Geotechnical Special Publication No.

223 © ASCE 2011 41

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Rheological Properties of the Polymer Modified Bitumen with Emphasis on SBS Polymer
and its Microstructure

Sarah Zorn1, Yusuf Mehta2, Kevin Dahm3, Eileen Batten4, Aaron Nolan5, Ralph Dusseau6
1 Graduate Research Assistant, Department of Civil and Environmental Engineering, Rowan University
Glassboro, NJ 08028, USA. E-mail: zorns97@students.rowan.edu
2 Associate Professor, Department of Civil and Environmental Engineering, Rowan University
Glassboro, NJ 08028, USA. E-mail: mehta@rowan.edu
3 Associate Professor, Department Chemical Engineering, Rowan University
Glassboro, NJ 08028, USA. E-mail: dahm@rowan.edu
4 Undergraduate Student, Department of Chemical Engineering, Rowan University Glassboro, NJ
08028, USA.
5 Research Associate, Department of Civil and Environmental Engineering, Rowan University
Glassboro, NJ 08028, USA. E-mail: nolan@rowan.edu
6. Professor, Department of Civil and Environmental Engineering, Rowan University
Glassboro, NJ 08028, USA. E-mail: dusseau@rowan.edu

ABSTRACT: The rheological properties of bitumen are improved by addition of small

quantities of polymers. A review of different polymers such as Styrene-Butadiene-Styrene (SBS)
Styrene-Butadiene-Rubber (SBR), Ethylene Vinyl Acetate (EVA) and Poly Phosphoric Acid
(PPA) with emphasis on SBS and its microstructure is presented in this paper. The polymers are
divided into two groups: elastomers and plastomers. SBS, an elastomer, has shown greater
potential compared to other modifiers when blended with bitumen and improves the mechanical
properties and rheological behavior of conventional bitumen. SBS is made up of styrene and
butadiene monomer units. It was found that maltene interacts preferentially with the
polybutadiene unit of SBS, whereas asphaltene interacts predominantly with the polystyrene
unit. SBR is another elastomer which also has polystyrene and polybutadiene units with a
different structural make up. EVA is a plastomer which when blended with bitumen has
improved the rheological properties and stability, provided the asphalt has asphaltene content
below a critical level. PPA is a liquid mineral polymer. Addition of PPA to asphalt contributes to
more interactions within the asphaltenes network, thus increasing the elastic behavior. A study
was also conducted to determine the influence of asphaltenes and maltenes on the rheological
properties of polymer modified binders.

INTRODUCTION

The physical, mechanical and rheological properties of the bitumen primarily depend on its
colloidal structure, which in turn is linked to the chemical composition and especially to the
proportion of asphaltenes and maltenes. Asphaltenes are polar materials of high molecular
weight (10,000 to 100,000) that are insoluble in n-heptane, a non-polar solvent, and constitute

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 Geotechnical Special Publication No. 223 © ASCE 2011 42

5% to 25% of the bitumen. Maltenes are constituted by resins; aromatic and saturated oils that
are soluble in n-heptane and possess low molecular weight. Different proportions of these
compounds (asphaltenes and maltenes consisting of resins and oils) may lead to different types
of bitumen microstructure. Knowing the bitumen rheology is beneficial in refining operations.
Refineries can produce good asphalt by selecting the proper starting crude, or tailoring the
refinery processes used to make asphalt (Brule B.et al., 1987 and Becker et al., 2001). Several
polymers (thermoplastics and elastomers) are mixed with bitumen in proportions below 10% to
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improve the properties of the binder (Bahia et al, 2001 and Gonzalez et al., 2004). The term
“polymer” refers to very large molecules made by chemically reacting many small molecules
(called monomers) to produce long chains. The polymers used for bitumen modification are
divided into two groups, namely elastomers and plastomers. The modifiers Styrene-Butadiene-
Styrene (SBS) and Styrene-Butadiene-Rubber (SBR) fall under elastomers category (Airey, 2003
and Hrdlicka et al., 2007), Ethyl-Vinyl-Acetate (EVA) falls under plastomers (Sengoz et al.,
2009, Hrdlicka et al., 2007) and Polyphosphoric acid (PPA) is a liquid mineral polymer having
generic composition Hn+2 PnO3n+1 (Aflaki and Tabatabee, 2009). 

PROBLEM STATEMENT

To meet the Superpave PG specifications set forth by State Highway Research Program
(SHRP), asphalt manufacturers either altered manufacturing practices or added modifiers such as
polymers to the asphalt binder. From past research, in general, it is reported that the addition of
modifiers improved the performance of hot mix asphalt concrete (HMA) (Hrdlicka et al., 2007).
Of all the modifiers tested until now, Styrene-Butadiene-Styrene (SBS) has shown greater
potential compared to other modifiers such as Styrene-Butadiene-Rubber (SBR), Ethyl-Vinyl-
Acetate (EVA) and Polyphosphoric acid (PPA) (Sengoz et al., 2009, Hrdlicka et al., 2007).
Considerable research has been undertaken regarding SBS polymer modified binders (PMB),
such as determining the fundamental characteristics of the same using conventional bitumen tests
like penetration, softening point, thin film oven test (TFOT), penetration and softening point
after TFOT, viscosity, Frass breaking point, effect of SBS on aging of SBS PMBs, evaluation of
the permanent deformation of SBS modified asphalt mixtures using dynamic creep test, storage
stability and compatibility of PMB. However, not much research is done on the influence of the
chemical composition of SBS (or chemical composition of PMB’s generally) which has
considerable effect on the rheological properties of the bitumen by interaction between bitumen
and polymer system. (Sengoz et al., 2009, Cortozo et al., 2004, Mouillet et al., 2008, Haddadi et
al., 2008, Ruan et al., 2003, Khodaii and Mehrara, 2009, Gonzalez et al., 2004, Sengoz and
Isikyakar, 2008, Wen et al., 2002, Fu et al., 2007, Zhang and Yu, 2009). By having the
information of the chemical composition of SBS and knowing how a particular chemical
component modifies or affects a particular mechanical property of the binder, asphalt
manufacturers can be benefitted. Asphalt manufacturers are benefited as they can add just the
right and necessary amount of a particular chemical component of SBS to the neat asphalt to
acquire the required property for the bitumen thus saving time and money and getting better
modified asphalt binders faster. Hence there is a need to emphasize the characterization of the
PMB’s with emphasis on SBS polymer modified binder (PMB) by studying the morphology, i.e
study of molecular structure of SBS with respect to the chemical composition of asphaltenes and
maltenes.

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OBJECTIVE

To review the rheological properties of the polymer modified bitumen with emphasis on SBS
polymer and its microstructure and to present the influence of chemical composition of
asphaltenes and maltenes on the rheological properties of different polymer modified binders
such as SBS, Elvaloy and Elvaloy+ PPA .
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PERFORMANCE OF DIFFERENT MODIFIERS

Performance of different modifiers based on the literature review of polymer modified binders
is presented below in the order of SBS, SBR, EVA and PPA.

Styrene-Butadiene-Styrene (SBS)

Styrene-butadiene-styrene (SBS) is the most widely used polymer to modify asphalts

(Yildirim, 2005). It is a tri-block copolymer or a thermoplastic rubber that falls under the
category of elastomers, which significantly increases strength at higher temperatures as well as
flexibility at lower temperatures (Hrdlicka et al., 2007). Block copolymers are produced by
joining two or more chemically different monomer blocks into a linear series. The molecular
structure of SBS can be linear or radial. In linear SBS, two polystyrene (PS) blocks are placed at
the end with polybutadiene (PB) an elastomeric block in the middle (Figure 1). In radial SBS, the
molecule of SBS has a star structure with more than three polystyrene blocks. This polar and
rigid polystyrene (PS) blocks in SBS make the polymer binder system more resistant to the
deformation. More polar groups in the polymer provide stronger interactions between the
polymer and the asphaltene and polar aromatic components of asphalt. (Becker et al., 2001).
Therefore, SBS can improve the mechanical properties and rheological behavior of conventional
asphalt compositions as it is provided with a two-phase morphology. The glassy polystyrene (PS)
domains connected together by the rubber polybutadiene (PB) segments. (Wen et al., 2002, Fu et
al., 2007).
It was also reported that SBS copolymers derive their strength and elasticity from physical and
cross linking of the molecules into a three-dimensional network. The researchers found that the
polystyrene end blocks impart the strength to the polymer while the rubbery matrix blocks of
polybutadiene gave the material its exceptional viscosity. That means the glassy ST domains of
SBS increase the stiffness of asphalt for high temperature use, whereas the rubbery BT
midblocks resist thermal cracking at low service temperatures. They also found that maltene, the
soluble fraction extracted from the asphalt by n-heptane, interacts preferentially with the
polybutadiene unit of SBS, whereas asphaltene, the insoluble fraction interacts predominantly
with the polystyrene unit. (J.Stastna et al., 2003, Kamiya et al., 2000). Viscosity increases with
interactions of asphaltene with polystyrene (PS) units of SBS (Sengoz and Isikyakar, 2008,
Kamiya et al., 2000, Airey, 2003). Researchers Kamiya et al., 2000, proposed a micro structural
model of modified asphalt for SBS mixing to asphalt at 185°C. Asphalt is a colloidal structure
containing two components, namely asphaltene in maltene (Figure 1a). By addition of a small
amount of SBS to the matrix at high temperature, molecular chains of SBS stay at the interface
between asphaltene and maltene and viscosity increases with preferential interactions of
asphaltene with PS units of SBS (Figure 1b). At SBS concentrations of less than 5 wt%,
favorable interactions between asphaltene and PS units in SBS occur and also unfavorable

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interactions between maltene and PS units may form unstable micelles. With further addition,
SBS on interface may become saturated, leading to the formation of SBS micelles in the maltene
phase (Figure 1c). When SBS reaches a critical value (about 10wt %), SBS and the asphaltene
phase become a continuous phase by phase inversion (Figure 1d). When SBS becomes matrix,
the system becomes stable since the entire interface is occupied by SBS. They also found that the
solubility parameter of maltene is close to that of PB while the solubility parameter of asphaltene
was similar to that of PS.
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FIG. 1. Schematic model of SBS/asphalt mixtures at 170-185°C. a: Asphalt, b: SBS

(<5%)/Asphalt, c: SBS (5-8%)/Asphalt, d: SBS(>10%)/Asphalt. (Kamiya et al., 2000)

Aging of SBS PMB

Aging of SBS PMB occurs through the oxidation of the unsaturated polybutadiene blocks
which could lead to chain scission or polymer degradation. Aging causes an increase in
asphaltenes that decrease the temperature susceptibility with respect to both stiffness and
viscosity of the base asphalt. (Mouillet et al., 2008, Ruan et al., 2003).

Compatibility

SBS block copolymers in order to be compatible with the asphalt, should be rich in both
butadiene (about 60-70%) and in polystyrene domains. To obtain PS rich domains, molecular
weights of the styrene fraction must exceed 10,000. (Becker et al., 2001). The chemical structure
and polarity of SBS make it suitable for blending with a fairly large number of asphalt types
without serious problems of solubility and phase segregation. (Polocco et al., 2006). But due to
the difference in the solubility parameter and density between SBS and asphalt, phase separation
would take place during storage at higher temperatures. (H.Fu et al., 2007 and Wen et al., 2002).
The extent to which a stable system is formed when the bitumen is modified by the addition of
thermoplastic rubber is dependent upon a number of factors such as: the amount and size of the
asphaltenes, the amount and size of the polymer molecules and the aromaticity of the maltene
phase. Also, the stability and homogeneity of the blend is highly dependent on the ratio between
the molecular weight of the asphaltenes and that of the resins. (Becker et al., 2001)

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Styrene-Butadiene-Rubber (SBR)

SBR is an elastomeric polymer and is most commonly used type of synthetic rubber. SBR
contains approximately 25% styrene and 75% butadiene. This has greater heat resistance but
lower tensile strength than natural rubber. SBR has only one PS block which enables SBR
polymer modified binder to flow easily and not to build stress when undergoing extension. Due
to the structural makeup of SBR, even with little oxidation, SBR is efficient at increasing the
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asphalt ductility. More butadiene structures contained in SBR molecules make SBR more readily
oxidized and decomposed in the aging process. Aging causes an increase in asphaltenes that
decrease the temperature susceptibility with respect to both stiffness and viscosity of the base
asphalt. Researchers aged polymer modified asphalt binders using both the rolling thin film oven
test (RTFOT) and the thin film oven test (TFOT). They found that two parallel reactions
occurred during the oxidation: oxidation of base asphalts and degradation of polymers. Oxidation
of modified binders resulted in an increase in asphaltenes in the base asphalt and a decrease in
molecular size of polymer modifiers, as indicated by size exclusion chromatography (SEC).
(Zhang and Yu, 2009, Ruan et al., 2003). Due to the difference in the stability parameter and
density between SBR and asphalt, phase separation would take place in SBR PMB during
storage at elevated temperatures.

Ethylene Venyl Acetate (EVA)

EVA is a semi-crystalline copolymer and is one of the principal plastomers used to improve
both the workability of asphalt during construction and its deformation resistance in service. The
EVA polymers are classified as plastomers as they modify bitumen by formation of a tough and
rigid network to resist deformation. EVA is a good modifier to improve thermal cracking as well.
(Haddadi et al., 2008, Sengoz et al., 2009, Hrdlicka et al., 2007, Gonzalez et al., 2004)

Polyphopsphoric Acid (PPA)

Polyphosphoric acid is a liquid mineral polymer having generic composition Hn+2PnO3n+1. PPA
has a minimum of two phosphorus atoms and a minimum average molecular weight of 258
(Aflaki and Tabatabaee, 2009). Addition of PPA to asphalt contributes to more interactions
within the asphaltenes network, thus increasing the elastic behavior. Typically the amount of
PPA added to asphalt binder is between 0.5-1.5 % which results in increase of the PG grade of
the asphalt binder. Researchers found that for the pure PPA modified asphalt, with increasing
PPA content, the softening point increases and the penetration decreases correspondingly, which
imply that the high temperature properties of asphalt would be improved by PPA. It was also
observed that PPA modification increased binder stiffness and reduced the intermediate and low
temperature performance of PPA modified binders.

EXPERIMENTAL

A study was conducted to evaluate the influence of chemical composition on the mechanical
properties of different polymer modified binders. Different polymer modified binders were
prepared using the base binder NuStar PG64-22 and modifiers such as Kraton D 1101 which is
an SBS modifier, Elvaloy AM and Elvaloy with PPA. The asphalt was seperated into asphaltenes

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and maltenes which are called Saturates, Aromatics, Resins and Asphaltenes (SARA) fractions
according to ASTM D 4124-01 procedure using n-Heptane. SARA analysis was performed on
the polymer modified binders and a base binder. The chemical composition was compared with
the mechanical properties of PMB’s especially to Jnr to evaluate the influence of the former on
the later. The results are included in Table 1.

Table 1. Binder testing summary

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SUMMARY OF FINDINGS AND CONCLUSIONS

A review of rheological properties of the polymer modified bitumen with emphasis on SBS
polymer and its microstructure along with the influence of the chemical composition on the
rheological properties of polymer modified binders such as SBS, Elvaloy and Elvaloy+ PPA is
presented in this paper.
SBS has shown greater potential compared to other modifiers when blended with bitumen. The
glassy ST domains of SBS increase the stiffness of asphalt for high temperature use, whereas the
rubbery BT midblocks resist thermal cracking at low service temperatures. Maltene interacts
preferentially with the polybutadiene unit of SBS, whereas asphaltene, interactes predominantly
with the polystyrene unit. Aging of SBS occurs through the oxidation of the unsaturated
polybutadiene blocks. A high content of resins and aromatics in the asphalt mixture means high
solvating ability and therefore good mobility of asphaltene micelles.The solubility parameter of
maltene is close to that of PB while the solubility parameter of asphaltene is similar to that of
PS.The chemical structure and polarity of SBS make it suitable for blending with a fairly large
number of asphalt types without serious problems of solubility and phase segregation.

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SBR, an elastomeric polymer, has greater heat resistance but lower tensile strength than natural
rubber. More butadiene structures containing in SBR molecules make it much easier to be
oxidized and decomposed in the aging process. Aging causes an increase in asphaltenes that
decrease the temperature susceptibility with respect to both stiffness and viscosity of the base
asphalt.
EVA improves both the workability of asphalt during construction and its deformation
resistance in service by formation of a tough and rigid network that resists deformation. EVA is a
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good modifier to improve thermal cracking as well. In EVA PMB, as the asphaltenes content
increased the compatibility of bitumen-polymer decreased. The higher the vinyl acetate content
in EVA PMB, the lower is the crystallinity and the higher is the polarity of the polymer and its
compatibility with asphalt.
PPA modification increased binder stiffness. Also when the molecular weight difference
between polymer and asphalt declined, the dispersion of polymer in asphalt was improved. It was
also found that the addition of PPA to asphalt contributes to more interactions within the
asphaltenes network, thus increasing the elastic behavior.
From the experimental study it can also be seen that the chemical composition of asphaltenes
and maltenes i.e Saturates, Aromatics, Resins & Asphaltenes (SARA) is sensitive to the polymer
modification. Therefore there is a potential that SARA components could provide valuable
information to the asphalt manufacturer to cost effectively modify the binder to achieve a target
mechanical property.
In conclusion, what type of modification is the best depends on different factors such as
availability of the modifier/material, cost, climatic conditions of the pavement, specific
requirements of the state DOT’s etc.,. More research needs to be done on other modifiers such
as SBR, Elvaloy and PPA.

REFERENCES

Brule, B., Brion, Y., And Tanguy, A. (1987). “Paving Asphalt Polymer Blends: Relationships
Between Composition, Structure and Properties,” Association of Asphalt Paving
Technologists, pp. 41-64.
Becker, Y., Méndez, M.P. and Rodríguez Y (2001). “Polymer modified asphalt,” Vision
Technologica, Vol. 9, N° 1.
Bahia, H.U., Hanson, D..I., Zeng, M., Zhai, H., Khatri, M. A. and Anderson R. M (2001).
“Characterization of Modified Asphalt Binders in Superpave Mix Design,” NCHRP Report
459, TRB, Washington D.C, 2001
Gonzalez, O., Munoz, M. E., Santamarıa, A., Garcia-Morales, M., Navarro, F. J., and Partal, P.
(2204). “Rheology and Stability of Bitumen/EVA Blends,” European Polymer Journal 40, pp.
2365-2372.
Airey, G. D. (2003). “Rheological Properties of Styrene Butadiene Styrene Polymer Modified
Road Bitumens,” Fuel 82, pp. 1709-1719.
Hrdlicka, G. M, Tandon, V., Prozzi, J., Smit, A., and Yildrim, Y. (2007). “Evaluation of Binder
Tests for Identifying Rutting and Cracking Potential of Modified Asphalt Binders,” Center for
Transportation Infrastructure Systems, Research Report 0-4824-1.
Sengoz, B., Topal, A., Isikyakar, G., and Dokuz, E. (2009). “Morphology and image analysis of
polymer modified bitumens,” Construction and Building Materials Vol. 23, pp. 1986-1992.

Road Materials and New Innovations in Pavement Engineering

 Geotechnical Special Publication No. 223 © ASCE 2011 48

Aflaki, S., Tabatabaee, N. (2009). “Proposals for Modification of Iranian Bitumen to Meet the
Climatic Requirements of Iran,” Construction and Building Materials, No.23, pp. 2141-2150.
Cortizo, M. S., Larsen, D. O, Bianchetto, H., and Alessandrini, J. L. (2004). “Effect of the
Thermal Degradation of SBS Copolymers during the Ageing of Modified Asphalts,” J. of
Polymer Degradation and Stability, No. 86, pp. 275-282.
Mouillet, V., Lamontagne, J., Durrieu, F., Planche, J. P., and Lapalu, L. (2008). “Infrared
Microscopy Investigation of Oxidation and Phase Evolution in Bitumen Modified With
Downloaded from ascelibrary.org by RMIT UNIVERSITY LIBRARY on 09/25/13. Copyright ASCE. For personal use only; all rights reserved.

Polymers,” Fuel 87, pp. 1270-1280.

Haddadi, S., Ghorbel, E., and Laradi, N. (2008). “Effects of the Manufacturing Process on the
Performances of the Bituminous Binders Modified with EVA”. Construction and Building
Materials, No. 22, pp. 1212-1219.
Ruan, Y., Davison, R. R., and Glover, C. J. (2003). “The Effect of Long-Term Oxidation on the
Rheological Properties of Polymer Modified Asphalts,” Fuel 82, pp. 1763-1773.
Khodaii, A., and Mehrara, A., (2009). “Evaluation of Permanent Deformation of Unmodified
and SBS Modified Asphalt Mixtures Using Dynamic Creep Test,” Construction and Building
Materials, No. 23, pp. 2586-2592.
Burak, S., and Isikyakar, G. (2008). “Analysis of Styrene-Butadiene-Styrene Polymer Modified
Bitumen Using Fluorescent Microscopy and Conventional Test Methods,” Journal of
Hazardous Materials, No. 150, pp. 424-432.
Burak, S., and Isikyakar, G. (2008). “Evaluation of the Properties and Microstructure of SBS
and EVA Polymer Modified Bitumen” Construction and Building Materials, No. 22, pp.1897-
1905.
Wen, G., Zhang, Y., Zhang, Y., Sun, K., and Fan, Y. (2002). “Rheological Characterization of
Storage-Stable SBS-Modified Asphalts,” Polymer Testing 21, pp. 295-302.
Fu H., Xie, L., Dou, D., Li, L., Yu, M., Yao, S. (2007). “Storage Stability and Compatibility of
Asphalt Binder Modified by SBS Graft Copolymer”. Construction and Building Materials,
No. 21, pp. 1528-1533.
Zhang, F., Yu, J. (2009) “The Research for High-Performance SBR Compound Modified
Asphalt,” Construction and Building Materials, Article in Press.
Yildirim, Y. (2007) “Polymer Modified Asphalt Binders,” Construction and Building Materials,
No. 21, pp. 66-72.
Stastna, J., Zanzotto, L., and Vacin, O,.J. (2003), “Viscosity Function in Polymer-Modified
Asphalts”. Journal of Colloid and Interface Science, pp. 200-207.
Kamiya, S., Tasaka, S., Zhang, X., Dong, D., and Inagaki, N. (2001). “Compatibilizer Role of
Styrene-butadiene-styrene Triblock Copolymer in Asphalt,” Polymer Journal, Vol. 33, No.3,
pp. 209-213.
Polacco, G., Stastna, J., Biondi, D., and Zanzotto, L. (2006). “Relation between polymer
architecture and nonlinear viscoelastic behavior of modified asphalt,” J. Current Opinion in
Colloid and Interface Science 11, pp. 230-245.

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