Construction and Building Materials 156 (2017) 902–910

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Construction and Building Materials

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

Effect of aging on chemical and rheological properties of SBS modified

asphalt with different compositions
Gengren Hao, Weidong Huang, Jie Yuan ⇑, Naipeng Tang, Feipeng Xiao
The Key Laboratory of Road and Traffic Engineering, Ministry of Education, Tongji University, Shanghai 201804, PR China

h i g h l i g h t s

Components distribution of SBS modified asphalt binder is presented.

⁄

Master curve of the complex modulus (|G |) and phase angle (d) of SBS modified asphalt are depicted.

Phase angle (d) is more sensitive to asphalt composition and aging.

Compared to complex modulus, the master curve of phase angle (d) has more characteristics.

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

Article history: The simultaneous polymer degradation and asphalt oxidation of polymer modified asphalt (PMA) binder
Received 1 August 2016 make it difficult to understand the rheological behavior of PMA in the aging process. The present study
Received in revised form 6 June 2017 was meant to investigate the rheological behavior of various PMAs before and after aging (Rolling Thin
Accepted 19 June 2017
Film Oven Test (RTFOT) and Pressure Aging Vessel (PAV)) by using rheological master curves in combi-
Available online 19 September 2017
nation with Gel Permeation Chromatography (GPC). The GPC test was performed to obtain the average
molecular weight (Mw) of the polymer and distribution of asphaltenes and maltenes.
Keywords:
The properties of chemical and rheological were analyzed comprehensively and the results indicated
SBS modified asphalt
GPC
that the phase angle (d) is more sensitive to asphalt composition (sulfur contents, polymer and base bin-
Master curve der characteristic) than the complex shear modulus. Besides, the d shape can strongly reflect the differ-
Molecular weight ences between the rheological responses of the modified asphalts under the different aging conditions. A
Aging plateau would occur if the SBS network was formed. Thus the d shape of SBS modified asphalt will be clo-
Sulfur ser to that of base binder when SBS structure was completely destroyed. Although the degradation of
R-value polymer became severer when sulfur was added, sulfur can promote the formation of three-
Cross-over modulus dimensional structures of styrene–butadiene–styrene (SBS) and improve the rheological property of aged
PMAs.
Ó 2017 Published by Elsevier Ltd.

1. Introduction plexity increases when polymer-modified asphalt (PMA) is

involved.
Aging of asphalt is induced by chemical and/or physical changes Due to its excellent engineering property and relatively low
that occur during the production of pavement and throughout its cost, styrene–butadiene–styrene (SBS) has been widely applied in
service life. This causes asphalt to become brittle and has a higher the modification of asphalt [2–5]. When SBS is blended with
susceptibility to surface cracking, thus reducing the overall service asphalt, the elastomeric phase of the SBS copolymer absorbs the
life and riding quality of the asphalt pavements. The principal maltenes (oil fractions) from the asphalt and swells up [6,7] finally
cause of asphalt aging and embrittlement is the atmospheric oxi- forming two parts: the asphalt phase and the SBS phase. Thus, the
dation of certain molecules within the formation of highly polar rheological changes in aged SBS modified asphalt are dependent on
and strongly interacting functional groups containing oxygen [1]. a combined effect of asphalt oxidation and polymer degradation
Aging is a highly complex process in neat asphalt binder and com- [8–11]. When assessing the quality of a chosen polymer-modified
asphalt through aging properties, both chemical and rheological
methods are required.
⇑ Corresponding author. There has been a lot of research conducted on SBS aging. Lu and
E-mail address: [email protected] (J. Yuan). Isacsson concluded that aging resulted in the degradation of the

http://dx.doi.org/10.1016/j.conbuildmat.2017.06.146
0950-0618/Ó 2017 Published by Elsevier Ltd.
 G. Hao et al. / Construction and Building Materials 156 (2017) 902–910 903

SBS polymer (a decrease in the polymer molecular weight) and the Table 2
oxidation of the asphalt (an increase in the content of polar oxygen The grain size of the sulfur.

containing molecules and an increase in asphalt molecular weight) Grain size >150 lm 75 lm–150 lm
[10]. Oxidative aging decreased the susceptibility of the asphalt to Mass percentage (%) 0 0.4
temperature, damaged the polymer network in binders, further
broadened the relaxation spectrum, and diminished polymer effec- 2.2. Gel permeation chromatography (GPC) test
tiveness in improving asphalt ductility [12]. SBS modified binders
were investigated by Fourier transform infrared (FTIR), atomic About 20 mg binder sample was dissolved in tetrahydrofuran (THF) in a 10 mL
volumetric flask for 24 h before GPC test. The solution was then filtered through a
force microscopy (AFM), and dynamic shear rheometer (DSR) to
weighted 0.45 lm PTFE filter and was collected in a 0.5 mL centrifugal tubes for
observe the changes in morphology and chemical structure GPC test. Waters 1515 High-Pressure Liquid Chromatography (HPLC) Pump and
[13,14]. Liu and Nielsen investigated the aging properties of SBS Waters 2414 Refractive Index (RI) detector were used to perform GPC test THF
modified asphalt from the laboratory to the field by DSR and Gel (HPLC grade) was selected as mobile phase solvents. A combination of three col-
Permeation Chromatography (GPC) [15]. umns was used for separating constituents of asphalt binder by molecular size.
The calibration curve was built with ShodexÒ Polystyrene Standards in order to
The results of the investigation indicate that the degree of SBS convert the retention time to molecular weight. A 100 lmL syringes was used to
modification is a function of asphalt source, asphalt–polymer com- take the sample from the prepared solution in the centrifugal tube as mentioned
patibility and polymer concentration [16–18]. Obviously, the in the solubility test. After removing the bubble in the syringe, the solution was
chemical and rheological properties of aged PMAs are also affected then injected into the manual sample injector and the solution passed through
the columns for 40 min at a flow rate of 1 mL/min. The original data was exported
by these factors. However, the comparison of chemical and rheo-
and normalized for further analysis (e.g. Fig. 1). The chromatogram was divided into
logical properties among different compositions of aged SBS mod- three slices based on the molecular weight of eluting species. The three fractions are
ified asphalt is seldom studied. polymers (molecular weight >19,000), asphaltenes (molecular weight from 19,000
In order to analyze the influence of different factors on the to 3000) and maltenes (molecular weight less than 3000) [20]. The contents of
chemical and rheological properties of the SBS modified asphalt asphaltenes and maltenes were calculated accordingly based on Eqs. (1) and (2).

after aging, a number of SBS modified asphalts were produced with Areaasphaltenes
Asphaltenes% ¼  100% ð1Þ
two base binders (ESSO70 and JINSHAN70), two types of polymers Total area under chromatogram
(radial SBS and linear SBS), and different sulfur contents (0, 0.15,
and 0.25). Aging was assessed via conventional aging tests, such Areamaltenes
Maltenes% ¼  100% ð2Þ
as the Rolling Thin Film Oven Test (RTFOT) and Pressure Aging Ves- Total area under chromatogram
sel (PAV). RTFOT and PAV are expected to simulate, respectively, The average molecular weight of polymer in the PMA is calculated as follows:
short-term aging during mixing and long-term aging in the field
X
n
wi  M i
[19]. The molecular weight distribution, weight average molecular M w ðpolymerÞ ¼ ð3Þ
i¼1
wi
weight (Mw) of the component, the master curve of complex mod-
ulus (|G⁄|), and phase angle (d) of SBS polymer modified asphalt X
n
Ni  Mi
were observed by means of Gel Permeation Chromatography M n ðpolymerÞ ¼ ð4Þ
i¼1
Ni
(GPC) and Dynamic Shear Rheological (DSR), respectively. The rela-
tionship between the chemical and rheological properties of differ- where Mw ðpolymerÞ is the average molecular weight; wi is the weight of molecular
ent formulation asphalts and the performance ranking of aged mass Mi and is proportional to the RI response; Mn ðpolymerÞ is the number average
PMAs were also analyzed. molecular weight; N i is the number of molecules of molecular mass Mi. The calcula-
tion of the average molecular weight of the polymer was performed on Origin soft-
ware. Two replicates were used for GPC test and the average values were reported.

2. Materials and methods 2.3. Frequency sweep test and construction of master curve

2.1. Materials and preparation of SBS modified asphalt binder A DSR was used to perform frequency sweeps between 0.1 and 30 Hz at temper-
atures between 5 and 75 °C. The 8 mm diameter, 2 mm gap, parallel plate testing
In this study, two base binder, two SBS modifier, and elemental sulfur were geometry was used for the tests between 5 and 25 °C and the 25 mm diameter,
selected to prepare modified binders in laboratory. Base binder was ESSO asphalt 1 mm gap was used at the temperature range of 35 to 75 °C. The strain amplitude
and JINSHAN asphalt. SBS 791-H was produced by Sinopec and SBS T161B was for the frequency sweep tests was within the linear viscoelastic (LVE) response of
produced by DuShanZi Petroleum and Chemical Corporation, China. SBS 791-H the binder. The sigmoidal model is developed in National Cooperative Highway
is a kind of linear polymer with an average molecule weight of 110,000 g/mol, Research Program (NCHRP) Project A-37A was taken to construct complex modulus
containing 30 wt% of styrene. SBS T161B is a kind of radial polymer with an master curve [21]. The reference temperature of 25 °C was chosen for the produc-
average molecule weight of 230,000 g/mol, containing 30 wt% of styrene. The tion of complex modulus and phase angle master curve [16].The sigmoidal model
amount of elemental sulfur ranges from 0% to 0.25% by weight of the base bin- is as follows:
der (see Table 1). a
Preparation of modified binders was divided into three stages. Firstly, SBS was log jG j ¼ m þ ð5Þ
1 þ eðbþc log f r Þ
added to base binder and sheared for 30 min at 180 °C with high shear mixer. Sec-
ondly, the blend was stirred for 60 min using the mechanical blender. Thirdly, a where log fr is log reduced frequency; m is the lower asymptote; a is the difference
cross-linking agent (Sulfur Table 2) was added to the blend and stirred for another between the values of the upper and lower asymptote; b and c define the shape
90 min. between the asymptotes[21].

Table 1
Simplified name and PG grade result.

Base Binder SBS type SBS% Sulfur% Sample ID PG Viscosity@135 °C

ESSO – 0 0 E70 63.3-23.6 0.493
linear 4.5 0.15 E4.5L0.15w 73.3-25.4 2.383
radial 4.5 0 E4.5R0w 72.4-22.0 1.34
0.15 E4.5R0.15w 74.7-25.9 2.937
0.25 E4.5R0.25w 75.4-25.4 3.883
JINSHAN – 0 0 J70 62.8-25.3 0.645
radial 4.5 0.15 J4.5R0.15w 75.2-26.1 6.358

Note: ‘‘V”, ‘‘R”, and ‘‘P” stand for: virgin, RTFOT and PAV, respectively.
904 G. Hao et al. / Construction and Building Materials 156 (2017) 902–910

same time, the asphaltenes peak increases dramatically in size

and shifts to an earlier time. This is because more asphaltenes
are formed from naphthenic and polar aromatics, in combination
with an increase in the size of the asphaltenes structures, due to
increasing interactions. These are also verified by the distribution
of components within SBS modified asphalt, as saw in Fig. 3(b).
The component within all binder samples was quantified in
Fig. 3(b). After aging, the percentage of asphaltene increased and
the percentage of maltenes decreased regardless of the asphalt
type. Even so, maltenes still accounted for a larger proportion of
the asphalt. In general, oxidation results in the development of
polar fractions from non-polar components, i.e., causing naphthene
(non-polar aromatics) to form resin (polar aromatics) and polar
aromatics to form asphaltenes [24]. Fig. 3(a) depicts that the
molecular weight of SBS modified asphalt decreased after the aging
process, which suggests that the aging of asphalt is a process of SBS
degradation and asphalt oxidation.

Fig. 1. Fractions of the chromatogram based on molecular weight. 3.2. The master curve of different asphalt

3.2.1. Base binder

The shift factors for the construction of complex modulus curve were then used
The changes in the rheological properties of the two base bin-
to build phase angle master curve. The newly developed double-logistic (DL) math-
ematical function by Asgharzadeh and Tabatabaee [22] was taken for the modelling ders and the modified asphalt with different formulas under differ-
of phase angle master curve. The shift factors for the construction of complex mod- ent aging conditions have been studied. The influence of aging on
ulus curve were then used to build phase angle master curve. The double-logistic the rheological behavior of the base binders is shown in Fig. 4(a,
(DL) function is as follows:
b). Decreases in the d values and increases in the |G⁄| values can
0   2 1
fr
be observed for all of the base asphalt after the aging procedure
SR  log
d ¼ dP  dP  Hðf r  f P Þ  @1  e fP A þ dL  Hðf P  f r Þ (both short-term aging and long-term aging). The complex modu-
0   2 1
lus curve is elevated over the whole frequency range and the phase
SL  log
fP
angle curve is lowered correspondingly. The effect of aging often
 @1  e fr A ð6Þ
causes an increase in the complex modulus, indicating a hardening
of the asphalt and a decrease in phase angle, which, in turn, indi-
where fr is reduced frequency; fP is the frequency where phase angle reaches the pla- cates an increase in the elastic behavior of the asphalt. This is a
teau value; dP is the plateau phase angle; SR is the shape parameter in the right side
result of the decrease in maltenes and the increase in asphaltenes.
of the plateau; dL stands for the left side the plateau phase angle; SL is the shape
parameter in the left side of the plateau; H (fr–fP) and H (fP–fr) are two Heaviside step Meanwhile, the clear increases of the |G⁄| values at lower frequen-
functions. cies (higher temperatures) and have the small variations at higher
frequencies (lower temperatures). In other words, with the
2.4. Aging index (R-value, cross-over modulus and glover-rowe) decrease of the frequency, the complex modulus difference
between Virgin, RTFOT, and PAV is becoming increasingly obvious.
The rheological index, R-value, is defined as the difference between the log of For the base binder, aging causes the asphaltenes to increase. The
the glassy modulus and the log of the dynamic modulus at the crossover frequency.
contribution of asphaltenes to the modulus of asphalt is decreased
Normally, R-value is higher for oxidized/aged asphalt [26]. Rowe [27] re-defined the
Glover parameter in terms of |G⁄|and d based on analysis of a Black Space diagram with the temperature increase.
and suggested use of the parameter |G⁄|(cosd)2/sind, termed the Glover-Rowe (G-R)
parameter, in place of the original Glover parameter. A higher G-R value indicates 3.2.2. SBS modified asphalt
increased brittleness.
The effect of aging on the rheological properties of the SBS mod-
ified asphalt differs from the base asphalt. The most obvious differ-
3. Results and discussion ence is the shape of the master curve of the phase angle. As showed
in Fig. 4(c–g), the master curve of the phase angle reaches a central
3.1. Components distribution analysis plateau at intermediate frequencies. These plateaus indicate that
the d values remain constant or do not greatly change from one
Fig. 2 shows the GPC curves for the E70, J70, E4.5R0.15w and the point to another. This can be attributed to the fact that the varia-
J4.5R0.15w binder before and after aging. For the GPC curve of the tions in the loss and the storage modulus (G” and G’, respectively)
two base binders, there are two peaks: the asphaltenes area and are such that the ratio of one to the other (tan d = G00 /G0 ) is almost
the maltenes area. But for the polymer-modified asphalt, there constant. These plateaus also suggest the formation of a polymer
were mainly three observable peaks from left to right correspond- network and a major contribution of the modifier to the mechani-
ing to the polymer, primarily for asphaltenes and primarily malte- cal response of the asphalt [16,25]. With respect to the SBS modi-
nes [23] The order of elution is related to the molecular weight fied asphalt, this polymer network may be explained by the
(Mw) of the component. High molecular weight species elute first, entanglements of the polystyrene and polybutadiene blocks found
followed by molecules with ever decreasing molecular weight. within the chemical composition of the modifier [16]. With the
After aging, the peaks shifting to later times, increasing in height, increase in aging, some have indicated that SBS modified asphalt
and increasing in width, suggests that the molecular weight was is more elastic at immediate and high frequencies, but more vis-
decreased, the number of molecules with this Mw was increased, cous at low frequencies (high temperature).
respectively. It indicates that large polymer molecules degrade into After short-term aging, some of the plateaus still exist, while
smaller ones and, thereby, increase the polymer molecular weight others have disappeared and great changes have begun to occur
distribution. The Mw and Mn of a polymer tend to go down during in terms of shape. However, almost all the plateaus disappeared
the aging of SBS modified asphalt, as indicated in Fig. 3(a). At the after long-term aging. Obviously, the effect of PAV on the shape
 G. Hao et al. / Construction and Building Materials 156 (2017) 902–910 905

100 100
E70-V
90 90 J70-V

Normalized Refractive Index

Normalized Refractive Index
80 E70-R
80 J70-R

J70-P
70 E70-P
70
60 60
50 50
40 40
30 30
20 20
10 10
0
12 14 16 18 20 22 24 26 0
12 14 16 18 20 22 24 26
Retention Time (min) Retention Time (min)
(a) (b)
100 100
E4.5R 0.15w-V J4.5R 0.15w-V

Normalized Refractive Index

90 90
Normalized Refractive Index

E4.5R 0.15w-R J4.5R 0.15w-R

80 80
E4.5R 0.15w-P J4.5R 0.15w-P
70 70
60 60
50 50
40 40
30 30
20 20
10 10
0 0
12 14 16 18 20 22 24 26 12 14 16 18 20 22 24 26
Retention Time (min) Retention Time (min)

(c) (d)
Fig. 2. GPC curves for the base binder E70 (a) and J70 (b) and SBS modified asphalt E4.5R0.15w (c) and J4.5R0.15w (d).

Mn of polymer Mw of polymer maltene asphaltene

J4.5R0.15w-P J4.5R0.15W-P
J4.5R0.15W-R
J4.5R0.15w-R
J4.5R0.15W-V
J4.5R0.15w-V
E4.5L0.15W-P
E4.5L0.15W-R
E4.5L0.15w-P
E4.5L0.15W-V
E4.5L0.15w-R
E4.5R0.25W -P
E4.5L0.15w-V
E4.5R0.25W -R
E4.5R0.25W -V
E4.5R0.25w -P
E4.5R0.15W-P
E4.5R0.25w -R
E4.5R0.15W-R
E4.5R0.25w -V E4.5R0.15W-V

E4.5R0W-P
E4.5R0.15w-P E4.5R0W-R
E4.5R0.15w-R E4.5R0W-V

E4.5R0.15w-V
J70-P
J70-R
E4.5R0w-P J70-V

E4.5R0w-R
E70-P
E4.5R0w-V E70-R
E70-V
0 50000 100000 150000 200000 250000 300000 350000 COMPONTENTS DISTRIBUTION

(a) (b)
Fig. 3. (a) The Mw and Mn of polymer after aging. (b) Components distribution of asphalt.

of the phase angle is greater than the effect of RTFOT. This may be It is known that the plateau region of the phase angle can be
due to the fact that the destruction of the SBS network structure is used as a sensitive indicator of the damage of a polymeric network
more serious under pressure within a long-term aging structure in asphalt [21,22]. From the above analysis, the same
environment. conclusion should also be expected.
The effect of aging on modulus variation is not significant.
Increases in the |G⁄| values can be observed for the entirety of 3.3. The phase angel shape characteristics of the base binder and SBS
the PMA after-aging procedure (both short-term aging and long- modified asphalt
term aging). The modulus change of SBS modified after aging is
more complicated than the base binder. Generally, short-term It is noticeable that shapes of virgin base binder and virgin SBS
aging has little effect on the complex modulus, with the exception modified asphalt are totally different. The PMA’s master curve of
of E4.5R0w. This relates to the aging mechanism, especially since the phase angle reaches a central plateau at intermediate frequen-
the aging of SBS modified asphalt is due to two causes: oxida- cies due to the existing SBS network structure. The shape of the
tion/hardening of base asphalt and degradation of SBS. The oxida- base binder is unchanged by aging and only its position moves
tion of the asphalt phase increases the modulus of PMA, but SBS down. Nevertheless, the shape of the SBS modified asphalt will
degradation has exactly the opposite effect. be discussed in terms of the two cases: one is the shape which
906 G. Hao et al. / Construction and Building Materials 156 (2017) 902–910

Fig. 4. Master curve of complex modulus (|G*|) and phase angle (d). (a) E70, (b) J70, (c) E4.5R0w, (d) E4.5R0.15w, (e) E4.5R0.25w (f) E4.5L0.15w, (g) J4.5R0.15w.

has the plateaus and the other is the shape which closer to the base 3.4. Effect of aging on different formulations
binder’s shape. In the first case, the performance would be better if
it showed a more elastic shape at lower frequencies. In the latter In order to assess the changes in the rheological properties of
example, the rheological property of the SBS modified asphalt is different formulations of asphalt under the same aging conditions,
similar to the base binder. So it is easy to assess the performance the master curves for all asphalt types were classified by virgin,
of aged asphalt through the shape characteristics of the phase RTFOT, and PAV.
angle.
 G. Hao et al. / Construction and Building Materials 156 (2017) 902–910 907

3.4.1. Before aging the virgin SBS modified asphalt, none of the sulfur content, poly-
3.4.1.1. Different sulfur. In Fig. 5(a), the master curves of the com- mer characteristics, and base binder source makes significant influ-
plex shear modulus (|G⁄|) and the phase angle (d) at 25 °C were ence on the complex modulus of asphalt (see Tables 3 and 4).
comparable for the three PMAs, in addition to the different
amounts sulfur (0, 0.15, and 0.25). For all the asphalt samples, 3.4.2. Short-term aging and long-term aging
when the frequency was increased, the modulus increased contin- 3.4.2.1. Different sulfur. The molecular weight (Mw) ratio of SBS can
uously. The modulus of modified asphalt increased compared with reflect the degree of SBS degradation, the molecular weight (Mw)
the base binder, especially at low frequencies (high temperatures). ratio was calculated using the following equations:
It is noteworthy that the modulus of the three modified asphalts
was unaffected by the sulfur content. MwðVÞ  MwðRÞ
Mw ratioðRÞ ¼ ð7Þ
However, the changes in the phase angle curve were noticeable. MwðVÞ
All the PMAs were more elastic than the base binders at low fre-
quencies. In addition, no matter how much sulfur is added, the MwðVÞ  MwðPÞ
Mw ratioðPÞ ¼ ð8Þ
modified asphalt will appear to plateau. Nevertheless, for PMAs, MwðVÞ
the degree of elasticity is dependent on the amount of sulfur: the
more sulfur, the more elastic the PMA. These results suggest that The bigger the Mw ratio, the harder the SBS degradation, that is,
sulfur increases the compatibility between polymer and asphalt the modulus of SBS modified asphalt decreases when there is a
by crosslinking polymer chains. It also suggests that the phase degradation of SBS. For short-term aging, the Mw ratio of
angle is more sensitive to asphalt modification than the complex E4.5R0w is the minimum, thus we see the complex modulus of
shear modulus and, therefore, the d values can strongly reflect E4.5R0w being greater than E4.5R0.15w and E4.5R0.25w at
the differences between the rheological responses of the modified (4.5 Hz to 0.5 Hz), as Fig. 6 shows. Although the SBS degradation
asphalt under the oscillatory shear loading. degree of E4.5R0w is the least significant, the viscous property of
E4.5R0w is greater than the other two PMAs. This is because sulfur
acts as a plasticizer, increasing the dispersion of the polymer and
3.4.1.2. Different polymer. Fig. 5(b) shows the master curves of the facilitating polymer swelling. Afterward, sulfur promotes
complex shear modulus (|G⁄|) and the phase angle (d) at 25 °C for crosslinking reactions and the subsequent formation of three-
the two PMB produced by two types of modifiers: radial SBS and dimensional structures. After long-term aging, E4.5R0w has a
linear SBS. In the same production process and the amount of sul- higher modulus than E4.5R0.15w and E4.5R0.25w, which is consis-
fur, there is no significant difference between the radial SBS and tent with the Mw ratio result (the SBS degradation degree of
linear SBS modified asphalt, both complex modulus (|G⁄|) and E4.5R0w is lighter than others).
phase angle (d). There is a plateau in the phase angle master curves of both
E4.5R0.15w and E4.5R0.25w, though E4.5R0.25w shows more elas-
3.4.1.3. Different base binder. Fig. 5(c) depicts the master curves of ticity than E4.5R0.15w, which means the SBS network structure
the complex shear modulus (|G⁄|) and the phase angle (d) at has not been destroyed after short-term aging. However, the shape
25 °C for the two different base asphalt (ESSO70 and Jinshan70) of E4.5R0w is the same as that of the base binder. This suggests
and the two different modified asphalts: E4.5R0.15w and that sulfur increases the compatibility between the asphalt and
J4.5R0.15w. It is clear that the variation in the |G⁄| values between the copolymers, promoting the formation of three-dimensional
the two base binders is extremely slight, a similar phenomenon structures. Therefore, the rheological property ranking after RTFOT
also occurs between two different PMBs. For phase angle, there is is as follows: E4.5R0.25w > E4.5R0.15w > E4.5R0w.
a little difference between the two kinds of modified asphalt, but After long-term aging, the phase angle shapes of all three PMAs
the overall trend is consistent. In addition to the marked reduction are the same with that of the base binder, which means the SBS
in the phase angle, i.e. considerable increase in the level of elastic- network structure is completely destroyed. The rheological prop-
ity, within the interval of low and intermediate frequencies of erty of these PMAs is closer to the base asphalt and the rheological
loading, the master curves of the E4.5R0.15w and J4.5R0.15w also property ranking is: E4.5R0.25wE4.5R0.15w > E4.5R0w. The rhe-
reach a central plateau at intermediate frequencies. ological property is not significantly promoted between
It has been recognized that the physical and mechanical proper- E4.5R0.25w and E4.5R0.15w. Meanwhile, considering the engi-
ties, as well as the rheological behavior of the conventional asphalt neering applicability (viscosity), 0.15% may be the optimal sulfur
compositions can be improved by the addition of SBS. It is well value.
known that the rheological properties of modified asphalt are
affected by various factors, including the source of the base binder, 3.4.2.2. Different polymer. The Mw ratios for E4.5R0.15w and
the chemical characteristics of the additive, and the sulfur/polymer E4.5L0.15w are very similar in both short-term and long-term
ratio (the degree of compatibility with the asphalt). However, for aging. The modulus of E4.5R0.15w and E4.5L0.15w is almost coin-

Fig. 5. Master curve of virgin asphalt. (a) Different sulfur, (b) different polymer, (c) different base binder.
908 G. Hao et al. / Construction and Building Materials 156 (2017) 902–910

Table 3
The molecular weight (Mw) ratio of polymer.

asphalt E4.5R0w E4.5R0.15w E4.5R0.25w

aging V R P V R P V R P
Mw 286701 211265 157362 317870 152957 82821 205651 119128 68960
Mw ratio 0.26 0.45 0.52 0.74 0.42 0.66

Table 4
The molecular weight (Mw) ratio of polymer.

asphalt E4.5R0.15w E4.5L0.15w

aging V R P V R P
Mw 317870 152957 82821 313564 144485 87600
Mw ratio 0.52 0.74 0.54 0.72

Fig. 6. Master curve of aged asphalt. (a) Different sulfur after RTFOT, (b) different polymer after RTFOT, (c) different base binder after RTFOT, (d) Different sulfur after PAV, (e)
different polymer after PAV, (f) different base binder after PAV.

cident. After long-term aging, their modulus is the same with the property ranking after RTFOT is E4.5R0.15w > J4.5R0.15w. After
base binder, which implies that the degradation of SBS is abundant. the long-term aging process, the rheological property of asphalt
The shape of the phase angle curve does not change and decreases, as showed by the curve below, thus the rheological
E4.5L0.15w shows slightly more viscosity than E4.5R0.15w. Thus, property ranking after PAV is E4.5R0.15w > J4.5R0.15w (see
the rheological property ranking after RTFOT is E4.5R0.15w > Table 5).
E4.5L0.15w. These results are explained by the fact that SBS chains
are more readily well integrated into the three-dimensional net-
work of the radial PMA than the linear PMA. After the long-term 3.5. Aging index
aging process, due to the full degradation of SBS, the shapes of
phase angle of PMAs are the same with that of base asphalt and To assess the influence of short-term aging on the |G⁄| values
the rheological property ranking is E4.5L0.15w > E4.5R0.15w. and the d values of the asphalt, three aging indices were utilized.
The R-value, crossover modulus, and Glover-Rowe of asphalt were
all quantified, as the below Table 6 shows.
3.4.2.3. Different base binder. The modulus of SBS modified asphalt For the same formulation asphalt, the greater the value of
is a combination of the SBS phase and base binder. With the GPC higher R-value, Glover-Rowe, and lower Cross-Over Modulus indi-
result, the degradation degree of J4.5R0.15w is lower and leads cates that the aging degree is deeper. It is easy to see that the value
to the modulus increase. However, the modulus of E70 is greater of R-value and Glover-Rowe of both base binder and SBS modified
than J70. These factors make the master curves of J4.5R0.15w asphalt are increases, the Cross-Over Modulus is decreases after
and E4.5R0.15w close in shape. aging. In order to assess the different formulations under the same
The shape of the phase angle, E4.5R0.15w, still has a plateau aging condition, it is necessary to normalize these indices (divide
even after the completion of the short-term aging process, but the aged value by virgin), as the below table indicates (see Table 7).
the shape of J4.5R0.15w is closer to the base binder, which means The rheological property rankings by the three normalized
the SBS network of J4.5R0.15w disappeared. The rheological aging indices and the master curve of the phase angle are listed
 G. Hao et al. / Construction and Building Materials 156 (2017) 902–910 909

Table 5
The molecular weight (Mw) ratio of polymer.

asphalt E4.5R0.15w J4.5R0.15w

aging V R P V R P
Mw 317870 152957 82821 292612 233298 138704
Mw ratio 0.52 0.74 0.20 0.53

Table 6
The aging index of asphalt.

Sample R-Value Normalize R-Value Cross-Over Modulus Normalize Cross-Over Modulus Glover-Rowe Normalize Glover-Rowe
E70 V 1.58 1.00 26476775 1.00 412 1.00
R 1.62 1.03 23813532 0.90 2692 6.53
P 1.89 1.20 12902636 0.49 45256 109.82
J70 V 1.63 1.00 23456731 1.00 387 1.00
R 1.74 1.07 18206524 0.78 1238 3.20
P 2.02 1.24 9626247 0.41 46573 120.43
E4.5R0w V 1.81 1.00 15573622 1.00 10067 1.00
R 1.88 1.04 13141828 0.84 40898 4.06
P 2.08 1.15 8334532 0.54 136822 13.59
E4.5R0.15w V 1.77 1.00 17160158 1.00 10350 1.00
R 1.80 1.02 15754315 0.92 15451 1.49
P 2.01 1.14 9684418 0.56 44592 4.31
E4.5R0.25w V 1.69 1.00 20615719 1.00 7353 1.00
R 1.69 1.00 20528352 1.00 10190 1.39
P 2.02 1.20 9594616 0.47 30606 4.16
E4.5L0.15w V 1.70 1.00 19957285 1.00 8109 1.00
R 1.84 1.08 14509301 0.73 15567 1.92
P 1.93 1.13 11874514 0.59 31443 3.88
J4.5R0.15w V 1.85 1.00 13978919 1.00 11501 1.00
R 1.88 1.01 13157077 0.94 21559 1.87
P 2.11 1.14 7816398 0.56 70644 6.14

Table 7
The rheological property ranking of asphalt.

Sample Aging index RTFOT PAV

Differ Sulfur content N:R-Value 0.25w > 0.15w > 0w 0.15w > 0w > 0.25w
N:|G*| 0.25w > 0.15w > 0w 0.15w > 0w > 0.25w
N:G-R 0.25w > 0.15w > 0w 0.25w > 0.15w > 0w
Master curve(d) 0.25w > 0.15w > 0w 0.25w  0.15w > 0w
Differ polymer N:R-Value E4.5R0.15w > E4.5L0.15w E4.5L0.15w > E4.5R0.15w
N:|G*| E4.5R0.15w > E4.5L0.15w E4.5L0.15w > E4.5R0.15w
N:G-R E4.5R0.15w > E4.5L0.15w E4.5L0.15w > E4.5R0.15w
Master curve(d) E4.5R0.15w > E4.5L0.15w E4.5L0.15w > E4.5R0.15w
Differ base binder N:R-Value J4.5R0.15w > E4.5R0.15w J4.5R0.15w > E4.5R0.15w
N:|G*| J4.5R0.15w > E4.5R0.15w E4.5R0.15w > J4.5R0.15w
N:G-R E4.5R0.15w > J4.5R0.15w E4.5R0.15w > J4.5R0.15w
Master curve(d) E4.5R0.15w > J4.5R0.15w E4.5R0.15w > J4.5R0.15w

in the table. There is good consistency between the result of the 4. Although the degradation of polymer became harder when sul-
normalized Glover-Rowe and the master curve of the phase angle. fur was added, sulfur can promote the formation of three-
dimensional structures of styrene–butadiene–styrene (SBS)
4. Conclusions and improve the rheological property of aged PMAs.
5. Considering the rheological property of aged PMAs and the
1. The phase angle is more sensitive to asphalt composition (sulfur engineering applicability (viscosity), 0.15% by weight of base
contents, polymer, and base binder characterize) than the com- binder may be the optimal sulfur value.
plex shear modulus. 6. The rheological properties of aged SBS modified asphalt are
2. The modulus of the aged SBS modified asphalt at low frequen- more sensitive than virgin to sulfur content, polymer character-
cies mainly depend on the degradation degree of SBS. The mod- izes, and base binder source.
ulus decrease alongside SBS degradation. 7. The rheological property ranking after RTFOT is 0.25w >
3. The d shapes can strongly reflect the differences between the 0.15w > 0w, E4.5R0.15w > E4.5L0.15w, E4.5R0.15w >
rheological responses of the modified asphalts after aging. A J4.5R0.15w and the rheological property ranking after PAV is
plateau would occur if the SBS network was formed. Thus the 0.25w0.15w > 0w, E4.5L0.15w > E4.5R0.15w, E4.5R0.15w >
d shape of SBS modified asphalt will be closer to base binder J4.5R0.15w.
when SBS structure was completely destroyed.
910 G. Hao et al. / Construction and Building Materials 156 (2017) 902–910

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