Construction and Building Materials 151 (2017) 464–478

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Rheological properties of asphalt binders modified with styrene-

butadiene-styrene (SBS), ground tire rubber (GTR), or polyphosphoric
acid (PPA)
Ali Behnood ⇑, Jan Olek
Post-Doctoral Research Assistant, Lyles School of Civil Engineering, Purdue University, 550 Stadium Mall, West Lafayette, IN 47907-2051, USA

h i g h l i g h t s

A neat binder was modified with styrene-butadiene-styrene (SBS), ground tire rubber (GTR) or polyphosphoric acid (PPA).

Rheological properties of neat and modified asphalt binders were investigated.

The multiple stress creep recovery (MSCR) protocol was successfully used to grade all the binders.

‘‘Percent difference” criterion of the MSCR protocol seems to be unjustified.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the rheological properties of modified binders have been investigated. For this purpose,
Received 11 March 2017 varying amounts of styrene-butadiene-styrene (SBS), ground tire rubber (GTR) or polyphosphoric acid
Received in revised form 17 June 2017 (PPA) modifiers were added to a neat binder. The dynamic shear rheometer (DSR) was used to grade
Accepted 19 June 2017
the original, RTFO-aged and PAV-aged binders based on the conventional performance grading (PG)
Available online 26 June 2017
and the multiple stress creep recovery (MSCR) systems. The bending beam rheometer (BBR) was used
to study the low-temperature properties of the asphalt binders. All of the modifiers were found to
Keywords:
improve the high temperature properties of the neat asphalt. With regard to the intermediate tempera-
Rutting
Multiple stress creep recovery
tures, SBS and PPA did not significantly affect the performance of the binder. However, GTR significantly
Modifiers decreased the stiffness of the binder. In addition, these modifiers were not found to have significant
Styrene-butadiene-styrene effects on the low temperature continuous grade of the binders. The MSCR protocol was successfully used
Ground tire rubber to grade all the binders; however, the ‘‘percent difference” criterion of the MSCR protocol seems to be not
Polyphosphoric acid applicable with regard to some binders and conditions.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction As the temperature of asphalt pavement drops during cold seasons,

During its service life, the asphalt pavement is exposed to a
variety of load and climatological conditions. Asphalt mixtures
should be able to sustain the traffic loads during hot periods of
summer as well as cold periods of winter. Asphalt binders, as one
of the main components of asphalt mixtures, are viscoelastic mate-
rials with time- and temperature-dependent behavior. That is, at
low and intermediate temperatures, they behave in a brittle-
viscoelastic manner while at high temperatures, they behave in a
fluid manner. Several distresses observed in asphalt pavements
can be related to the viscoelastic behavior of the asphalt binders.
⇑ Corresponding author.
E-mail addresses: abehnood@purdue.edu (A. Behnood), olek@purdue.edu
(J. Olek).
the pavement contracts, which can lead to cracking due to the
increased stiffness of the asphalt binder. This type of distress is
called thermal cracking, and results in cracks oriented transverse
to the centerline. Rutting, another type of distress observed in
asphalt pavements, is more common during hot seasons. Rutting
is the permanent deformation in the wheel path induced by traffic
loads, when the viscosity or stiffness of the asphalt binder is
reduced due to high temperatures.
To overcome or to mitigate the distresses of asphalt mixtures
that are related to the viscoelastic behavior of the asphalt binders,
engineers and material scientists have made attempts to modify
the properties of asphalt binders and mixtures using different
types of modifiers [1–7]. Ideally, a good modifier improves the
properties of an asphalt binder by increasing its complex modulus

http://dx.doi.org/10.1016/j.conbuildmat.2017.06.115
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478
at high temperatures and decreasing that parameter at intermedi-
ate and low temperatures.
In recent years, the use of polymers such as styrene-butadiene-
styrene (SBS) copolymer to enhance the performance of asphalt
binders and mixtures has been given lots of attention. The addition
of polymers to asphalt binders improves the adhesion and cohe-
sion [8], increases the stiffness and viscosity [4,9–11] and reduces
the temperature susceptibility of the binders [4,9]. In addition,
asphalt mixtures containing polymer-modified binders have been
found to show improved rutting resistance and fatigue perfor-
mance [4,12]. However, polymer-modified binders are consider-
ably more expensive than unmodified binders.
Therefore, finding cost-effective and more environmentally
friendly ways to modify binders, which could improve the perfor-
mance of the binder from different points of view, is a critical task
for pavement engineers and material scientists. From economic
and environmental points of view, the use of recycled additives
instead of virgin materials could have several benefits such as
reducing the pressure on landfills. The use of ground tire rubber
(GTR) from end-of-life tires, as an alternative for polymers, is a
valuable approach to enhance the properties of asphalt binders.
Another approach of more economically modifying the asphalt bin-
ders could be possible by the use of small amounts of inexpensive
modifiers. In this sense, polyphosphoric acid (PPA) might be a good
alternative for polymers since small amounts of this additive have
been reported [13–15] to have a comparable effects on the perfor-
mance of asphalt binders as that achieved by addition of polymers.
This study aims to investigate the effects of adding styrene-
butadiene-styrene (SBS), ground tire rubber (GTR) and polyphos-
phoric acid (PPA) on the rheological properties of asphalt binders.
For this purpose, the properties of modified binders were evaluated
at a wide range of simulated service climate conditions. Dynamic
shear rheometer (DSR) was used to study the high temperature
and intermediate temperature properties of the asphalt binders.
A bending beam rheometer (BBR) was used to evaluate the perfor-
mance of the binders at low temperatures.
2. Experimental details
In this section, the materials as well as the methods to prepare the modified
binders will be discussed.
2.1. Materials
To study the effects of various types of modifiers on the rheological properties
of asphalt binders, a neat binder was modified based on the experimental matrix
shown in Table 1. Three types of modifiers were used in this research: (a) a SBS
block copolymer (Kraton D1192) supplied in pellet form, (b) a 30 mesh ambient
produced GTR from passenger car tires, and (c) a PPA with the P2O5 content of
85%. The content of the modifiers was selected based on the common ranges of their
applications in the asphalt industry [14,16–22]. It should be noted that although the
use of combined modifiers to alter the properties of the neat binder would likely
also produce some interesting results, such modifications were not attempted in
this study.
Table 1
Binder IDs, types of modifiers and their percentages used in the study.
Binder ID Type of modifier Modifier content (wt.%)
Neat binder (PG 64-22) – 0
2%SBS SBS 2
3%SBS SBS 3 der at creep stress levels of, respectively, 0.1 kPa (R0.1) and 3.2 kPa
4%SBS SBS 4 (R3.2) are calculated as follows [24]:
8%GTR GTR 8 P20
12%GTR GTR 12
16%GTR GTR 16
0.3%PPA PPA 0.3
0.6%PPA PPA 0.6
1.2%PPA PPA 1.2
465
2.2. Preparation of binder test specimens
All modified binders used in this study were prepared by mixing the neat
asphalt binder (i.e., PG 64-22) with the appropriate modifier. However, the specific
mixing procedures varied, depending on the type of the modifier used. Specifically,
in order to prepare the SBS-modified binders, a high-concentration SBS-modified
binder (i.e., 18% SBS) was prepared first. That SBS-modified binder was subse-
quently diluted to obtain the test specimens with desired concentration of SBS.
The high-concentrate SBS-modified binder was prepared by adding SBS copolymer
(18 wt.% of the binder) to the heated neat asphalt binder (i.e., at 175 ± 1 °C). The
resulting mix was then blended and sheared for 30 min in a high shear mixer at
4000 rpm. The mix was again heated to 175 ± 1 °C and diluted by adding the appro-
priate amount of the neat binder that was pre-heated to 150 ± 1 °C. The modified
blend was then manually stirred for 10 min (at room temperature) to ensure the
homogeneity of the final product.
A different method was used to prepare the GTR- and PPA-modified binders. In
these cases, the neat asphalt binder was first heated to 150 ± 1 °C and then the
desired amount of PPA or GTR was added to the hot asphalt. In the next step, the
mix was blended and sheared for 20 min in a high shear mixer at 4000 rpm. The
final step involved manually stirring of the mix for 1 h (at room temperature) to
ensure a homogenous product.
To address potential inhomogeneity issues, the test specimens were collected
from different locations within the bulk binder sample. In addition, replicate spec-
imens were tested on different days. When combined, the results obtained from
these diverse test specimens were characterized by low coefficient of variation, thus
indicating relative homogeneity of the test specimens.
3. Test program
Fig. 1 shows the summary of the tests that were conducted on
the neat and laboratory-modified binders. The tests conducted on
these binders included:

Superpave performance grading (PG) (AASHTO M 320)
o Dynamic shear rheometer (DSR) tests (AASHTO T 315)
o Bending beam rheometer (BBR) tests (AASHTO T 313)

Multiple stress creep recovery (MSCR) tests (AASHTO T 350)

Frequency sweep test using DSR
The AASHTO M 320 specification and associated testing proto-
cols (AASHTO T 315 and AASHTO T 313) were utilized to grade
both, the modified and the unmodified (neat) binders. Since
asphalts harden (i.e., change their visco-elastic properties) during
various stages of pavement construction (i.e., mixing, transport
and placement of the hot mix) as well as after the pavement has
been constructed, the grading was performed using the original
(also referred to as virgin or unaged) binders, the rolling thin film
oven (RTFO)-aged binders and the pressure aging vessel (PAV)-
aged binders. The low temperature stiffness of the binders was
evaluated using the bending beam rheometer (BBR).
In the current study, the MSCR test was performed on RTFO-
aged binders according to AASHTO T 350 [23]. The test was per-
formed at different temperatures by first applying a stress of
0.1 kPa for twenty cycles followed by a stress of 3.2 kPa for ten
cycles. Each cycle consisted of 1 s of shear creep followed by a
recovery period of 9 s. The shear stress of 0.1 kPa characterizes
the behavior of a binder in the linear viscoelastic region while
the 3.2 kPa stress level reflects a binder’s behavior in the non-
linear viscoelastic region for most modified and unmodified bin-
ders. The MSCR test generates two key parameters as per AASHTO
M 332 [24]. These parameters are: (a) the percent recovery (R) and
(b) the nonrecoverable creep compliance (Jnr).
The values of the average percent recovery for the asphalt bin-
N¼11 ½2r ð0:1; NÞ
R0:1 ¼ ð1Þ
10
P10
N¼1 ½2r ð3:2; NÞ
R3:2 ¼ ð2Þ
10
466 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478
Fig. 1. Summary of the tests used to study the rheological properties of the neat and modified binders.
where 2r ð0:1; NÞ. and 2r ð3:2; NÞ. are the percent recovery at 0.1 kPa
and 3.2 kPa at cycle number N, respectively, and N is the cycle num-
ber at each stress level.
It should be noted that the ‘‘percent recovery” parameter is not
currently utilized as a grading parameter in AASHTO M 332 speci-
fication [24]. However, this parameter is used by some states as an
indicator of the presence of polymer modifier in the binder (i.e. the
‘‘PG plus” grading states). On the other hand, the nonrecoverable
creep compliance (Jnr) parameter was found [25–27] to provide a
much stronger correlation with rutting resistance than the Super-
pave PG criterion (i.e. the G⁄/sind value). The binder grading
methodology adopted by the AASHTO M 332 specification utilizes
the Jnr based criteria which are (a) the average value of nonrecov-
erable creep compliance at 3.2 kPa (Jnr3.2) for a given traffic level
and (b) the 75% max. value for the difference in the nonrecoverable
creep compliance between 0.1 kPa a 3.2 kPa (J nrdiff ) to account for
various categories of traffic loading (i.e. the expected traffic level
and load rate (speed)). The different categories of traffic loading
considered in the AASHTO M specification are as follows: Standard
(S), Heavy (H), Very Heavy (V), and Extremely Heavy (E).
T values of the average nonrecoverable creep compliances at
0.1 kPa (Jnr0.1) and 3.2 kPa (Jnr3.2) are expressed as [24]:
P20
N¼11 ½J nr ð0:1; NÞ
J nr0:1 ¼
10
P10
N¼1 ½J nr ð3:2; NÞ
J nr3:2 ¼
10
where Jnr(0.1, N) and Jnr(3.2, N) are the nonrecoverable creep com-
pliances at 0.1 kPa and 3.2 kPa at cycle number N, respectively,
and N is the cycle number at each stress level.
The percent difference in nonrecoverable creep compliance
between 0.1 kPa and 3.2 kPa is calculated as:
½J nr3:2  J nr0:1   100
J nrdiff ¼
J nr0:1
4. Test results
The results of the aforementioned binder tests are given in this
section
4.1. Dynamic shear rheometer tests
Two replicate samples were used to complete the grading of
each of the original, RTFO-aged and PAV-aged binders. Fig. 2 shows
the averages values of the DSR test results obtained for the original
binder at various temperatures. The results shown in Fig. 2(a) indi-
cate that all of the three modifiers used in this study (i.e. the SBS,
PPA and GTR) improved the performance of binders at high tem-
peratures by increasing the complex shear moduli and thus ren-
dering the modified binders stiffer compared to the neat (i.e.
unmodified) binders. In addition, these modifiers decreased the
phase angle of the modified binders, thus making them less viscous
(Fig. 2(b)). With regard to PPA-modified binders, the phase angle
shows a linear upward trend with respect to temperature. On the
other hand, the relationships between the phase angle and the
temperature appear to be non-linear for the SBS and GTR modified
binders.
Bonferroni’s multiple comparison test is one of the several tests
that considers all possible pairwise differences of means at the
same time. In other words, it is used to determine which means
amongst a set of analyzed means are different from the others. This
post-ANOVA analysis allows to draw more detailed conclusions
regarding the differences between means. The significance of the
impact of modifiers on the properties of the binders illustrated in
Fig. 2 was confirmed statistically using the Bonferroni’s compar-
ison of means at a significance level of 95% (i.e. a = 0.05) [28].
Although not presented in details here due to space limitation,
the Bonferroni’s pairwise comparison showed that, at all test tem-
ð3Þ
peratures, the 0.6%PPA and 2%SBS binders were not statistically
different (i.e. p < a = 0.05) and thus they can be used interchange-
ably. In addition, when comparing the values of the rutting param-
ð4Þ
eter (G⁄/sin d), binders modified with 1.2% PPA and 4% SBS were
also found not to be statistically different at all the test tempera-
tures. These observations are also confirmed by trends shown in
Fig. 2(c) in that the curves associated with these binders plot very
close to each other.
Further analysis of Fig. 2(c) reveals that when tested at the tem-
perature of 52 °C, binders modified with 4% SBS and 8% GTR also
show similar values of the rutting parameter. However, as the test-
ð5Þ
ing temperature increases, the rutting parameter for binder with
8%GTR becomes smaller than that observed for the binder with
4%SBS. It should be noted that this finding might be true for the
particular combinations of base binder and modifiers studied in
this part of research. Considering that the effects of PPA are highly
dependent on crude source [29], further research is required to
make a more general conclusion. Similar trends (i.e. an increase
in the magnitude of differences in the rutting parameter values
with the increase in the testing temperature) can be seen for all
of the other binders used in the study.
Fig. 3 shows the averages of the RTFO-aged binder test results at
various temperatures. These results were also analyzed
 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478 467

35

30

25 PG64
2%SBS

G* (kPa)
3%SBS
20
4%SBS
8%GTR
15
12%GTR
16%GTR
10 0.3%PPA
0.6%PPA
5 1.2%PPA

0
46 52 58 64 70 76 82 88
(a)
Temperature (°C)
90

85
PG64
2%SBS
Phase Angle (degree)

80 3%SBS
4%SBS
8%GTR
75 12%GTR
16%GTR
0.3%PPA
70 0.6%PPA
1.2%PPA

65
46 52 58 64 70 76 82 88
(b)
Temperature (°C)
35

30

25 PG64
2%SBS
(kPa)

3%SBS
20
4%SBS
G*/sin

8%GTR
15
12%GTR
16%GTR
10 0.3%PPA
0.6%PPA
5 1.2%PPA

0
46 52 58 64 70 76 82 88
(c)
Temperature (°C)

Fig. 2. The DSR test results for the original binders: (a) complex modulus (G*), (b) phase angle (d) and (c) PG rutting parameter (G*/sin d).

statistically using the Bonferroni’s comparison of means of rutting found to be statistically similar. In addition, binders modified with
parameter [28]. Similar to the results of original binder presented 1.2% PPA and 4% SBS also did not show statistically significant
in Fig. 2, the RTFO-aged binders with 0.6%PPA and 2%SBS were differences.
468 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478

60

50

PG64
40 2%SBS
3%SBS
G* (kPa) 4%SBS
30
8%GTR
12%GTR
20 16%GTR
0.3%PPA
0.6%PPA
10
1.2%PPA

0
46 52 58 64 70 76 82 88
(a)
Temperature (°C)
90

85

80 PG64
Phase Angle (degree)

2%SBS
75
3%SBS
4%SBS
70
8%GTR
12%GTR
65
16%GTR
60 0.3%PPA
0.6%PPA
55 1.2%PPA

50
46 52 58 64 70 76 82 88
(b)
Temperature (°C)
70

60

PG64
50
2%SBS
(kPa)

3%SBS
40
4%SBS
G*/sin

8%GTR
30
12%GTR
16%GTR
20
0.3%PPA
0.6%PPA
10 1.2%PPA

0
46 52 58 64 70 76 82 88
(c)
Temperature (°C)

Fig. 3. The DSR results for the RTFO-aged binders: (a) complex modulus (G*), (b) phase angle (d), (c) G*/sin d.

Fig. 4 shows the average test results for the complex modulus the effects of SBS and PPA modifiers on, respectively, the complex
(G⁄), phase angle (d) and the intermediate temperature parameter modulus and the intermediate temperature parameter are negligi-
(G⁄sin d) of the PAV-aged binder obtained for the intermediate ble as all curves representing these modifiers shown in Fig. 4
temperatures (19–31 °C). It can be seen (Fig. 4(a) and (c)) that (a) and (c) are relatively close to each other. On the other hand,
 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478 469

12000

10000

PG64
8000 2%SBS
3%SBS
4%SBS
G* (kPa) 6000
8%GTR
12%GTR
4000 16%GTR
0.3%PPA
0.6%PPA
2000
1.2%PPA

0
(a) 19 22 25 28 31
Temperature (°C)
55

50
PG64
2%SBS
Phase angle (degree)

45 3%SBS
4%SBS
8%GTR
40 12%GTR
16%GTR
0.3%PPA
35 0.6%PPA
1.2%PPA

30
(b) 19 22 25 28 31
Temperature (°C)
8000

7000

6000 PG64
2%SBS
(kPa)

5000
3%SBS
4%SBS
4000
G*.sin

8%GTR
12%GTR
3000
16%GTR
2000 0.3%PPA
0.6%PPA
1000 1.2%PPA

0
(c) 19 22 25 28 31
Temperature (°C)

Fig. 4. The DSR results for the PAV-aged binders: (a) complex modulus (G*), (b) phase angle (d), (c) the intermediate temperature parameter (G*sin d).

for the same range of the intermediate temperatures, the GTR neat binders shown in Fig. 4(c). Furthermore, the change in the
modifier was found to significantly impact the intermediate tem- intermediate temperature parameter was also found to be strongly
perature parameter of the asphalt binder used in the study as depended on the percent of the GTR modifier used. With regard to
demonstrated by the separation of the curves for modified and the phase angle of the binders, it was found to be significantly
470 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478
affected by all modifiers used in this study (see Fig. 4(b)). The find-
ings related to the role of the GTR we statistically confirmed by
performing the Bonferroni’s analysis shown in reference [28].
As expected, unlike the nonlinear trend of phase angles at high
temperatures, Fig. 4(b) shows that phase angles of the PAV-aged
binders at intermediate temperatures show almost linear trend.
This is due to the fact that at the intermediate temperatures the
binders behave more elastically.
Due to the near-superposition of most of the curves in Fig. 4(c),
the ratios between the intermediate temperature parameter of the
modified binder to the intermediate temperature parameter of the
neat binder were calculated (Table 2) to better differentiate the
effects of various modifiers on the intermediate properties of mod-
ified binders. Analysis of these ratios will aid in the evaluation of
the intensity of the effect of modifiers at intermediate tempera-
tures. It can be seen from Table 2 that the GTR modifier signifi-
cantly impacts the intermediate temperature parameter of the
asphalt binder used in the study (as demonstrated by its diver-
gence from the value of 1.00).
4.2. Bending beam rheometer (BBR) test
The Bending Beam Rheometer (BBR) test is a commonly used
method to study the properties of asphalt binders at low tempera-
tures. The properties that are measured in the BBR tests are low
temperature stiffness and relaxation of asphalt binders. In the cur-
rent study, the BBR test was performed following the protocol out-
lined in the AASHTO T 313 specification.
The BBR tests were conducted for each laboratory-modified bin-
der at three different temperatures (i.e., 6 °C, 12 °C and 18 °C)
to establish their master curves. Two replicate samples were pre-
pared for each temperature-binder combination. Fig. 5 shows the
averages of the slope and stiffness for each temperature-binder
combination. Fig. 5(a) shows that GTR significantly decreases the
stiffness of the asphalt binder at low temperatures, especially at
higher percentages of addition. A slight reduction in the stiffness
of the asphalt binders modified with SBS or PPA can also be seen
in Fig. 5(a).
In addition to the stiffness of the binder, the slope of the master
stiffness curve (m-value) is an important parameter to report. This
parameter (m-value) is an indication of how quickly an asphalt
binder relaxes the stresses. That is, a higher m-value is an indica-
tion of a greater ability of the binder to relax the stress. Fig. 5(b)
shows that, PPA increases the m-value while both, the GTR or
SBS additives, decrease it, relative to the base asphalt.
The Bonferroni’s analysis of means of the stiffness values was
performed to further investigate the significance of the modifiers
on the low temperature properties of the asphalt binders. Due to
space limitation, the details of this analysis are not reported here
but can be found in reference [28]. These results of the Bonferroni’s
pairwise comparisons indicate that, irrespective of the test temper-
Table 2
Ratio between the intermediate temperature parameter of the modified binder to the intermediate temperature parameter of the neat binder.
Binder ID Temperature (°C)
31
2%SBS 1.02
3%SBS 1.02
4%SBS 1.01
8%GTR 0.92
12%GTR 0.92
16%GTR 0.84
0.3%PPA 1.05
0.6%PPA 0.95
1.2%PPA 1.04
ature, the stiffness of all the GTR-modified binders and the binder
modified with 1.2% PPA was significantly reduced compared to the
stiffness of the neat binder. In addition, 4% SBS was found to also
significantly reduce the stiffness of the asphalt binder at 18 °C.
Similarly, the Bonferroni’s comparison of means of m-value was
also performed in order to investigate the significance of the type
and percentage of the modifiers on the low temperature properties
of the tested asphalt binders. Although the PPA was found to
slightly increase the m-values of the binders, its effect was not sta-
tistically significant. Among the testing temperatures, binders
modified with SBS or GTR show significant reduction in their m-
values (compared to the neat binder) only at 6 °C. It should be
noted that BBR method has some limitations. Specifically, the
effects of elastomers are typically not properly reflected in the
value of the m-parameter due to the fact that they increase tensile
strength of the binder and reduce its stress relaxation capabilities.
4.3. Multiple stress creep recovery (MSCR) test
The MSCR tests were conducted in accordance with the require-
ments of the AASHTO T 350 specification. For each test-
temperature-binder combination, two replicate specimens were
prepared and tested. Fig. 6 shows the variation of creep compliance
at 3.2 kPa and 0.1 kPa stress levels as well as the percent difference
of the creep compliance between these two stress levels with
temperature.
As already mentioned earlier (Section 3), the AASHTO M 332
specification uses the creep compliance based criteria (i.e. the
average value of nonrecoverable creep compliance at 3.2 kPa
(Jnr3.2) for a given traffic level and the 75% max. value for the differ-
ence in the nonrecoverable creep compliance between 0.1 kPa and
3.2 kPa (J nrdiff .) to grade the binders. The results shown in Fig. 6(a)
indicate that the Jnr3.2 criterion can be successfully used to grade
both, the unmodified and the modified binders.
The percent difference between the creep compliances at
3.2 kPa and 0.1 kPa is the second criterion in the MSCR protocol
to grade asphalt binders. Based on this criterion, an asphalt binder
is considered to be rutting susceptible if it shows a difference in the
nonrecoverable creep compliance of more than 75%. Based on this
criterion, asphalt binder modified with 4% SBS used in this study
can be considered as rutting susceptible at 76 °C since it shows
slightly higher than 75% difference between creep compliance at
3.2 kPa and 0.1 kPa (Fig. 6(c)).
In a recent study conducted by Faxina et al. [30], it was
observed that for a binder modified with 2% PPA, the percent dif-
ference between creep compliance at 3.2 kPa and 0.1 kPa was as
high as 93.22%. However, the same researchers also observed that
this binder showed the highest percent recovery and lowest creep
compliance at both stress levels. In the current study, similar
behavior was observed for the binder modified with 8% GTR at
70 °C and 76 °C. In addition, binders modified with 12% GTR and
28 25 22
0.99 0.97 0.94
0.97 0.94 0.90
0.96 0.92 0.89
0.88 0.84 0.82
0.87 0.83 0.78
0.77 0.72 0.67
1.01 0.99 1.00
0.92 0.89 0.88
0.97 0.93 0.90
 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478 471

400
Neat binder
350
2%SBS
300
3%SBS
250

Stiffness (MPa)
4%SBS
200
8%GTR
150
12%GTR
100
16%GTR
50
0.3%PPA
0 0.6%PPA
0 -6 -12 -18 -24

(a) Temperature (°C) 1.2%PPA

0.420 Neat binder

0.400
2%SBS
0.380
3%SBS
0.360
0.340 4%SBS
m value

0.320 8%GTR
0.300
12%GTR
0.280
16%GTR
0.260
0.240 0.3%PPA
0.220 0.6%PPA
0 -6 -12 -18 -24

(b) Temperature (°C) 1.2%PPA

Fig. 5. BBR tests results: (a) stiffness, (b) slope (m-value).

16% GTR could not be graded at testing temperatures higher than
58 °C and 52 °C, respectively, since they showed a value of more
than 75% for percent difference criterion. It can also be seen
(Fig. 6(c)) that as the amount of modifier increases, the percent dif-
ference between creep compliances increases.
Fig. 7 shows the variation of average percent recovery at 3.2 kPa
and 0.1 kPa stress levels as well as the percent difference of the
average percent recovery between these two stress levels with
temperature. As shown in Fig. 7, the modifiers used in this study
increases the percent recovery of the binder at both stress levels.
The highest increments in the average percent recoveries are asso-
ciated with the binders modified with GTR. Therefore, GTR can be
considered as an excellent modifier for mitigation of the rutting
problem since it can recover most of its deformation. This observa-
tion contradicts the finding in the previous paragraph where GTR-
modified binders did not pass the ‘‘percent-difference” criterion.
For that reason, one may conclude that the ‘‘percent-difference”
criterion is not justified.
Fig. 7 also shows that the average percent recovery of the bin-
ders (i.e., bot modified and unmodified) decreases by increasing
the temperature. The trend of reduction is sharper at higher stress
level (i.e., 3.2 kPa) than lower stress level (0.1 kPa).
As shown in Figs. 8–11, the GTR-modified binders tested here
show the least amount of accumulated strain in the MSCR tests
at different temperatures. That is, these GTR-modified binders
are more resistant to deformation (or rutting) than the other bin-
ders, depending on the addition rate. The effectiveness of GTR in
reducing the permanent deformation of the asphalt binders and
mixes has been also reported in previous research [3,26]. Overall,
these observations suggest that the ‘‘percent difference” criterion
of the MSCR cannot be universally applied as it depends on the
type of the modifier and the testing conditions (e.g. testing
temperature).
Table 3 shows the summary of the designated grades of the bin-
ders based on the conventional and MSCR systems. The continuous
grade (by conventional PG testing) indicates the actual pass/fail
points at high and low temperatures. The low-temperature grade
designations of the binders are not significantly different. It should
be mentioned that the m-value is the dominant criterion in desig-
nating the low temperature grades of the binders. Table 3 also
shows the calculated DTc values. The DTc is the difference between
Tc(stiffness) (i.e., exact temperature where stiffness at 60 s of loading
equals to 300 MPa) and Tc(m-value) (i.e., exact temperature where m-
value at 60 s of loading equals to 0.300). The value of DTc is a good
parameter to identify the sensitivity to non-load related distresses
(i.e. thermal cracking) [31] as well as fatigue cracking [32]. As the
value of DTc decreases and becomes more negative, the binder
losses some of its relaxation properties (i.e., the ability of recovery
to its initial stage). Therefore, the binder would be more suscepti-
ble to non-load related cracking. As shown in Table 3, as the
amount of SBS or GTR increases, the value of DTc decreases (i.e.,
it becomes more negative), suggesting a higher susceptibility of
472 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478

5
Neat binder

Jnr @3.2 kPa (1/kPa)

2%SBS
4
3%SBS
Standard
Grade 4%SBS
3
8%GTR
12%GTR
2
High Grade 16%GTR
0.3%PPA
Very High
1
Grade 0.6%PPA
Extremely 1.2%PPA
High Grade
0
52 58 64 70 76 82 88
(a) Temperature ( C)

4
Neat binder
Jnr @0.1 kPa (1/kPa)

2%SBS
3 3%SBS
4%SBS
8%GTR
2 12%GTR
16%GTR
1 0.3%PPA
0.6%PPA
1.2%PPA
0
52 58 64 70 76 82 88
(b)
Temperature ( C)

500
450
400 Neat binder
Percent Difference

350 2%SBS
300 3%SBS
4%SBS
250
8%GTR
200 12%GTR
150 16%GTR
100 0.3%PPA
0.6%PPA
50
1.2%PPA
0
52 58 64 70 76 82 88
(c)
Temperature ( C)

Fig. 6. Variation vs. temperature of (a) creep compliance at 3.2 kPa, (b) creep compliance at 0.1 kPa, (c) percent difference between 3.2 kPa and 0.1 kPa.

the binder to non-load related cracking. However, in the presence is not appropriate in in the case of selection of high temperature PG
of PPA, the value of DTc increases (i.e., it becomes less negative), grade. Based on grade-bumping concept, on a typical freeway in a
suggesting that the binder becomes less susceptible to a non- PG 64 climate with a traffic level greater than 0.3 million ESALs and
load related cracking. a standing traffic (speeds under 20 km/h), two grade bumps would
Table 3 shows that, in some cases, the MSCR test can be be recommended suggesting the use of PG 76 (e.g., binder modified
expected to optimize binder formulation to avoid the use of with 12% GTR). However, based on the MSCR test and AASHTO T
over-engineered binders and higher cost. This is due to the fact 350 specification, it would be possible to use the binder modified
that the new specification addresses the expected traffic levels with 8% GTR which is less expensive than the one modified with
through creep compliance instead of grade-bumping. Since rutting 12% GTR. On the same road and considering the same traffic level
is a nonlinear phenomenon, using linear grade bumping approach and slow traffic speed, if it was decided to use PPA to modify the
 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478 473

100

Average Percent Recovery @ 3.2 kPa

90
80 Neat binder
70 2%SBS
60 3%SBS
4%SBS
50
8%GTR
40 12%GTR
30 16%GTR
20 0.3%PPA
0.6%PPA
10
1.2%PPA
0
52 58 64 70 76 82 88
(a) Temperature ( C)

100
Average Percent Recovery @ 0.1 kPa

90
80 Neat binder
70 2%SBS
60 3%SBS
4%SBS
50
8%GTR
40 12%GTR
30 16%GTR
20 0.3%PPA
0.6%PPA
10
1.2%PPA
0
52 58 64 70 76 82 88
(b)
Temperature ( C)
100
Percent Difference in Average Percent

90
80 Neat binder
70 2%SBS
3%SBS
Recovery

60
4%SBS
50
8%GTR
40 12%GTR
30 16%GTR
20 0.3%PPA
0.6%PPA
10
1.2%PPA
0
52 58 64 70 76 82 88
(c) Temperature ( C)

Fig. 7. Variation vs. temperature of (a) average percent recovery at 3.2 kPa, (b) average percent recovery at 0.1 kPa, (c) percent difference in average percent recovery.

binder, 0.6% PPA would be required to get a PG 70 binder. However, expensive than the one required using PG system. Therefore, a con-
it would again be possible to use lower amount of modifier (i.e., clusion regarding the cost-effectiveness of the MSCR protocol could
0.3% PPA) based on MSCR test based approach. not be made.
Further analysis of the data indicates that, in some other cases,
using the PG system for binder selection may be more cost-
4.4. Frequency sweep test
effective than using the MSCR system. For example, on a typical
highway in a PG 64 climate condition with a traffic level of more
Constructing the master curve of an asphalt binder is a useful
than 30 million ESALs, one grade bump would be required to get
technique to study the relationship between binder stiffness and
a PG 70 binder (e.g., 2%SBS). However, based on MSCR system, a
reduced frequency over a range of frequencies and temperatures.
Very high grade binder should be assigned for this condition. The
To construct the master curve of laboratory-modified binders,
amount of SBS that would be required to make a PG 64V binder
complex shear moduli (G⁄) at high and intermediate temperatures
from this particular neat binder is 4%, which is higher than 2%. That
were obtained by conducting frequency sweep tests and taking the
is, for this project, MSCR system requires a binder that is more
average of two replicate tests. With regard to low temperature
474 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478

80 600
70 Neat binder
Neat binder 500
60 2%SBS
2%SBS
400 3%SBS
50
Strain (%)

Strain (%)
3%SBS
4%SBS
40 4%SBS 300
8%GTR
30 8%GTR
200 12%GTR
20 16%GTR
16%GTR
0.3%PPA 100
10 0.3%PPA
0.6%PPA
0 0 0.6%PPA
0 10 20 30 1.2%PPA 0 10 20 30
1.2%PPA
(a) Cycles (a) Time (s)
1600 12000
1400 Neat binder
Neat binder 10000
1200 2%SBS 2%SBS
1000 8000 3%SBS
Strain (%)

3%SBS

Strain (%)
800 4%SBS 4%SBS
6000
8%GTR 8%GTR
600
16%GTR 4000 12%GTR
400
0.3%PPA 16%GTR
200 2000
0.6%PPA 0.3%PPA
0
0 10 20 30 40 1.2%PPA 0 0.6%PPA
0 10 20 30 40
(b) Cycles (b)
1.2%PPA
Time (s)
Fig. 8. Accumulated strain in the MSCR test at 52 °C after the completion of (a)
Fig. 10. Accumulated strain in the MSCR test at 64 °C after the completion of (a)
0.1 kPa stress level, (b) 3.2 kPa stress level.
0.1 kPa stress level, (b) 3.2 kPa stress level.

1200
250
Neat binder
Neat binder 1000
200 2%SBS
2%SBS
800 3%SBS
3%SBS
Strain (%)
Strain (%)

150 4%SBS
4%SBS 600
8%GTR
8%GTR
100 400 12%GTR
12%GTR
16%GTR
50 16%GTR 200
0.3%PPA
0.3%PPA
0 0.6%PPA
0 0.6%PPA
0 10 20 30 0 10 20 30 1.2%PPA
1.2%PPA (a)
(a) Time (s) Time (s)

25000
4500
4000 Neat binder Neat binder
20000 2%SBS
3500 2%SBS
3000 3%SBS 3%SBS
Strain (%)

15000
Strain (%)

2500 4%SBS 4%SBS

2000 8%GTR 8%GTR
10000
1500 12%GTR 12%GTR
1000 16%GTR 5000 16%GTR
500 0.3%PPA 0.3%PPA
0 0.6%PPA 0 0.6%PPA
0 10 20 30 40 0 10 20 30 40
1.2%PPA 1.2%PPA
(b) Time (s) (b) Time (s)

Fig. 9. Accumulated strain in the MSCR test at 58 °C after the completion of (a) Fig. 11. Accumulated strain in the MSCR test at 70 °C after the completion of (a)
0.1 kPa stress level, (b) 3.2 kPa stress level. 0.1 kPa stress level, (b) 3.2 kPa stress level.
 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478 475

Table 3
Summary of the binder grading based on PG and MSCR systems.

Binder ID DTc Continuous grade Grade designation

PG system MSCR system
Neat 1.7 66–25 PG64-22 PG 52E-22 PG 58H-22 PG 64S-22
2%SBS 3.0 71–24 PG70-22 PG 52E-22 PG 58V-22 PG 64H-22 PG 70S-22
3%SBS 3.4 73–24 PG70-22 PG 58E-22 PG 64H-22 PG 70S-22
4%SBS 5.6 76–23 PG76-22 PG 58E-22 PG 64V-22 PG 70H-22 PG 76S-22
8%GTR 4.9 73–25 PG70-22 PG 58E-22 PG 64V-22
12%GTR 5.7 78–24 PG76-22 PG 58E-22
16%GTR 8.4 80–24 PG76-22 PG 52E-22
0.3%PPA 1.3 69–25 PG64-22 PG 52E-22 PG 58V-22 PG 64H-22
0.6%PPA 1.0 72–26 PG70-22 PG 52E-22 PG 58V-22 PG 64H-22 PG 70S-22
1.2%PPA 1.1 75–27 PG70-22 PG 58E-22 PG 64V-22 PG 70H-22 PG 76S-22

Note: Blank cells indicate that the binder was not able to meet the requirements for other grades.

properties of asphalt binders, the results of BBR tests were used. close to this temperature, structural changes (transitions) from a
Table 4 shows the test conditions that were used to construct the hard, glassy material to a soft, rubbery material occur. A higher
master curves of the asphalt binders. For high temperatures (i.e., Td indicates a binder that is hard over a wider range of tempera-
52 °C, 58 °C, 64 °C and 70 °C), the 25-mm DSR geometry was used. tures. For temperatures above Td, the Williams-Landel-Ferry
For intermediate temperatures (i.e., 10 °C, 16 °C, 22 °C, 28 °C, 34 °C (WLF) equation, expressed as Eq. (9), has been found to accurately
and 40 °C), 8-mm DSR geometry was used. Regarding the low tem- describe the shift factor of asphalt binders [34,35].
peratures (i.e., 6 °C, 12 °C and 18 °C), the stiffness (S(t)) of each
asphalt binder obtained from the BBR test was converted to com- 19ðT  T d Þ
log aðTÞ ¼ ð9Þ
plex shear moduli (G⁄) using the most common relationship relat- 92 þ T  T d
ing G⁄ to S(t), expressed as [33]:
where all the terms are as previously defined.
SðtÞ 1 However, for temperatures below Td, the Arrhenius equation,
G  ; x ð6Þ
expressed as Eq. (10), has been found to more accurately describe
3 t
the shift factor of asphalt binders [35].
The Christensen-Anderson mathematical model [33], which can
 
characterize the viscoelastic properties of asphalt binder, was used 1 1
to construct the master curves of aged binders. This model can be log aðTÞ ¼ 13; 016:07  ð10Þ
T Td
expressed as:
"  ðlog2Þ=R #R=ðlog2Þ where all the terms are as previously defined.
xc The rheological parameters (R, xc and Td) of the Christensen-
G ðxÞ ¼ Gg 1 þ

ð7Þ
xr Anderson model have specific physical significance. Table 5 shows
the values of the rheological parameters of the studied binders. The
where G⁄(x) is complex shear modulus at the frequency of x, Gg is value of the crossover frequency (xc) is related to the overall hard-
glassy modulus (assumed to be equal to 1 GPa), R is rheological ness of the binder. As the crossover frequency decreases, the hard-
index (shape factor), xc is the crossover frequency at the defining ness of the binder increases. The modified binders show lower
temperature, and xr is the reduced frequency at the defining tem- values of crossover frequency compared to the neat binder. In addi-
perature (Td). tion, as the amount of modifier increases, the value of the crossover
The xr is a function of shift factor and it can be expressed as: frequency decreases. In other words, the addition of the studied
modifiers increases the hardness of the binders. While this increase
xr ¼ x  10log aðTÞ ð8Þ
in the hardness will have a positive effect on the behavior of the
where log a(T) is the shift factor as a function of temperature, T is binder at high temperatures (it will increase the rutting resis-
the test temperature (K), and all other variables are as previously tance), it will decrease the performance at low temperature (due
defined. to increased cracking tendency).
The shift factor is a representation of the amount of shifting that The rheological index (R) is the difference between log of the
is required for data obtained at each test temperature to be shifted glassy modulus and log of the dynamic modulus at the crossover
to a defining temperature (Td). The defining temperature, which is frequency. This parameter is a representative of the rheological
related to the glass transition temperature, is an indicator of the
temperature dependency of the binder. In other words, around or
Table 5
Binders rheological properties.
Table 4 Binder ID Rheological Properties
Test conditions used in constructing the master curves of asphalt binders.
R xc (rad/s) Td (°C)
Condition Intermediate and high temperatures Low
Neat binder 2.558 0.859 21.15
temperature
2%SBS 2.712 0.239 20.05
Test device DSR BBR 3%SBS 2.781 0.201 20.75
Property measured Complex shear modulus Stiffness 4%SBS 2.940 0.076 20.35
Temperature (°C) 10, 16, 22, 28, 34, 40, 52, 58, 64, 70 -6, -12, -18 8%GTR 2.888 0.138 19.95
Frequency (x) (rad/s) 0.001, 0.159, 0.251, 0.398, 0.631, Not 12%GTR 3.094 0.059 21.85
1.000, 1.59, 2.51, 3.98, 6.31, 10.0, 15.9, applicable 16%GTR 3.353 0.011 20.15
25.1, 39.8, 63.1, 100 0.3%PPA 2.699 0.462 21.45
Time (s) Not applicable 8, 15, 30, 60, 0.6%PPA 2.768 0.178 19.95
120, 240 1.2%PPA 3.017 0.097 21.95
476 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478

1.E+09

1.E+08

1.E+07
Neat binder
1.E+06 2%SBS
3%SBS
G* (Pa) 1.E+05
4%SBS
8%GTR
1.E+04
12%GTR
1.E+03 16%GTR
0.3%PPA
1.E+02 0.6%PPA
1.2%PPA
1.E+01

1.E+00
1.0E-08 1.0E-06 1.0E-04 1.0E-02 1.0E+00 1.0E+02 1.0E+04 1.0E+06
(a)
Reduced Frequency (rad/s)
8

6
y = -0.1564x + 3.5961
R² = 0.9905
4
y = -0.1553x + 3.4037
R² = 0.9900
2
Log shift factor

y = -0.1571x + 3.725 y = -0.156x + 3.5258

R² = 0.9906 R² = 0.9903
0
y = -0.1554x + 3.4149 y = -0.1556x + 3.4446
R² = 0.9901 R² = 0.9902
-2
y = -0.1567x + 3.6495 y = -0.1552x + 3.3796
R² = 0.9905 R² = 0.9900
-4
y = -0.1552x + 3.3813
R² = 0.9900
-6
y = -0.1572x + 3.7373
R² = 0.9906
-8

-10
-24 0 24 48 72 96
(b)
Temperature (°C)

Fig. 12. Master curves of the neat and laboratory-modified binders.

index of the binder. A higher value of the rheological index is
attributed to a flatter curve that indicates a more gradual transition
from elastic behavior to steady-state flow. That is, a higher value of
R indicates a less brittle binder at intermediate temperatures and
frequencies. The rheological index of the binders is increased after
the addition of the modifiers; which suggests that the modified
binders are less brittle at intermediate temperatures. Similar find-
ings were also reported in the previous studies [35].
Turning to the significance of the defining temperature (Td), it is
an indicator of the temperature dependency of the rheological
properties of the binder (expressed as the change in the tempera-
ture shift factor). Specifically, as the defining temperature
increases, the temperature dependency of the shift factor of the
binder also increases. Table 5 shows that the differences in Td val-
ues of the tested binders are all within a narrow range of less than
2 °C.
Fig. 12 shows the developed master curve for the laboratory-
modified binders. It can be seen that all of the modifiers improve
the properties of the asphalt binders at high temperatures and
low frequencies by increasing the stiffness of the asphalt binders.
At low temperatures and high frequencies, GTR modified binders
show reduced stiffness compared to the neat binder. In addition,
higher percentages of SBS or PPA also reduce the stiffness of the
asphalt binders at low temperatures and high frequencies.
5. Summary and conclusions
In this research, three different modifiers were added to the
control neat binder to study their effects on the rheological proper-
ties and time-temperature dependent behavior of the modified
binders. The modifiers used included styrene-butadiene-styrene
(SBS), ground tire rubber (GTR) and polyphosphoric acid (PPA).
The dynamic shear rheometer (DSR) was used to grade the original,
RTFO-aged and PAV-aged binders based on the conventional per-
formance grading (PG) system. In addition, the DSR was used to
grade the RTFO-aged binders based on the multiple stress creep
recovery (MSCR) system. The bending beam rheometer (BBR) was
used to study the low-temperature properties of the asphalt bin-
ders. The experimental finding from this study can be summarized
as follows:
1. All of the modifiers were found to improve the high tempera-
ture properties of the neat asphalt binder as they increase the
stiffness and complex shear modulus and decrease the phase
 A. Behnood, J. Olek / Construction and Building Materials 151 (2017) 464–478
angle. There is a linear relationship between the effects of PPA
and SBS on the rheological properties of this base asphalt bin-
der, specifically it has been found that 2% SBS was equivalent
to 0.6% PPA and 4% SBS was equivalent to 1.2% PPA. However,
further research is required to make a more generalized
conclusions.
2. The SBS and PPA modifiers do not significantly affect the inter-
mediate temperature properties of the neat binder used in this
study. However, GTR decreases the stiffness of the binder and
the amount of reduction is higher for lower temperatures.
3. The results of BBR tests showed that although all of the modi-
fiers reduce the stiffness of this asphalt binder, only GTR shows
significant effects on the stiffness of the binder (i.e. it increases
the rutting parameter). For the temperatures and addition
levels used in this study, that increase is in the range of 140%
to 370% compared to the neat binder. With regard to the m-
value, the results showed that it was increased by adding PPA
to the neat asphalt and that it was decreased by adding the
SBS to the same base asphalt. The effect of GTR on the m-
value was not found to be significant. The overall effect of these
modifiers on the low temperature continuous grade is at most a
2-degree Celsius difference. Based on the calculated DTc values,
SBS and GTR make the modified binder more susceptible to
non-load related cracking while the PPA makes it less suscepti-
ble to non-load related cracking.
4. The MSCR protocol was successfully used to grade all the bin-
ders; however, the ‘‘percent difference” criterion of the MSCR
protocol seems to be not applicable for certain combination of
binders and exposure conditions (e.g., GTR modified binders
at higher temperatures).
5. Master curves of the binders showed that the modifiers
studied in this research increased the overall hardness of
the binder as indicated by the reduction in cross over fre-
quency. In addition, they reduced brittleness at intermediate
temperatures.
Acknowledgments
This research was conducted at the Binder Laboratory of the
North Central Superpave Center (NCSC); the authors would like
to acknowledge the support that has made the operation of this
facility possible. The authors would like to thank Dr. Rebecca
McDaniel of NCSC for reviewing this paper and providing com-
ments and suggestions and acknowledge the technical assistance
of Dr. Ayesha Shah, also of NCSC. This work was partially supported
by the Joint Transportation Research Program administered by the
Indiana Department of Transportation and Purdue University. The
binders used in the experiments were provided by Seneca Petro-
leum Co Inc, Crestwood, IL., and the authors acknowledge their
support.
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