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org/scea Study of Civil Engineering and Architecture (SCEA) Volume 3, 2014
Using SEPS as A Novel Modifier for Bitumen
Nazanin Moshtagh 1, Farhad Zafari2, Mohammad Rahi3, Hossein Nazockdast4
1,2 Polymer Engineering Department, Amirkabir University of Technology, Tehran, Iran
3 Head of Research and Development Department, Pasargad Company, Tehran, Iran
4 Associated Professor, Polymer Engineering Department, Amirkabir University of Technology, Tehran, Iran
1 nazanin.moshtaq@gmail.com; 2farhad_zafari@yahoo.com; 3mohamadrahi@yahoo.com; 4nazdast@aut.ac.ir
Abstract are necessary. The properties of PMBs are dependent
The unique properties (high flexibility, high traction, sealing on the polymer characteristics and content and
abilities, heat resistant) of Kratons such as SEPS and their bitumen nature, as well as the blending process.
considerable effects on improving the original bitumen
Asphalt mixtures with a high stiffness modulus at low
properties, encouraged using these additives as effective
modifiers. In this study, soft base asphalt has been modified temperatures are most prone to low‐ temperature
by addition of different amounts of SEPS and the rheological cracking. To reduce the risk of this type of cracking,
properties and hot storage stability of the Polymer Modified the binder should have good flexibility (low stiffness
Bitumens (PMBs) have been studied, several tests have been and high ability of stress relaxation) at the lowest
conducted to determine the resulted effects, such as classical pavement temperature.
tests and rheological analaysis. The results of classic tests
showed that adding SEPS reduced penetration, temperature In this context styrene – (ethylene‐co‐propylene) –
susceptibility, and ductility and increased the softening styrene triblock copolymers (SEPS) is used to modify
point and elastic recovery. Rheological properties of bitumen. SEPS offers many of the properties of natural
modified specimens were investigated with DSR in rubber, such as flexibility, high traction, and sealing
temperature sweep and frequency sweep and creep tests
abilities, but with increased resistance to heat,
before and after aging in RTFO. The results indicated that
weathering, and chemicals and regardless of its wide
the rheology of the modified binders is largely dependent
on the polymer content At low polymer content, the applications for adhesive adhesives, sealants and
modified binders showed dispersed polymer particles in a coatings, it is not used in asphalt modification so far.
continuous bitumen matrix. At a sufficiently high polymer
In this study, bitumen has been modified by addition
contents, a continuous polymer phase was observed.
Regardless of the nature of the two phases, the storage of different amounts of SEPS and the rheological
stability of the modified binders decreased as polymer properties and hot storage stability of the PMBs have
content increased. Polymer modification improved bitumen been studied. The master curves of the viscoelastic
rheological properties such as the increased elastic responses material functions have been prepared in linear
at high temperatures and the reduced creep stiffness. In this conditions over a wide frequency range. The results,
study the FTIR test was employed to investigate the
combined with viscosity measurements, the outcomes
chemical bonding changes of neat and polymer modified
of classical tests, explain some structure property
asphalt and the results proved the strong interaction
between polymer and bitumen due to creation of new relationships and allow the determination of the range
chemical bonds. of compositions where stable mixes can be obtained.
Fourier Transform Infrared Spectrums (FTIR) of all
Keywords
unaged and aged samples has been investigated. The
SEPS; Polymer Modified Bitumen; Rheology; Aging; FTIR detailed tests and discussions of the results obtained
from the testing are discussed in the following sections.
Introduction
In the recent decades asphalts are widely employed in Materials and Methods
several applications, but the most important one is
Material and Sample Preparation
related to the paving industry. Unfortunately, high‐
temperature rutting and low temperature cracking of One bitumen from vacuum distillation of 85/100 Pen
asphalt cement or coating layer due to severe grade was blended with 2, 4 and 6 percentages of
temperature susceptibility limits its further application. Styrene–ethylene–propylene–styrene block copolymer
Therefore, the improvements of functional properties (SEPS). The SEPS polymer is Kraton G1780M (Shell),
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b Gap between the plates
bitumen gradually (about 5 g/min) while keeping the
c Sweep frequency
temperature within the range of 180±1 oC during the
polymer addition and the subsequent 2h of mixing. TABLE 2 PARAMETERS FOR TEMPERATURE SWEEP TEST
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The values for the Rotational viscosity of the SEPS as the separation index, I s. DSR results obtained at 10
PMB samples as a function of the SEPS content FIG. 1. rad/s are plotted in FIG. 2.
1.00E+05 basebitumen The acceptable stability of the specimen is if the
2%SEPS difference between the softening point of top and
Rotational Viscosity (mPa.s)
1.00E+04
4%SEPS bottom of the sample is below 2.5 oC. The difference
6%SEPS between the softening points indicates how stable the
1.00E+03
mixture is. As TABLE 4 shows the differences between
1.00E+02 the top and bottom softening points in all samples,
except sample with 6% SEPS, are less than 2.5 oC. The
1.00E+01
less difference between complex modulus of top and
1.00E+00 bottom there is, the more stable binders are .As FIG. 2
80 100 120 140 160 180 200 shows samples containing 2 and 4% SEPS have zero
Temperature (◦C) separation index. At low polymer concentrations, the
FIG.1 ROTATIONAL VISCOSITY VS. TEMPERATURE content of maltenes (more compatible with the
As expected, there is an increase in the asphalt polymer) is probably sufficient to swell the
viscosity with the polymer addition. The Brookfield macromolecules without inducing instability in the
viscosity variation is in agreement with the softening micellar structure of asphalt, and the resins may
point values of the SEPS PMB. A PMB with high stabilize the polymer‐rich phase as they are supposed
viscosity favors a thicker film formation surrounding to do with asphaltenes, with the result that no phase
the aggregates which increases the cohesive forces separation occurs. At higher polymer concentrations, a
between the components and gives the expected larger quantity of polar aromatics is subtracted from
improvement in the paving in terms of resistance to maltenes and, therefore, the colloidal structure of
water and environmental conditions at operating asphaltene micelles or micellar aggregates is no longer
temperatures. On the other hand, by increasing the stabilized and tends to collapse.
temperature the difference in viscosity between the
0.7
PMB samples decreases, which favors the polymer basebitumen
0.6 2%SEPS
mixing during the asphalt modification and paving
0.5 4%SEPS
application. 0.4 6%SEPS
Is at 10rad/s[1]
0.3
Storage Stability 0.2
0.1
As described previously, a tube test was used to 0
determine the storage stability of polymer modified ‐0.1 0 20 40 60 80 100
bitumens. After vertically storing the tube at 180 Ԩ for ‐0.2
three days, DSR (temperature sweeps between 30 and ‐0.3
‐0.4
90 Ԩ) at 10 rad/s and also softening points(TABLE 4) Temperature [°C]
of the samples taken from the top and bottom of the
FIG. 2 THE ISOCHRONAL PLOT OF SEPARATION INDEX (Is)
tubes has been investigated and compared with
FOR BINDERS AT 10 RAD/S.
binders before hot storage.
TABLE 4 STORAGE STABILITY OF BINDERS Rheological Properties
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At high frequencies (low temperatures) no significant modulus and frequency. The difference between the
differences are detectable between the four binders. curves decreased after RTFO aging and all the samples
This is not surprising because it is well known that shifted to lower phase angles that are the causes of
similar systems have almost universal behavior when hardening.
the glass transition region is approached. At lower
100 2%SEPS
frequencies, the difference between binders with 4 and
90 4%SEPS aged
6% Polymer and 0 and 2% Polymer is significant. With
a small polymer quantity, the PMB is similar to neat 80 6%SEPS aged
bitumen and polymer acts as filler rather than a real
Phase angle [°]
70 basebitumen aged
modifier and has an effect mainly on the moduli
60
values. However, in samples with more polymer
content the binders are more likely to have a 50
polymeric behavior 40
1.00E+09 30
1.00E+08 20
1.00E+07
10
Complex modulus [Pa]
4%SEPS unaged
1.E+04
resistance to deformation, while phase angle reflects 6%SEPS unaged
the viscoelastic character. These binder parameters are 1.E+03
appears almost superposed over that of base bitumen. 1.E+04
basebitumen unaged
The differences among the curves become more and 1.E+03
2%SEPS unaed
more evident in shape and absolute values when a
1.E+02 4%SEPS unaged
greater quantities of polymer (4 and 6%) are added
and the curves show a sort of plateau in G* which 1.E+01 6%SEPS unaged
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Storage Modulus [Pa]
100 2%SEPS unaged 1.E+04
Tan (delta)[1]
4%SEPS unaged
1.E+03
6%SEPS unaged
10 1.E+02
1.E+01
1 1.E+00
0 20 40 60 80 100 30 40 50 60 70 80 90
1.E‐01 Temperature [°C]
Temperature[°C]
FIG. 6(A) STORAGE MODULUS FOR RTFO AGED SAMPLES
FIG.5 (C) DAMPING FACTOR OF UNAGED SAMPLES
1.E+06
The isochronal plots show a difference between the
base asphalt and the SEPS modified asphalt, 1.E+05
Complex Modulus [Pa]
decreased tan δ at intermediate and high temperatures FIG. 6(c) DAMPING FACTOR FOR RTFO AGED SAMPLES
are synonymies with the plateau region defined for Effect of temperature on G*/sinδ is shown in FIG. 7 for
polymers and demonstrates the ability of the polymer both aged and unaged samples. The Super‐pave
to form a continuous elastic network especially for parameter G*/sinδ was specified as the stiffness
SEPS (high content) modified asphalt. indicator for evaluating the rutting resistance of both
Oxidative ageing causes hardening of bitumen and unmodified and polymer modified binders. Rutting is
degradation of polymer, and consequently, changes in defined as the progressive accumulation of permanent
the rheological properties of polymer modified deformation of each layer of the pavement structure
binders.Oxidative ageing causes hardening of bitumen under repetitive loading. Obtained results indicate
and degradation of polymer, and consequently, that for unaged and aged specimens this parameter
changes in the rheological properties of polymer considerably increased by increasing the SEPS content.
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Strain [1]
20
1.E+06
15
1.E+05
10
|G*|/sin(delta) [Pa]
1.E+04
5
1.E+03
basebitumen unaged 0
1.E+02
2%SEPS unaged 0 50 100 150 200
Time [s]
1.E+01 4%SEPS unaged
6%SEPS unaged
(b)
1.E+00
0 20 40 60 80 100 FIG. 8 THE RESULTS OF CREEP TEST OF BITUMEN BINDERS AT
Temperature[°C] AT 50 OC FOR (A)UNAGED AND (B) AGED SAMPLES
(a) Results indicate that increasing the SEPS content and
1.E+06
aging in RTFO have noticeable effect on reducing the
1.E+05
creep. The residual strain for samples containing 4%
|G*|/sin(delta)[Pa]
1.E+04
and 6% SEPS is extremely close to zero and this fact is
1.E+03 a strong evidence of creation of polymeric network
1.E+02 basebitumen aged and continuous phase. As shown in these Figures, for
2%SEPS aged all cases the differences between obtained diagrams
1.E+01 4%SEPS
6%SEPS aged have increased by increasing the number of cycles.
1.E+00
After RTFO aging the creep resilience decreased for
30 40 50 60 70 80 90
Temperature [°C] PMBs and this can be result of polymer degradation.
(b)
FIG. 7 RUTTING FACTOR FOR UNAGED(A) AND RTFO AGED FTIR Spectroscpy
(B) SAMPLES
Fourier transform spectroscopy is a measurement
The results of creep test at 50 C have been shown in o technique whereby spectra are collected based on
FIG. 8. At each loading cycle, the loading and recovery measurements of the coherence of a radiative source,
time was equal to 1s and 9s, respectively and loading using time‐domain or space‐domain measurements of
cycles repeated for 20 times (10 cycles with 100 Pa the electromagnetic radiation or other type of
loading and 10 cycles with 3200Pa loading). radiation. In this study the FTIR test was employed to
Instantaneous elastic strain of asphalt developed investigate the chemical bonding changes of neat and
during the stage of loading stress, and the viscoelastic polymer modified asphalt and the results are shown in
strain of asphalt accumulated to the total creep strain FIG. 9. In the Figure, the strong peaks around 2850 cm‐1
at the time of unloading. The instantaneous elastic and 2920 cm‐1 are typical C‐H stretching vibrations in
strain of asphalt disappeared after unloading, and the aliphatic chains. The band at around 1030 cm‐1 is
delayed elastic stain recovered gradually. The assigned to stretching sulfoxide. The aliphatic
unrecoverable viscoelastic strain is the permanent branched band (bending C‐H of CH 3 ) and aliphatic
strain. index band (bending C‐H of ‐ (CH 2)n‐) are observed
80 at 1376 cm‐1 and 1460 cm‐1 respectively. The 1600 cm‐1
basebitumen unaged
70 and 1690 cm‐1 bands correspond to the aromatic band
2%SEPS unaged
60
4%SEPS unaged (stretching C=C aromatic) and carbonyl band,
50
6%SEPS unaged (stretching C=O conjugated). As it can be seen by
40
30
adding the SEPS content the peaks area around 690 to
20 800 cm‐1 (related to aromatic C‐H) have increased.
10 Whereas,the areas for stretching OH group, centering
0 around 3742 cm‐1 has increased by adding SEPS which
0 50 100 150 200 proves the creation of chemical interactions between
(a) polymer and asphalt.
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FIG. 9 THE FTIR OF BITUMEN BINDERS
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