Construction

and Building

MATERIALS

Construction and Building Materials 21 (2007) 6672

www.elsevier.com/locate/conbuildmat

Polymer modied asphalt binders

Yetkin Yildirim

Department of Civil Engineering, University of Texas at Austin, 3208 Red River CTR 318, Austin, TX 78705, USA
Received 19 August 2004; received in revised form 5 July 2005; accepted 21 July 2005
Available online 19 September 2005

Abstract
This paper is a review of research that has been conducted on polymer modied binders over the last three decades. Polymer
modication of asphalt binders has increasingly become the norm in designing optimally performing pavements, particularly in
the United States, Canada, Europe and Australia. Specic polymers that have been used include rubber, SBR, SBS and Elvaloy.
Specications have been designed and pre-existing ones modied to capture the rheological properties of polymer modied binders.
The elastic recovery test is good at determining the presence of polymers in an asphalt binder, but is less successful at predicting eld
performance of the pavement.
2005 Elsevier Ltd. All rights reserved.
Keywords: Polymer modied binder; Asphalt; Binder specications; Elastic recovery; SBR; SBS; Elvaloy; Rubber

1. Introduction

2. History, use, and benets

The addition of polymers, chains of repeated small

molecules, to asphalt has been shown to improve performance. Pavement with polymer modication exhibits greater resistance to rutting and thermal cracking,
and decreased fatigue damage, stripping and temperature susceptibility. Polymer modied binders have
been used with success at locations of high stress, such
as intersections of busy streets, airports, vehicle weigh
stations, and race tracks [1]. Polymers that have been
used to modify asphalt include styrenebutadienestyrene (SBS), styrenebutadiene rubber (SBR), Elvaloy,
rubber, ethylene vinyl acetate (EVA), polyethylene,
and others. Desirable characteristics of polymer modied binders include greater elastic recovery, a higher
softening point, greater viscosity, greater cohesive
strength and greater ductility [1,2].

Processes of asphalt modication involving natural

and synthetic polymers were patented as early as 1843
[3]. Test projects were underway in Europe in the
1930s, and neoprene latex began to be used in North
America in the 1950s [1]. In the late 1970s, Europe
was ahead of the United States in the use of modied asphalts because the European use of contractors, who
provided warranties, motivated a greater interest in decreased life cycle costs, even at higher initial costs. The
high preliminary expenses for polymer modied asphalt
limited its use in the US [4]. In the mid-1980s, newer
polymers were developed and European technologies
began to be used in the US [5,6]. At the same time,
the prevalence of a long-term economic outlook in the
country increased [1]. In Australia, the current National
Asphalt Specication includes guides and specications
regarding polymer modied binders [7].
The United States Federal Highway Administration
(FHWA) has developed a life cycle cost analysis approach, which can be used to evaluate the life cycle costs

Tel.: +1 512 232 1845; fax: +1 512 475 7914.

E-mail address: yetkin@mail.utexas.edu.

0950-0618/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2005.07.007

Y. Yildirim / Construction and Building Materials 21 (2007) 6672

of pavement containing asphalt rubber binders as well

as other treatments. The ndings indicated that asphalt
rubber is cost eective as it is used, for example, in Arizona and California, although the estimated life of the
pavement is based on interviews and engineering judgment, and can be rened as the pavement ages and
long-term eld performance is included in the model [8].
A 1997 survey of state departments of transportation
in the United States found that 47 states of the 50 reported that they would be using modied binders in
the future, 35 of them saying that they would use greater
amounts [9]. Several research teams around the world
have worked on evaluating the benets of polymer modication on pavement performance, and tests and specications for binders are continually being developed.
In a 2001 study for the Ohio Department of Transportation, Sargand and Kim [10] compared the fatigue
and rutting resistance of three PG 7022 binders, one
unmodied, one SBS modied, and one SBR modied.
It was found that the modied binders were more resistant to both fatigue and rutting than the neat binder,
even though all three had the same performance grade.
According to a 2003 Nevada study, the viscosity of
polymer modied binders tends to be signicantly
greater than that of non-modied binders at 60 C,
although penetration changes only slightly at all temperatures [11].
In 2003, Newcomb [12] discussed the concept of perpetual pavements in Hot Mix Asphalt, claiming that it is
a misconception that fatigue cracking is inevitable.
Many full-depth hot mix asphalt (HMA) pavements
built 3040 years ago have yet to exhibit any fatigue
cracking, and Newcomb claims that research shows that
increasing polymer modied binders at the bottom of
the asphalt layer may raise the fatigue limit of the pavement.
A 2003 US Army Corps of Engineers study [13]
points out that for optimal economy, it is desirable to
choose an asphalt modier that resists multiple distresses, such as rutting, fatigue, thermal cracking and
water damage. It was found that the choice of polymer
may have a signicant impact on fatigue properties,
and that the mixtures boasting the highest fatigue life
contained reactive styrenebutadiene crosslinked polymer. Other polymers tested were a chemically modied
crumb rubber, SBR, linear block SBS and a proprietary
modied SBS.

67

tegic Highway Research Program (SHRP). Bahia et al.

in their 1998 article for the Journal of AAPT note, however, that this blanket testing method failed to test the
extreme grades required by the new, modied binders,
resulting in the initiation of new testing protocols for
modied binders [14].
New test protocols include measuring the softening
point using a ring and ball apparatus (ASTM E 28) to
determine the resistance to ow at high temperatures
and a force ductility test that measures tensile properties
[15]. Several tests have been developed to look at elastic
recovery, one of the major areas of improvement in elastomer modied asphalt. Thompson and Hagman developed a torsional recovery test, included in California
specications for identifying the presence of elastomers
[1]. The elastic recovery test using a ductilometer, described later in this paper, is included in the Task Force
31 Specications and is used in the US and Europe [1].
King et al. [1] point out that many tests exist to identify whether modication is present, such as the IR, low
temperature ductility and torsional recovery. The West
Coast User Producer Group tried to use performance
based asphalt (PBA) specications, which involve a high
temperature viscosity test and low temperature penetration and ductility tests, as specications for modied asphalt, but they were not as good at predicting
performance with modied asphalt as they were with
neat asphalt [1].
In 1998, Blankenship et al. [16] conducted eld and
laboratory tests in Kentucky and found that PG 7022
made using dierent methods of modication gave different results for laboratory tests. They used the Dynamic Shear Rheometer (DSR) and Bending Beam
Rheometer (BBR) tests to identity ve dierent PG
7022 binders, two SBS-modied, one SBR modied,
one chemically modied, and one neat and compared
their behavior in various tests. These binders were found
to dier as far as rutting, moisture damage and modulus
testing, although the rutting dierence was no more than
10 mm between the binders.
In 2004, Yildirim et al. [17] utilized a design method
for determining the modication level of asphalt binders
using waste toner, which contains styrene acrylic copolymers. Binder designs were performed including blending
time, performance grading, storage stability and, mixing
and compaction temperature calculations. Test results
indicated that the stiness of the blend increases as the
percentage of the toner content increases.

3. Test methods
4. Specic modiers
As discussed by King et al. in the 1999 Journal of the
AAPT [1], there are several test methods that have been
developed or altered for modied binders. Previously,
both modied and unmodied binders alike were tested
according to the same methods, supported by the Stra-

4.1. Rubber
Crumb rubber modier (CRM) and asphalt-rubber are terms that refer to applications in which ground

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Y. Yildirim / Construction and Building Materials 21 (2007) 6672

recycled rubber and paving asphalt are combined [1].

Characteristics of asphaltrubber are dependent on rubber type, asphalt composition, size of rubber crumbs,
and time and temperature of reaction [1]. Usually, the
rubber is recycled from used automotive tyres, which
has the additional benets of saving landll space that
would otherwise be occupied by tyres and reducing cost
[1,18].
Natural rubber modication results in better rutting
resistance and higher ductility but the modier is sensitive to decomposition and oxygen absorption. Due to its
high molecular weight, it has problems of low compatibility [18]. Recycled tyre rubber reduces reective cracking, which increases durability. There are some practical
problems in using natural rubber: it needs high temperatures and long digestion times in order to be dispersed
in the bitumen [18].
In 1991, the Intermodal Surface Transportation Eciency Act (ISTEA) section 1038 was passed into law in
the USA. In its Declaration of Policy, ISTEA states It
is the policy of the United States to develop a National
Intermodal Transportation System that is economically
ecient, environmentally sound, provides the foundation for the Nation to compete in the global economy,
and will move people and goods in an energy ecient
manner [19]. The act required that, starting in 1994,
5% of roads built with federal funds must use pavement
made with crumb rubber, processed recycled tyres, or
modied asphalt. By 1997, 20% of roads built with federal funds were required to use recycled tyres in the
pavement [20].
On the other hand, the Used Tyre Working Group
[21] describes the United Kingdom as still being in the
process of evaluating a pilot project involving road surfacing that contains recycled tyres.
4.2. Styrenebutadienestyrene
Styrenebutadienestyrene (SBS) is a block copolymer that increases the elasticity of asphalt [18]. According to a 2001 review in Vision Tecnologica by Becker
et al. [18], it is probably the most appropriate polymer
for asphalt modication, although the addition of SBS
type block copolymers has economic limits and can
show serious technical limitations. Although low temperature exibility is increased, some authors claim that
a decrease in strength and resistance to penetration is
observed at higher temperatures. Nonetheless, SBS is
the most used polymer to modify asphalts, followed by
reclaimed tire rubber [18].
The Danish Road Directorate [22] found that an
SBS-modied binder course showed no superior rut
resistance compared to other Danish asphalt courses.
Asphalt cores taken from the job site indicated that
separation had occurred, and that the polymer phase
was not homogeneously distributed, which might have

been the cause of the poor performance of the pavement.

As reported in the Journal of Material in Civil Engineering, transmission electron microscopy was used in
2002 to better understand the behavior of SBS in asphalt
binders [23]. Depending on the sources of asphalt and
polymer, morphology varies: there can be a continuous
asphalt phase with dispersed SBS particles, a continuous
polymer phase with dispersed globules of asphalt, or
two interlocked continuous phases. It is the formation
of the critical network between the binder and polymer
that increases the complex modulus, an indication of
resistance to rutting.
In 2003, in the Journal of the AAPT, Mohammed
et al. [24] looked at the possibility of recycling SBS modied asphalt for resurfacing pavement. They found that
the impact of the extraction and recovery process on the
binder was minimal. Eight-year-old SBS modied binder was recovered from Route US61 in Louisiana, and
was found to have experienced intensive oxidative age
hardening. At low temperatures, the binder was quite
brittle. Blends of virgin and recovered polymer modied
binder were found to be stier than anticipated at both
low and high temperatures. It was also found that as the
percentage of recovered binder increased, rutting resistance increased, while fatigue resistance decreased.
In 2004, the Florida Department of Transportation
and FHWA published a report [25] looking at the eect
of SBS modication on cracking resistance and healing
characteristics of Superpavee mixes. They found that
SBS beneted cracking resistance, primarily due to a reduced rate of micro-damage accumulation. SBS did not,
however, have an eect on healing or aging of the asphalt mixture.
The possibility of using SBS-modied binders in India has been investigated recently [26]. Calculations indicated that the surface life of the DelhiAmbala
expressway would be almost doubled while the thickness
of the bituminous layers would be reduced, although the
cost per km would be greater for polymer modied
binders.
4.3. Styrenebutadienerubber
Styrenebutadienerubber (SBR) has been widely
used as a binder modier, usually as a dispersion in
water (latex). An Engineering Brief from 1987 available
at the US Federal Aviation Administration website [2]
describes the benets of SBR modied asphalt in
improving the properties of bituminous concrete pavement and seal coats. Low-temperature ductility is improved, viscosity is increased, elastic recovery is
improved and adhesive and cohesive properties of the
pavement are improved. The benet of latex is that the
rubber particles are extremely small and regular. When
they are exposed to asphalt during mixing they disperse

Y. Yildirim / Construction and Building Materials 21 (2007) 6672

rapidly and uniformly throughout the material and form

a reinforcing network structure.
According to Becker et al., SBR latex polymers increase the ductility of asphalt pavement [18], which allows the pavement to be more exible and crack
resistant at low temperatures, as found by the Florida
Department of Transportation [25]. SBR modication
also increases elasticity, improves adhesion and cohesion, and reduces the rate of oxidation, which helps to
compensate for hardening and aging problems [25].
In a 1999 laboratory test at the Texas Transportation
Institute, it was found that coating smooth, rounded,
siliceous gravel aggregates with cement plus SBR latex
for use in HMA increased stability according to Hveem
and Marshall standards, as well as tensile strength, resilient modulus and resistance to moisture damage. Coated
aggregates have greater resistance to rutting and cracking [27].
Water-based SBR latex has been widely used to improve chip retention in emulsions, but SBS has gradually replaced latex because of its eect of greater
tensile strength at strain, and because it is compatible
with a broader range of asphalts [1]. Elastomers such
as SBR and SBS have a signicant eect on the results
of the ductility test at both 4 and 25 C; while SBR modied asphalts have high ductility at all temperatures,
SBS modied asphalts tend to have lower ductility [1].
4.4. Elvaloy
The Duponte website [28] describes Elvaloy as an
ethylene glycidyl acrylate (EGA) terpolymer that chemically reacts with asphalt. As a result of the reaction,
problems with separation during storage and transportation are avoided. Roads using Elvaloy have been in
use since 1991.
In 1995 Witczak, Hafez and Qi [29] studied the laboratory performance of asphalt modied with Elvaloy
at the University of Maryland. Two dierent grades of
asphalt were each modied by 0%, 1.5% and 2.0% Elvaloy by weight of binder. The susceptibility of the mixtures to moisture damage was found to be greatly
decreased by the addition of Elvaloy. In addition, an

% Recovery

69

Elvaloy in combination with granite had a signicantly

higher (poorer) fracture temperature than with diabase,
limestone or granite aggregate treated with hydrated
lime.
At the DuPont Institute, Babcock et al. [31] devised a
lap shear test for high temperature binder properties,
which appears to agree with high temperature DSR
measurements. The results indicated that binder failure
at temperatures above 6 C tends to be cohesive failure,
due the loss of integrity within asphalt. On the other
hand, around 6 C and colder, failure is adhesive, from
a loss of adhesion between the binder and the substrate.
Since this indicates that cold temperature failure of a
road may be the result of loss of adhesion to the aggregate, a chemically reactive polymer is expected to perform better, and reactive elastomeric terpolymer does
in fact perform better in this test than SBS or the control
neat bitumen.

5. Elastic recovery test

Elastic recovery (or elasticity) is the degree to which a
substance recovers its original shape following application and release of stress. A degree of elastic recovery
is desirable in pavement to avoid permanent deformation. When a tire passes over a section of pavement,
it is desirable for that pavement to have the ability to
give, but it is equally important for it to recover to its
original shape, according to the Asphalt Institute website [32].
5.1. Measurement and calculation
The elastic recovery of asphalt is measured with the
aid of a ductilometer, which is used to elongate an asphalt specimen at a constant rate. After a period of time,
the elongated specimen is cut and then allowed to rest.
After the period of rest is complete, the distance between
the ends of the cut specimen is measured [33].
The elastic recovery is the ratio between the dierence
in elongation between cutting and the end of the rest
period, and the total elongation applied [33].

Initial elongation  Observed elongation after rejoining sample

 100
Initial elongation

analysis of repeated load permanent deformation behavior showed that increasing concentrations of Elvaloy
resulted in a marked decrease in deformation.
In a study on low-temperature rheological properties
of polymer modied binders, the FHWA [30] found that

5.2. Binder characterization

The elastic recovery test is used to test polymer modied binders by the departments of transportation of several states in the US and several other countries, as well

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Y. Yildirim / Construction and Building Materials 21 (2007) 6672

as by researchers around the world. According to the

Spring 2002 edition of the Asphalt Technology News
[34], Kansas, Louisiana and Texas require use of the elastic recovery test to ensure that binders have been modied. Michigan also uses it, although it does not require
it, and Kentucky uses it to test PG 7622 binders. It is
also used to characterize polymer modied binders in
Quebec, Sweden, Finland and Switzerland [35].
In 1981, Oliver developed the elastic recovery test
for the Australian Road Research Board to measure
deformation response of rubber modied binders
[36,37]. He found that binders with natural (truck-tyre)
rubber showed greater elastic recovery than synthetic
(car-tyre) rubber. In 1997, it was reported to the Australian Asphalt Pavement Association that even low
concentrations of SBS caused an increase in elastic
recovery, softening point, viscosity and cohesive
strength [38].
In 1990, Valkering and Vonk [39] compared SBS and
EVA modied binders to neat binders and found that
SBS modied binders had signicantly higher elastic
recovery than neat binders. Compared to SBS, EVA
modied binders showed a lesser degree of improvement
in elastic recovery and also lost ductility and elastic
recovery much more rapidly.
Braga and Corrieri [40] used the elastic recovery test
to compare the resistance to thermal degradation of
SBS and heterophasic polyolen (TPO) modied binders. Aged SBS polymers following showed a lower resistance to thermal degradation than aged TPO binders.
Several studies have investigated the relationship between measurements of elastic recovery and other measures of performance, in both laboratory and eld tests.
In the Transportation Research Record 1996, Bonemazzi et al. [41] compared the performance of binders
modied with an array of polymers (atactic propylene
ethylene copolymer, low- and high-density polyethylene,
ethylene/propylene rubber, ADFLEX, ethylene methacrylate copolymer, EVA, thermoplasticpolyolenic terpolymer, and SBS linear and radial block copolymers)
in tests of penetration and elastic recovery as well as
the rheometer dynamic test. All the tests were shown
to be good measurements of polymer contribution to
binder performance.
In 1997, Oliver [42] examined the relationship between
the rheological properties of asphalt mixes and rutting
resistance using the wheel tracking test. While a relationship between polymer consistency and rut resistance was
found, no relationship was apparent between rut resistance and elastic recovery or softening point.
In the Journal of the AAPT, 1998, Bahia, Perdomo
and Turner [9] compared ve modied binders, measuring elastic recovery, ductility and resilience. They found
that these conventional measurements were inconsistent
in ranking the suitability of polymer modied binders.
Specically, rankings changed as strain level changed.

Superpavee testing results were equally inconsistent in

ranking modied binders.
In a 1988 Iowa Department of Transportation report,
Lee and Demirel [43] compared viscosity, penetration,
softening point, force ductility, elastic recovery and several other characteristics of binders with SBS, polyolephins, neoprene, SBR latex and hydrated lime. There
was no correlation between the dierent types of measurement.
John DAngelo, on the Asphalt Institute web page
[44], points out that the literature suggests that most
tests of modied binders may only measure whether a
polymer modier is present, not its eect on the eld
performance of the modied binder.

6. Conclusions
In the 1980s, polymer modied asphalts began to be
used in the US and by 1997 all but three states were already using modied binders or intended to use them in
the future and federal regulations supported their use.
Pavements made with modied binders are more resistant
to fatigue, thermal cracking, rutting, stripping, and temperature susceptibility than neat binders. Polymer modied binders tend to exhibit increased viscosity and elastic
recovery, although penetration does not appear to be
inuenced by modication. An ideal modier will increase binder resistance to multiple types of distresses.
Modication is not without its drawbacks, however, since
compatibility between an asphalt and a modier is not assured, and separation during storage or application, if
not addressed, can result in poorly performing pavement.
Since Superpavee specications were designed for
neat binders, they are inappropriate for polymer modied binders. In fact, asphalts modied with dierent
polymers can behave very dierently even when they
have the same performance grade. Test methods that
have been developed or altered for modied binders include measuring the softening point and elastic recovery,
and a force ductility test. There is disagreement about
whether bending beam rheometer (BBR) tests, developed for Superpavee, are acceptable for polymer modied binders. In general, it seems that the results of
rheological tests are not indicative of the performance
of polymer modied binders. Several tests exist to identify whether modication is present, such as the IR, low
temperature ductility and torsional recovery. In 1991,
the ISTEA required that an increasing proportion of
roads use modied asphalt.
Dierent polymers impact characteristics of asphalt
to diering degrees.
 Natural rubber improves rutting resistance and ductility, but is sensitive to decomposition and often has
problems of compatibility.

Y. Yildirim / Construction and Building Materials 21 (2007) 6672

 The use of tyre rubber as an asphalt modier is environmentally responsible and results in decreased rutting and reective cracking, but special conditions,
such as high mixing temperatures and long digestion
times, need to be maintained to prevent separation
from the asphalt binder.
 The addition of SBR to asphalt improves low-temperature ductility, increases viscosity, improves elastic recovery and improves the adhesive and cohesive
properties of the pavement. Water-based SBR latex
was used commonly to improve chip retention in
emulsions.
 SBS has been replacing SBR due to the formers
wider compatibility and greater tensile strength under
strain. SBS is now the polymer most used to modify
asphalt. SBS increases the elasticity of asphalt and
SBS modied asphalt can be recycled. SBS modied
binders have been found to perform better at low
temperatures than neat binders or binders modied
with chemically reactive polymers.
 Elvaloy is a modier that forms a chemical bond
with the asphalt, avoiding problems of separation
during storage, transportation and application. It
increases pavement moisture resistance and results
in modied asphalt performing better in high temperature DSR tests.
Elastic recovery of asphalt, a measurement widely
used to test polymer modied binders, can be measured
by elongating an asphalt sample, cutting it, allowing it
to rest, and determining the degree to which the elongated specimen returns to its original length.
The elastic recovery test has been shown to be a good
measurement of polymer contribution to binder performance, although no relationship appears to exist between rut resistance and elastic recovery. Elastic
recovery and other conventional measurements are
inconsistent in ranking polymer modied binder performance and may only measure whether or not a modier
is present in an asphalt specimen, not its contribution to
the asphalts performance.
Polymer modied binders have had proven success
in the eld and the laboratory, and a continuing eort
is being made to develop a correlation between results
from laboratory tests and eld performance.

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