptobenzothiazole with the epoxide groups,20 and TESPT was added to reduce
any reversion by acting as a sulfur donor.44

RHEOMETRY, MOONEY VISCOSITY, AND CURING

Rheometry was carried out, 1 day after mixing, on a Monsanto MDR 2000E rheometer at 150
8C and 0.58 arc. Mooney viscosities were measured on a Mooney viscometer at ML (1þ4) at 100 8C.
Test pieces (buttons, Akron discs, rubber sliders, and sheets) were cured in compression molds
using a steam or electric press, at 150 8C for 40 or 90 min to model new and typical retreaded truck
tire cure times.

VOLUME SWELLING MEASUREMENTS

Volume swelling measurements were made in duplicate on vulcanized compound by

swelling a weighed amount of compound (250–300 mg) in toluene (25 ml) in a stoppered flask at
room temperature in the dark for 7 days. The swollen rubber was then weighed after removing
excess solvent and then dried under vacuum to constant weight. Volume swelling values were
calculated.
Swelling measurements were also carried out under an atmosphere of ammonia, swelling the
compound in toluene in an open vessel within a closed desiccator that also contained a beaker of
32% aq. ammonia solution.

TIRE RETREADING

Buffed Michelin tire casings size 295/80 R22.5 152/148 M (downgraded to a K after
retreading) were retreaded using a cold-feed strip winding extruder (Orbitread) and cured at 150 8C
for 90 min. This cure time is typical of the retread industry, where heating is from the mold surface
only, thus, there is a considerable overcure on the surface of the tire. The tread pattern used was an
MZA, similar to a Michelin (universal) tread pattern (steer or drive).

PHYSICAL TESTING

Tensile testing was carried out according to ISO 37:2005, BS903:A2. Median values from five
measurements are quoted. Hardness was measured using the ISO 48:2007 method.

WET SKID

Skid resistance was measured using a pendulum apparatus, the British Portable Skid-
Resistance Tester, to BS EN 13036-4 at room temperature (19–22 8C) on wet concrete or outdoors
on wet tarmac or ice at ambient temperature (8 8C and1 8C). The wet concrete block or tarmac test
396 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

surfaces were rewetted after each sweep. Pendulum test values are reported as the average of the last
five swings (of eight swings), per the standard.

FRICTIONAL TESTING

The coefficient of friction was measured under dry conditions and wet with water using a Plint
machine.45 The test surface was silicon carbide paper P500. The speed of the test was 1 mm/s. The
load applied was 10 N, giving a nominal contact pressure of 1 MPa. Friction was tested at room
temperature in summer (27–29 8C). The values are reported as an average of the central 12 mm of
each run, and of six runs made for each sample. Each sample is measured on a fresh piece of the
P500 paper.

WEAR TESTING

Laboratory Akron Abrasion wear testing was done using the method of BS 903: A9: 1988
(Method B), BS ISO 4649: 2002 set to a slip angle of 12.58. Carborundum and fuller’s earth dust
(2:1) was applied to remove debris and stickiness. Test pieces are molded disks, 12.5 mm thick364
mm diameter. The value of abrasion volume loss is reported, and the abrasion resistance index
calculated from the relative volume loss against the standard rubber (S2).
In-service wear trials were undertaken with retreaded bus/truck tires fitted to the rear drive axle
of 50-seater coaches. The tread depths were measured in 24 places across the tire approximately at
monthly intervals. Small samples were cut from the tread after about 18,000 km for examination.
The service was an average of 52 km/day on urban routes.

DYNAMIC MECHANICAL ANALYSIS

Dynamic mechanical analysis (DMA) was undertaken using a Metravib DMAþ1000 test
system (01-dB Metravib, Limonest, France). The DMA system was configured with universal
tension jaw fixtures and was operated via Metravib’s Dynatest software interface, which recorded
the stiffness of the materials and phase shift data, enabling calculation of the modulus and tan d
parameters of interest. Test strips of nominal length 55 mm and width 10.7 mm were cut from
vulcanized 2.2 mm thick sheet for testing. The thickness of each test pieces was measured using a
Mitutoyo digital thickness gauge. A static tensile strain, 2%, and a dynamic strain signal of
amplitude 0.2%, at a frequency of 1 Hz, were applied. Measurements were recorded as a function of
temperature in the range between 80 8C to þ90 8C with a scanning rate of 1 8C/min. The
measurements were made in duplicate. The samples were conditioned for 16 hours under standard
laboratory temperature and humidity conditions.

ROLLING RESISTANCE

The rolling resistance of the retreaded truck tires was measured according to ISO 18164 at 80
km/h on a 1.7 m diameter drum; the results were corrected to 25 8C on a 2 m drum using the method
of the standard.

ROUGHNESS

To quantify the roughness of a surface, the Surtronic 3þ surface roughness machine was used
with the standard pick-up, type 112-1502, with a 5 lm stylus tip radius. A horizontal length of 4 mm
was scanned seven times for each sample, and the result reported as roughness average (Ra) in
 SILICA-REINFORCED ENR TIRE TREADS 397

micrometers. The equipment was calibrated before each use with a reference specimen, type 112/
1534 Ra ¼ 6.0 lm.

‘‘NETWORK VISUALIZATION’’–TRANSMISSION ELECTRON MICROSCOPY46,47

Before use, styrene (99%, Aldrich Chemical Co., St. Louis, MO, USA) was washed free of its
inhibitor with 1.0 M NaOH solution, washed with water, dried over anhydrous calcium chloride,
and then dosed with 10 ppm diphenylpicrylhydrazyl (Aldrich) to inhibit premature styrene
polymerization. The rubber samples were acetone-extracted overnight using a Soxhlet apparatus
and dried in a vacuum oven prior to swelling to equilibrium in a styrene solution containing 2 wt%
di-n-butyl phthalate and 1 wt% benzoyl peroxide or azobisisobutyronitrile as the radical initiator,
for between 2 and 3 days. The swollen sample was then trimmed to approximately 232310 mm in
size before sealing in a gelatin capsule with a covering of the styrene solution. The capsule was then
heated at 68 8C in a metal block to radical initiate polymerization of the styrene. Polymerization,
observed as a hardening of the styrene, was usually completed overnight, although a further period
of heating was used if the capsule had not hardened sufficiently for sectioning.
Ultrathin sections, estimated at between 80 and 120 nm in thickness, were cut from the swollen,
embedded vulcanizate, at ambient temperature, using an RMC PowerTome PC ultra-microtome
with a 458 glass knife fitted with a trough filled with distilled water. Sections were collected on
distilled water on nickel grids and relaxed briefly with xylene vapor. Where appropriate, samples
were alternatively sectioned using the ultra-microtome fitted with a CR-X cryo-unit with a 458
diamond knife. Sections were collected with the aid of ethanol on nickel grids. Sections were either
left unstained or stained using osmium tetroxide vapor for 1 h. The stained and unstained sections
were examined using a Philips CM12 transmission electron microscope operating at 80 kV.

RESULTS AND DISCUSSION

PHYSICAL PROPERTIES

The physical properties of the silica-filled ENR-25 tread compound were roughly matched to
its NR/BR black-filled control. Hardness and tensile test results are compared in Table IV.

ROLLING RESISTANCE

Laboratory dynamic mechanical spectra are used to predict rolling resistance and wet grip
properties for tire compounds which, in the tire, involve frequencies that are too high to be
measured.48 This is achieved by reducing frequencies to a measurable level (e.g., 1 Hz) at lower
temperatures by applying the time–temperature equivalence principle. Loss tangent (tan d), which
is the ratio of dynamic loss modulus (E 0 0 ) to storage modulus (E 0 ), relates to hysteresis and to the
energy loss of the rubber material. An ideal tire compound should give a low tan d at 50–80 8C to
provide low rolling resistance. A low tan d at 60 8C also relates to minimizing the heat build-up of
the tire tread, a concern for truck tires. The dynamic properties of both the black-filled NR/BR and
silica-filled ENR-25 truck tread compounds were measured using temperature sweeps from80 8C
toþ90 8C at a frequency of 1 Hz (E 0 and tan d plots are provided in Figure 1). With tan d at 60 8C as a
predictor of the tread compound’s contribution to tire rolling resistance, this would suggest that the
silica-filled ENR-25 compound has improved rolling resistance compared with the black-filled NR/
BR compound (Table V).
Rolling resistance results of Michelin truck carcasses retreaded with a black-filled NR/BR
formulation currently used in commercial vehicles and a silica-filled ENR-25 formulation are
398 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

TABLE IV
MOONEY VISCOSITY, RHEOMETRY, HARDNESS, AND TENSILE PROPERTIES OF NR/BR AND ENR BUS/TRUCK
TIRE TREAD COMPOUNDS

NR/BR 70/30 ENR-25

Compound 53 phr black 55 phr silica

Mooney viscosity
ML(1þ4) @ 100 8C 65–66.5 50–52.5
Rheometry at 150 8C
ML, dNm 1.57 1.48
MH, dNm 10.93 13.64
MH–ML, dNm 9.25 12.16
tmax, min 24:41 45:56
tS1, min 10:49 7:42
a
Reversion at 40 min, % 0.47
a
Reversion at 90 min, % 3.10
Hardness, IRHD 69 67
Tensile propertiesb
M100, MPa 2.81 2.68
M300, MPa 13.3 14.3
Tensile strength, MPa 25.2 26.0
Elongation at break, % 515 465
a
Torque still rising at 90 min.
b
The physical property data in the table are based on a 90 minute cure time.

compared in Table VI. The tires share the same Michelin casing; thus the contribution for the tread
and the casing can be considered separately. The casing contribution was determined by measuring
the rolling resistance coefficient of a buffed casing; 3.91 kg/tonne load. The whole tire rolling
resistance is relatively high, since retreaded tires are heavier than virgin ones, and a deep tread
pattern was used. The black-filled NR/BR tire has very high rolling resistance compared with the
silica-filled ENR-25 tire. The whole tire rolling resistance of the ENR retreaded tire was 17% lower
than the NR/BR retreaded tire, a whole fuel efficiency class lower. Allowing for the 44% casing
contribution, a 30% drop in tread rolling resistance results; the low rolling resistance predictor of tan
d at 60 8C providing little indication of the magnitude of reduction between the silica-filled ENR-25
and black-filled NR/BR tread compounds (a mere 13% drop, Table V). The cause of this reduction
in rolling resistance is two-fold: first the switch to silica filler, which has been heralded for the
reduction in rolling resistance in passenger tires since 1992,3,4 and second the use of ENR. The
dynamic Tg of ENR-25 differs significantly from that of an NR/BR blend; however, in tests used to
indicate the rolling resistance, such as dynamic measurements recorded at 60 8C, the tan d is
sufficiently far from the glass transition so as not to be affected. For the black-filled NR/BR
compound, the plot of tan d as a function of temperature (Figure 1) is found to be horizontal after the
transition from glass to rubbery states, whereas for the silica-filled ENR-25 compound, tan d
continues to reduce as the temperature increases up to 90 8C. Baker et al.17 showed black-filled
ENR-25 retreaded tires and black-filled NR retreaded tires to have similar rolling resistances. In the
present case, where both silica and carbon-black fillers are used, dispersion of those fillers and
rubber–filler interactions will also influence tan d. Increased rubber–filler interaction compensates
somewhat for a higher Tg, such that tan d at 60 8C for the silica-filled ENR-25 compound has a lower
value, thus indicating lower rolling resistance, but not at 0 8C, suggesting increased wet grip.
 SILICA-REINFORCED ENR TIRE TREADS 399

FIG. 1. — Dynamic mechanical properties E 0 and tan d recorded as a function of temperature with a scanning rate of 1 8C
min1. A static tensile strain, 2%, and a dynamic strain signal of amplitude 0.2%, at a frequency of 1 Hz, were applied.

Similarly, a reduction in rolling resistance is seen for passenger tires where a traditional petroleum-
derived s-SBR/BR silica/silane compound is replaced with ENR-25 and has been reported by
TARRC previously.49 The ability of ENR-25 to reduce hysteresis resides in its interaction with
silica, thought to comprise mainly of hydrogen-bonding interactions,22 and the unusually high
degree of dispersion of silica in ENR-25.50

WET TRACTION

Wet grip is an important safety factor for vehicles. The British Highway Code states that
passenger car stopping distances will be at least doubled in wet51 conditions and ten times greater in
icy or snowy weather than on dry roads,52 because the tires have less grip on the road. Motorists
consider stopping distance for passenger vehicles an important safety factor, but for haulage
companies the focus is more on tire longevity and fuel savings. The stopping distance of a truck is
much greater, since it has more inertia, and it will change when loaded compared with unloaded;

TABLE V
DYNAMIC MECHANICAL ANALYSIS ‘‘PREDICTOR VALUES’’a

Tan d Tan d at 0 8C Tan d at 60 8C

Tire compound peak temperature, 8C (wet skid) (rolling resistance)

Black-filled NR/BR tread 59.3 0.145 0.143

Silica-filled ENR-25 tread 27.4 0.261 0.125
a
Values are the mean of the duplicate runs
400 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

TABLE VI
TIRE ROLLING RESISTANCEa

Tire Rolling resistance coefficient Contribution of the treadb

Black-filled NR/BR tread 8.88 4.97

Silica-filled ENR-25 tread 7.4 3.49
a
Drum rolling resistance to ISO 18164: 2005; tire size: 295/80 R22.5 152/148 K; 80 kph, 85% load (3017.5 kg) measured on
a 1.7 m diameter drum; the results were corrected to a 2 m drum using the method of the standard.
b
Based on 3.91 casing contribution.

however, no information regarding stopping distances of commercial vehicles is included in the

British Highway Code.
Wet skid has been measured using the British Portable Skid-Resistance Tester (BPSRT), both
in the laboratory using a concrete slab surface and outside on tarmac and ice. The British Portable
Skid-Resistance Tester test was first developed in the 1940s for slip resistance of floors in
government buildings and was later redesigned by the UK Transport Research Laboratory.
Nowadays it is a common method used to check the resistance of both wet and dry surfaces to
slipping and skidding, and due to its portable nature it can be used both on site and in the laboratory,
with results from laboratory testing being considered reliably comparable to real life situations. It
measures the frictional resistance between a rubber slider mounted on the end of a pendulum arm
and the surface.
As shown in Table VII, the ENR-25 bus/truck tread compound performs much better than the
black-filled NR/BR compound: the BPSRT values are larger, which equates to shorter stopping
distances on the road. Similarly, silica-filled ENR-25 passenger tire treads have been shown to
perform better than silica-filled s-SBR/BR compounds.25,53 It is believed that water reversibly
reduces the ENR-to-silica interaction at the road–tire interface, increasing hysteresis and thus
improving the wet grip.12
Laboratory dynamic mechanical analysis of tire tread compounds using reduced frequencies at
lower temperatures has been used to predict the wet skid properties of tire compounds by
assessment of the glass–rubber transition zone (between the Tg and plateau region of E 0 ).48,54 The
position of the Tg peak alone is insufficient to be used as criterion for wet skid resistance; a higher Tg
is taken to correspond to higher wet skid performance, however, other factors influence the wet skid
performance aside from the Tg temperature of the elastomer. Within the transition zone, which is
between20 8C and 0 8C for the silica-filled ENR-25 compound (Figure 1), a high tan d is desirable
for good ice grip and wet grip properties. It is noted also that tan d at 0 8C is often quoted as a
predictor for wet grip properties.55,56 In addition to the BPSRT, the tan d values from dynamic
mechanical analysis also suggest that the silica-filled ENR-25 bus/truck tread compound has
improved wet traction properties when compared with the black-filled NR/BR compound (Table

TABLE VII
BRITISH PENDULUM SKID TESTING

Pendulum skid, BPSRT number

Tire compound Wet concrete Wet tarmac Ice

Black-filled NR/BR tread 64.6 59 30.6

Silica-filled ENR-25 tread 75.6 75 40
 SILICA-REINFORCED ENR TIRE TREADS 401

FIG. 2. — Plint data: friction against silicon carbide paper P500 at 1 mm/s with a 10 N load applied.

V). In the case of the bus/truck tread compound, the BPSRT confirms the prediction of the dynamic
mechanical thermal spectroscopy.
Frictional testing using a Plint machine to obtain the coefficient of friction on silicon carbide
P500 paper showed that, in both wet and dry conditions, the silica-filled ENR-25 truck tread has a
greater coefficient of friction compared with the black-filled NR/BR tread compound (Figure 2).
The coefficient of friction measured for the black-filled NR/BR tread compound did not change
between dry and wet runs; however, an interesting reduction in the coefficient of friction occurs for
the silica-filled tread compound where water is present. Notwithstanding this reduction in the
coefficient of friction, the ENR-25 bus/truck tread still has better grip than the NR/BR tread. It is
known that water modifies the ENR-25–silica interaction in the compound, and this in turn changes
the physical properties of the surface of the tread; tensile measurements on silica-filled ENR-25–
based passenger treads for samples before and after exposure to water (28 days) and after
subsequent drying (4 days over KOH) provide an insight into the role of water.57 The modulus of the
ENR-25 compound was lower with absorbed water; after drying, the compound stiffened in
comparison with both the sample without exposure to water and after soaking in water,
demonstrating the reversible nature of the interaction.

TABLE VIII
LABORATORY WEAR: AKRON ABRASION

Abrasion Calculated loss

Tire compound resistance index, % Volume loss, mm3 per cycle, nm

Black-filled NR/BR tread 119 17.7 1.3

Silica-filled ENR-25 tread 220 9.6 0.7
402 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

TABLE IX
IN-SERVICE WEAR: COACH TRIALS

Distance covered Calculated depth loss

Tire in period, km Average km/day per revolution, nma

Black-filled NR/BR tread 18,014 52 0.803

Silica-filled ENR-25 tread 18,014 52 1.258
a
Calculation based on 3.3 m circumference of truck tire.

WEAR

Good abrasion resistance is essential for tires. The wear performance of the two tread materials
(black-filled NR/BR and silica-filled ENR-25) was assessed by laboratory Akron abrasion
measurement and in-service wear trials of retreaded tires fitted to coaches. The Akron abrasion
resistance index is the wear performance of the sample relative to the Standard, which is a 50 phr
black-filled NR compound. The results of the laboratory wear test are given in Table VIII: as
expressed by the abrasion index, the silica-filled ENR-25 tread outperforms the black-filled NR/BR
control by a factor of almost two.
The abrasion results from in-service coach tread wear trials of the two bus/truck tread
compounds is calculated as nanometers worn per revolution and are reported in Table IX. TARRC
had no control over the type of usage the coaches experienced and had tread depth measurements
and samples taken when access to the vehicle could be gained. However, the first 18,000 km usage
over the winter and spring period could be classified as urban. This type of journey would involve
school runs with a lot of maneuvering at lower speeds on tight roads with vehicles parked on either
side. The opposite abrasion resistance ranking is found in the on-the-road testing as compared with
the laboratory Akron testing.
Samples of the two tread materials (silica-filled ENR-25 and black-filled NR/BR) were taken
from the laboratory Akron abrasion test pieces and from retreaded tires under test by the coach test
fleet. The worn surfaces were assessed by light microscopy and TEM.
Light microscopy (LM) showed the Akron test pieces to have a pattern of ridges parallel to the
rotation direction of the disc (Figure 3). The pitch of the ridges varied across the width of the test
piece, with the smaller pitch at the area in less contact with the abrasive wheel at the 12.58 slip angle.

FIG. 3. — Light microscope images of the surfaces of worn Akron abrasion discs (a) black-filled NR/BR and (b) silica-filled
ENR-25 tire tread compounds. The rotation direction of the disc points horizontally toward the right. Illumination came from
the bottom left at a fairly low angle.
 SILICA-REINFORCED ENR TIRE TREADS 403

FIG. 4. — Light microscope image of the surface of worn truck treads, (a) black-filled NR/BR and (b) silica-filled ENR-25.
The rotation direction of the tire is horizontal. Illumination came from the bottom left at a fairly low angle.

The Akron abrasion test is much more severe than normal tire wear on the road. It is thought that
these ridges are formed from the brutal scoring of the abrasive disc and the action of the
carborundum and fuller’s earth scraping and becoming embedded in the surface of the disc as it
rotates. The carborundum and fuller’s earth are used to prevent the abraded rubber sticking to the
abrasive wheel and the production of a sticky layer of degraded rubber on the abrasive wheel.58 This
also mimics road detritus: the dust particles can be seen in the LM images (Figure 3).
Light microscopy for the bus/truck coach tread conversely showed a pattern of ridges
perpendicular to the wear direction (Figure 4). This distinct abrasion pattern only appears to occur
for the NR/BR coach tread used as the control/reference (Figure 4a) for the ENR-25 treads, whose
abraded surface is shown in Figure 4b. This type of characteristic abrasion pattern, as first
characterized by Schallamach in these laboratories, occurs where the sample has been subjected to
sliding abrasion.59 Much work has gone into assessing the cause of such periodic patterns in
treads,59–64 and this topic will not be covered here. In these coach tire tread samples the
perpendicular pattern is thought to occur through the forces acting on the tire during acceleration
and braking, because the tire is situated on the coach at the rear drive axle and experiencing
essentially uniaxial abrasion, as opposed to the steer axle, which would see much more variation in
slip angle and intrinsic abrasion. The roughness of some sample surfaces was measured using the
Surtronic 3þsurface roughness machine, which drags a stylus across the sample: the results showed
as anticipated that a coarser surface corresponds to a higher wear rate.65 The roughness for the tire
samples taken after urban usage was Ra¼7.3 lm for the silica-filled tread compared to Ra¼3.3 lm
for the carbon-black-filled NR/BR tread. There is a difference in friction between the two sets of
tires on the coach: where the NR/BR tire tread has a lower coefficient of friction, it may be
anticipated more sliding will occur for this tire, increasing the tendency for an abrasion pattern to
form.
‘‘Network visualization’’–Transmission electron microscopy is a useful tool for observing
rubber–filler interactions23 and filler micro-dispersion by particle size distribution.50 ‘‘Network
visualization’’ has previously been applied to a variety of elastomer systems,47,66 aiding in the
understanding of polymer blends, cross-link and filler distribution, and the polymer interfaces in
these systems.46,47 The rubber sample, normally vulcanized, is swollen to equilibrium in a
polymerizable solvent, usually styrene, containing a radical initiator. The sample is then heated to
initiate polymerization of the monomer solvent, and, once hardened, the result is a swollen rubber
sample embedded in a polymer matrix, which is then sectioned for TEM analysis. Sections stained
404 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

FIG. 5. — Unstained–TEM micrographs of (a) black-filled NR/BR and (b) silica-filled ENR-25 tire tread compounds taken
from the worn surfaces of Akron abrasion test pieces.

with osmium tetroxide enable the unsaturated rubber chains to be identified. During the monomer
polymerization process, a constrained phase separation occurs. For vulcanized samples it is usual to
see an image showing a mesh structure consisting of regions of stained rubber network separated by
regions of unstained polymer matrix. The dimensions of the phase separated mesh structure can be
related semi-empirically to the physical cross-link density of the vulcanized sample.47 Network
visualization has generally been used to characterize interfaces within composite materials.
Ladouce-Stelandre et al.67 exploited this method to demonstrate the effectiveness of coupling
agents in silica-filled s-SBR and successfully demonstrated this by visualization of voids (vacuoles)
around the filler particles. These ‘‘vacuoles’’ form around the silica particles in SBR without
coupling agent, because the styrene, during the swelling process and the subsequent
polymerization, has been able to penetrate between the rubber and filler where there is little or
no rubber–filler interaction. However, with a coupling silane, giving a good filler–polymer
interaction, these vacuoles are not present. For ENR, even without the use of coupling silane, there
is good interaction and no vacuoles are observed. In this study, the network visualization technique
was used to examine the microstructure of the abraded surfaces from Akron abrasion test pieces and
from samples cut from coach tire treads undergoing in-service wear testing after about 18,000 km.
A previous study by Smith and Veith68 of black-filled (75 phr, N285) SBR tire treads worn
using a trailer operating at a higher severity (1.58 slip angle) also looked at a cross-section through
tread samples. Using the ebonite method69 to harden but not swell the sample, Smith and Veith68
reported the beginning of porosity of a very small size within the subsurface; the article, however,
does not mention the origin of the holes. They also observed road silt submerged below the surface
of the degraded layer. The tire surface layer differs from the bulk due to stress softening and set
resulting from repeated cyclical high level stresses when the wheel is in motion. For black-filled
compounds, the loss of electrical conductivity after abrasion was used to suggest that the surface
deformation had broken the black structure.70
The filler morphology and its micro- and macro-dispersions are generally regarded as being
important for abrasion resistance. Macro-dispersion was measured optically at low magnification
(DisperGrader). Micro-dispersion of silica-filled samples is measured by assessing the aggregate size
distribution evaluated by image analysis of TEM micrographs of unstained ‘‘network visualization’’
sections.50 Work to date shows silica to have exceptional micro-dispersion in ENR compounds.71
Figure 5 compares two TEM micrographs of cross-sections of the surface layer of samples
taken from Akron abrasion discs of black-filled NR/BR and silica-filled ENR-25 tread compound.
These micrographs are unstained; the rubber cannot be seen, so that the carbon-black and silica
 SILICA-REINFORCED ENR TIRE TREADS 405

TABLE X
VOLUME SWELLING: TOLUENE

Vr in toluene
Tire Vr in toluene exposed to ammonia

Black-filled NR/BR tread 0.218 0.211

Silica-filled ENR-25 tread 0.224 0.202

aggregates are more readily observed. Foreign particles can also be observed on or within the rubber
sample; these are particles of carborundum and fuller’s earth, the latter having clay particles whose
layered structure can be seen. The two compounds appear to have been swollen to different extents
within the styrene–polymer matrix, with images of the black-filled NR/BR sample appearing to
contain less filler. However, the results from bulk volume swelling in toluene shown in Table X are
relatively similar. Swelling in toluene is expected to be similar to that of styrene, since the solubility
parameters are similar.72
Rubber–filler interaction is important for wear resistance, and poor rubber–filler coupling will
result in poor abrasion resistance. Network visualization–TEM micrographs of sections of the
unsaturated rubber stained by osmium tetroxide to visualize the rubber network are shown in Figure
6. These were taken from the worn surfaces of Akron abrasion test pieces. The rubber surface is
supported by the polystyrene above. In the NR/BR compounds the BR phase (minor phase) has
stained darker than the NR phase, and it is here or on the phase boundary that most of the black
appears to be located. This is consistent with work by Hess et al. assessing carbon-black distribution
in NR/BR blends.66 Although it is not known whether the areas examined under TEM
magnification are located on the top surface of scored ridges or at the bottom, there appears to be
good interaction between the NR/BR and carbon black. For the silica-filled ENR-25 tread
compound the rubber network is visible as a fine mesh; there is good interaction between the rubber
and filler observed.
Figures 7 and 8 show the analogous network visualization images (TEM micrographs) of the
black-filled NR/BR and silica-filled ENR-25 tire tread compounds taken from tire tread samples
that have been run on the road. The rubber network around the filler particles and linking the filler
particles is made visible by staining. This shows vacuoles (regions of polystyrene) around the filler
particles, suggesting that the rubber–filler network was weak enough for polystyrene to nucleate
and grow between the rubber and silica. There appears to be a reduction in the volume fraction of

FIG. 6. — Stained ‘‘network visualization’’–TEM micrographs of (a) black-filled NR/BR and (b) silica-filled ENR-25 tire
tread compound taken from the worn surface of Akron abrasion test pieces.
406 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

FIG. 7. — Stained ‘‘network visualization’’–TEM micrographs of (a) black-filled NR/BR and (b) silica-filled ENR-25 tire
tread compounds taken from the worn surface of in-service truck treads. In (c) and (d) some of the voids are highlighted.

rubber at the surface resulting from the reduction in rubber–filler interaction, together with a
breakdown in the rubber network, possibly through oxidation. It is plausible that the high local
strains around these weakened parts of the network would lead to a gradual opening up of the
network and eventual detachment of vulcanized particles. Such particles that had been detached,
either partially or completely, were observed; an example of this is shown in Figure 9. Voided
regions, surrounding filler particles, are not seen within the bulk network of either the black-filled
NR/BR tread compound or the silica-filled ENR-25 compound; Figures 10 and 11, respectively,
both show good, coherent rubber–filler networks.
The above observations indicate that a possible refinement of existing mechanisms of tire
abrasion is the weakening of rubber–filler interactions, visualized using TEM as the formation of
voids around filler particles. It may be seen that repeated cyclical deformation of the tread blocks as
the tire rotates and the high local stresses seen at the surface of the tire tread generated by road
asperities are responsible for degradation of the rubber–filler interface. Oxidation close to the
surface may also be involved. Localized high temperatures generated during service will weaken
any hydrogen-bonding type rubber–filler interactions, although this effect is reversible; however
the ENR truck tire tread system is partially silane-coupled, and any breaking of this coupling or of
the polymer chains themselves would be permanent. NR/BR binding to carbon black is mainly, if
not entirely, a physical interaction, which will also break at high temperatures.73,74 Such weakened
parts of the network, once initiated, are believed to propagate sub-surface and surface cracks/
fractures in the tread when the tread is further deformed.
We propose that the progressive failure of rubber–filler interaction through fatigue processes at
the interface is visualized using TEM as the formation of voids around the filler particles. It may be
reasonable that if these weakened regions are rendered more difficult to create, the wear process
 SILICA-REINFORCED ENR TIRE TREADS 407

FIG. 8. — Stained ‘‘network visualization’’–TEM micrographs of (a) black-filled NR/BR and (b) silica-filled ENR-25 tire
tread compounds taken from the worn surface of in-service truck treads. In (c) and (d) some of the voids are highlighted.

might be expected to be retarded. This is consistent with observations in the laboratory that abrasion
resistance is enhanced when silane levels and silanization are increased in compounds. These
observations are consistent with the work published by Ladouce-Stelandre et al.,67 in which
vacuoles were only observed in filled vulcanizates (silica-filled s-SBR) where a threshold silane
level exists, above which the rubber–filler interface is strong enough to minimize the Payne Effect.
Levels of coupling agent used in silica-filled tire tread compounds are normally above such a
threshold. It may be of benefit therefore to investigate the size and frequency of the vacuoles seen at
the surface in abraded rubber compounds and to relate this to wear.

FIG. 9. — Unstained–TEM micrograph of silica-filled ENR-25 tire tread compound taken from the worn surface of in-
service truck tread. (a) Without labels (b) labeled.
408 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 88, No. 3, pp. 390–411 (2015)

FIG. 10. — Stained ‘‘network visualization’’–TEM micrographs of (a) black-filled NR/BR and (b) silica-filled ENR-25 tire
tread compounds taken from deep within Akron abrasion test pieces.

CONCLUSIONS
TARRC has developed silica-filled ENR tire treads providing very low rolling resistance and
excellent wet grip for both passenger and bus/truck applications, when compared with a benchmark
commercial low rolling resistance passenger tire that has a silane-coupled silica-reinforced solution
styrene-butadiene rubber/butadiene rubber (s-SBR/BR) tread24,25 or a conventional black-filled
NR/BR truck tread. Use of this ecologically sustainable rubber, with its negative carbon footprint,
provides a route to greener tires. Wear tests under different conditions, in the laboratory (Akron
abrasion test) and on the road, have been carried out, which show a reversal of ranking depending
upon test conditions. These results demonstrate that correlation between laboratory abrasion and
on-the-road tire wear is poor. The worn surfaces have been examined using LM and TEM
techniques. By LM, scoring of the Akron test piece surface was observed, while for the tire tread
samples, characteristic abrasion patterns were seen for black-filled NR/BR tire treads but not for
silica-filled ENR tire treads. For TEM, the samples were embedded in a polystyrene matrix and the
rubber silica network viewed (both stained and unstained). For on-the-road worn samples, road
debris and detritus made assessment of the surface particularly challenging. The mechanisms of
wear for black-filled NR/BR and silica-filled ENR appear to have similarities with evidence of
failure of the rubber–filler interface in close proximity to the tread surface, visualized as voids that
form around the filler particles when embedded in polystyrene and resulting in a reduction in the

FIG. 11. — Stained ‘‘network visualization’’–TEM micrographs of (a) black-filled NR/BR and (b) silica-filled ENR-25 tire
tread compound taken from deep within in-service truck treads.
 SILICA-REINFORCED ENR TIRE TREADS 409

volume fraction of rubber. Comparison of laboratory and road wear TEM micrographs illustrates
that the mechanism of wear is quite dissimilar between Akron abrasion tests and on-the-road tire
wear. The Akron abrasion test is much more severe than normal tire wear, but the test pieces did not
show breakdown in the filler–rubber interface at the abraded surface. Work investigating the
surface of worn passenger and bus/truck treads (by TEM) will continue, and comparisons between
surfaces worn at different severities will be made.

ACKNOWLEDGEMENTS
The authors would like to thank John Peters for organizing the road wear studies and conducting
the measurements with Don Nicholson; South Mimms Travel for use of their vehicles; Jonathon
Clark for wet skid measurements and preparation of test pieces; Sarah Moazami, Ruth Barnett, Cath
Zouine, and Glynis Mewitt for Akron, tensile, and hardness testing; Charlie Forge for the dynamic
measurements; John Kingston for assistance with use of the Plint machine; and Robin Davies, Kathy
Lawrence, and Jolanta Bonfante for transmission electron microscopy work. The authors would also
like to thank the Tun Abdul Razak Research Centre for permission to publish this work.

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[Paper 84, Presented at the Fall 186th Technical Meeting of Rubber Division, ACS (Nashville, TN), 14–16 October 2014]

[Received September 2014, Revised April 2015]