Journal of Cleaner Production 220 (2019) 1231e1238

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Journal of Cleaner Production

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

Internal aging indexes to characterize the aging behavior of two

bio-rejuvenated asphalts
Xing Cai a, Jiayun Zhang b, Gang Xu a, Minghui Gong c, Xianhua Chen a, Jun Yang a, *
a
School of Transportation, Southeast University, #2 Southeast University Road, Nanjing, 210096, PR China
b
Shanghai Municipal Engineering Design Institute, #901 North Zhongshan No.2 Road, Shanghai, 200092, PR China
c
Sobute New Materials Co. Ltd, State Key Laboratory of High Performance Civil Engineering Materials, 118 Liquan Road, Nanjing, 211103, PR China

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

Article history: Profound progress has been made in bio-rejuvenators to enhance aged asphalt's low temperature per-
Received 15 October 2018 formance and reduce its high temperature viscosity. However, limitation still exists in the knowledge
Received in revised form how long service life of rejuvenated asphalt is and whether regeneration is effective since aging behavior
17 February 2019
of rejuvenated asphalt is neglected. Furthermore, aging evaluation is based on different tests dependent
Accepted 18 February 2019
Available online 21 February 2019
on temperature, which may lead to various results. This study aims to evaluate the aging behavior of bio-
rejuvenated Pen70 and SBS modified asphalts using internal aging indexes that characterize the physical
property. Original Pen70 and SBS asphalts under identical aging conditions were set as the control group.
Keywords:
Aging behavior
Fourier transform infrared spectroscopy test (FTIR) was conducted to quantify aging extent through
Bio-rejuvenator oxidation aging functional groups. Activation energy was achieved through rotational viscometer (RV).
Asphalt Dynamic shear modulus was acquired through dynamic shear rheological test (DSR) and characterized
Activation energy by two springs, two parabolic elements, and one dashpot (2S2P1D) model. For both Pen70 and SBS, the
Dynamic shear modulus two potential aging indexes related with activation energy and viscosity of dashpot separately were
found linearly correlated with related chemical aging functional groups. Through comparison, it indicates
that bio-rejuvenation was a process of physical blending. It couldn't restore the crosslinking structures of
SBS polymers. Besides, the physical property of bio-rejuvenated Pen70 degenerated faster, while that of
bio-rejuvenated SBS stayed stable. A benefit period was proposed for the rejuvenation of Pen70 while the
rejuvenation of SBS was not bound by time. Further work is needed to validate findings in the present
study.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction Generally, using bio-binder as a substitute or a modifier for tradi-

tional asphalt binder is the focus of previous research.
The pavement industry is confronted by many new challenges According to the literature, bio-binder has the potential to
such as the increasing price of petroleum-refined asphalt binders, soften hard asphalt binder and improve its low-temperature
the unceasing reduction of fossil oil reserves, and the considerable property. It is found that as a modifier, bio-binder derived from
amounts of greenhouse gas emission. Bio-materials derived from swine manure through a thermochemical liquefaction process can
waste natural resources are widely researched and used as binders reduce the viscosity of the base asphalt binder as well as improve
in asphalt mixtures, which may be the keys to solving the above the low-temperature cracking susceptibility (Fini et al., 2011, 2012;
problems. These bio-materials are termed “bio-binder”. Bio-binder Mills-Beale et al., 2014). More recently, the research shows that Soy
is a renewable and environmentally friendly material which has fatty acid can also make hard asphalt binders become less stiff and
been developed to partly replace the petroleum asphalt binder. In more workable (Seidel and Haddock, 2012). Due to the softening
the past few years, great achievements have been made in the area. effects of different types of bio-binders, it is possible to apply bio-
binder as a bio-rejuvenator for aged asphalt binder and mixture.
As the previous research, bio-binder based on waste edible vege-
* Corresponding author. table oil can rejuvenate aged asphalt binder and improve its aging
E-mail addresses: 230179752@seu.edu.cn (X. Cai), zhangjiayun@smedi.com resistance, rutting resistance and elastic recovery performance
(J. Zhang), xugang619@hotmail.com (G. Xu), gongminghui@cnjsjk.cn (M. Gong),
chenxh@seu.edu.cn (X. Chen), yangjun@seu.edu.cn (J. Yang).
(Chen et al., 2014). Besides, the chemical and rheological properties

https://doi.org/10.1016/j.jclepro.2019.02.203
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
1232 X. Cai et al. / Journal of Cleaner Production 220 (2019) 1231e1238

of aged asphalt will be enhanced with the addition of bio-binder (2) Exploring different aging mechanisms of Pen70 and SBS as-
rejuvenator based on biodiesel residue (Gong et al., 2016). Bio- phalts and investigating which one is more suitable for bio-
binder from swine manure also has the potential to be a bio- rejuvenation.
rejuvenator for reclaimed asphalt shingles as well as high
reclaimed asphalt pavements. The results indicate that this bio-
binder can not only improve the ductility and fracture energy of 3. Materials and experimental plan
reclaimed asphalt shingles, but also enhance the fatigue property
and cracking characteristic and have no negative effect on the 3.1. Materials
moisture susceptibility/rutting characteristic of the high reclaimed
asphalt pavement (Oldham et al., 2015; Dong et al., 2018). Addi- 3.1.1. Base asphalt
tionally, it is found that bio-rejuvenator derived from linseed oil can Pen70 and SBS modified asphalts were used in this study as the
lower stiffness and increase fracture energy of vacuum tower original asphalts. Pen70 asphalt is commonly used in fabrication of
distillation bottom asphalt mixtures, which performs better than polymer modified asphalt and SBS modified asphalt is another
the commercial rejuvenators (Podolsky et al., 2016; Zhang et al., choice. The dosage of SBS polymers in SBS modified asphalts was
2018b, 2019). Over all, it is proved that bio-binder can be a prom- 4 wt%. Table 1(a) shows the basic properties of the two asphalts.
ising and high performance bio-rejuvenator for aged asphalt
binder.
3.1.2. Bio-rejuvenator
However, the aim of the above work is limited to characterizing
The bio-rejuvenator was derived from a cotton oil (basic prop-
the rheological and chemical properties of bio-modified or bio-
erties are shown in Table (2) with the dibutyl phthalate (DBP) as its
rejuvenated asphalt binders. Only a few researches have been con-
plastic modifier to obtain better rejuvenation performances of bio-
ducted on the aging behavior of bio-rejuvenated asphalt. It is
rejuvenated asphalt. The cotton oil is an eco-friendly waste mate-
important to study the aging resistance of bio-rejuvenated asphalt
rial as a by-product of biodiesel. The dosage of DBP was set as 7.5 wt
because the judgement of rejuvenation effect depends not only on
% of cotton oil according to the previous study. The bio-rejuvenator
the instant pavement performance of rejuvenated asphalt, but also
was prepared by mixing the cotton oil and DBP at 105
C for 30 min
on whether the service life of rejuvenated asphalt is long enough to
through a homogenizer at 100 rpm (Zhu et al., 2017).
make rejuvenation cost-effective. The existing research has
demonstrated that the aging of virgin asphalt is slower than that of
the rejuvenated asphalt (Ongel and Hugener, 2015). It is also found 3.1.3. Bio-rejuvenated asphalt
that the physio-chemical oxidation doesn't reverse after rejuvena- To obtain aged asphalts for rejuvenation, the original asphalts
tion. And the aging behavior is vital in identifying how rejuvenators (Pen 70 and SBS) were aged through the Thin Film Oven Test (TFOT)
affect the RAP binder (Cavalli et al., 2018a, 2018b). Up to now, the at 163
C for 5 h (ASTM D 1754, 2015). Before rejuvenation, only 5 h-
aging indexes used for evaluation are usually based on direct test TFOT aging was conducted here to simulate aging during mixing
results, such as viscosity, ductility or modulus and phase angle. The and paving, just as a tentative step to investigate the influence of
research indicates that these aging indexes always have inconsistent rejuvenation on the aging behavior of aged asphalts. According to
correlation with each other (Zhang et al., 2018a). It is comprehensible the previous research, the dosages of bio-rejuvenator for aged Pen
due to the fact that they are based on different tests and represent 70 asphalt and SBS modified asphalt were 3 wt% and 4 wt%,
different performances. It is ideal to find an internal aging index that respectively (Zhu et al., 2017). As the bio-rejuvenator has a great
can characterize the physical mechanical property of aged asphalt, compatibility with asphalt (Dong et al., 2018), the mixing process of
which will not be influenced by different test conditions. And then the bio-rejuvenator and aged asphalts lasted for 15 min using a
performances under different conditions can be deduced from the high speed shearing machine at the speed of 5000 rpm at 125
C,
index and the service life of the asphalt can be estimated. Thus, this with the mixing container put in an oil bath box to keep the tem-
paper pays attention to evaluating the aging behavior of two bio- perature constant. The properties of the two bio-rejuvenated as-
rejuvenated asphalts (bio-rejuvenated Pen70 asphalt and bio- phalts were recovered to the original level, as shown in Table 1(a).
rejuvenated SBS modified asphalt) with chemical and mechanical
test methods. The original Pen70 and SBS modified asphalts under 3.2. Methods
identical aging conditions were set as the control group. Two internal
aging indexes obtained from rheological tests were proposed to 3.2.1. Aging method
characterize the aging extents. Additionally, correlations between The original unaged asphalt samples (Pen70, SBS), as well as the
chemical aging index and the two indexes were discussed. Further bio-rejuvenated asphalt samples (bio-rejuvenated Pen70 and SBS)
research on the internal aging indexes would be worthwhile. were conducted using TFOT aging at 163
C for 5 h (ASTM D 1754,
2015) and 15 h, respectively. According to the research, if the ag-
2. Objectives and scope ing time is a good choice, the thin film oven test (TFOT) can be used
to simulate long-term aging (Huang et al., 1996). Thus aging from
The study focuses on evaluating the aging behavior of bio- 5 h to 15 h using TFOT was used here to simulate the process of
rejuvenated Pen70 and bio-rejuvenated SBS modified asphalts aging deepening. But in the following figures, a concept of accu-
from both the chemical and mechanical perspectives. Fourier mulative aging time is proposed to represent aging process instead
transform infrared spectroscopy test (FTIR), asphalt rotational vis- of aging time. ‘Accumulative aging time’ means sum of aging time
cosity test and dynamic shear rheological test were used for anal- before and after rejuvenation. That is, the indexes of the bio-
ysis. Relationships among the results were analyzed utilizing linear rejuvenated asphalts (Pen70r, SBSr) before aging are plotted at
regression to discover internal aging indexes. Thus, the objectives 5 h on the x-axis, regarded as the improved 5 h-TFOT aged asphalts.
are as follows: In doing so, the indexes of the bio-rejuvenated asphalts after 5 h-
TFOT aging are plotted at 10 h on the x-axis because the 5 h aging
(1) Comparing the aging behavior of original and bio- time before rejuvenation was added to the accumulative aging
rejuvenated asphalts, evaluating the aging development time. In doing so, the accumulative aging time of Pen70r and SBSr
process of bio-rejuvenated asphalts; samples are 5 h, 10 h and 20 h.
 X. Cai et al. / Journal of Cleaner Production 220 (2019) 1231e1238 1233

Table 1
(a) Basic properties of Pen70 and SBS asphalts.

Parameters Unit Pen70 SBS

Original Aged Rejuvenated Original Aged Rejuvenated

Penetration (25 C,100 g,5s) (EN 1426) 0.1 mm 66 51 65 62 53 65
Ductility (10
C,5 cm/min) cm 52 10.2 53.2 62 40.3 56.1
o
Softening point (EN 1427) C 46 52 46.8 56 61 57.2
Viscosity (135
C) (EN 12595) Pa$s 0.59 0.65 0.40 1.96 2.24 1.70
Mass loss after Thin Film Oven Test (TFOT) (EN 12607-1) % 0.2 0.2

Parameters Unit Cotton oil

3
Density (15 C) g$cm 1.03
Acidity mgKOH$g1 50
o
Flash point C 240
Viscosity (60
C) Pa$s 0.163

3.2.2. Fourier transform infrared spectroscopy test 4. Results and discussion

Fourier transform infrared spectroscopy test (FTIR) was
employed to investigate the transformation of functional groups of 4.1. Analysis of chemical change by FTIR spectroscopy
asphalt samples (Pen70, SBS, bio-rejuvenated Pen70 and SBS)
during the aging process (after 5,15 h TFOT process, respectively). To investigate how aging happened in different asphalts before
The samples for the FTIR test were prepared with a liquid- and after rejuvenation, FTIR test was employed to quantify changes
membrane method and the FTIR were measured by a NEXU870 of the related functional groups. Before this, the compositions of
Spectrometer. The spectra were recorded from 4000 to 400 cm1 at the bio-rejuvenator and its transformation during aging were
a resolution of 4 cm1 averaging 32 scans for each measurement. studied firstly. The results would be a foundation of searching for
internal aging indexes.

3.2.3. Asphalt rotational viscosity

4.1.1. Bio-rejuvenator compositions
A series of viscosity measurements were performed on four
Additional analysis was done first to detect compositions of the
asphalts (Pen70, SBS, bio-rejuvenated Pen70 and SBS) during the
bio-rejuvenator without any binder, as well as any degradation due
aging process (after 5,15 h TFOT process, respectively) through the
to oxidation. The bio-rejuvenator was placed alone in an oven for
Brookfield Rotational Viscometer. At least two replicates were
TFOT aging at 163
C. The procedure was to ensure that the rejuve-
tested for each type of asphalt at 115
C, 125
C, 135
C and 145
C,
nator stays stable during aging process. It is obvious from Fig. 1(a)
and the shear rates were controlled according to AASHTO Desig-
that the bio-rejuvenator was composed of alcohol (1290 cm1,
nation: T 316-13.
1125 cm1, 1076 cm1), esters (1243 cm1), carboxylate (1701 cm1),
aldehyde compound (1737 cm1), ketones (1711 cm1) and so on. As
TFOT aging deepened, the alcohols gradually transformed into al-
3.2.4. Dynamic shear rheological test
dehydes and ketones. There was a little change in the characteristic
An Anton Par SmartPave 102 dynamic shear rheometer equip-
peak of carbonyl, which means the oxidation of the bio-rejuvenator
ment was adopted in investigating both the viscous and elastic
was less. Thus it could be concluded that the bio-rejuvenator didn't
behavior of aged asphalt specimens (Pen70, SBS, bio-rejuvenated
change significantly their chemical compositions after 15 h-TFOT
Pen70 and SBS after 5, 15 h TFOT process, respectively). For pre-
aging.
cise characterization under a broad range using analytical model,
the frequency sweep test was run to obtain the complex shear
modulus G* and the phase angle d for the specimens under strain- 4.1.2. Chemical indexes during aging process
controlled modes (within the linear viscoelastic response, strain The spectra for bio-rejuvenated asphalts are shown in Fig. 1(b).
value ¼ 1%) with frequency between 0.1 and 30 Hz (0.1, 0.2, 0.5, 1, Only the spectra ranging from 2000 to 600 cm1 are presented
2,5, 10, 15, 20, 25 and 30 Hz) at temperature between 5 and 60
C (5, because the characteristic peaks in this range are the most repre-
15, 30, 45 and 60
C) (AASHTO T 316-13, 2013). The test specimen of sentative. Related spectrum peaks are labeled in the figure. The
8 mm in diameter by 2 mm thick was conducted between 5 and characteristic peak around 1734 cm1 represents the stretching
30
C, while the specimen of 25 mm in diameter by 1 mm thick was vibration of carbonyl (C¼O) in the saturated fatty aldehyde. The
tested between 30 and 60
C. Finally, time-temperature super-
position principal (TTSP) was applied to develop dynamic modulus
master curves at 30
C. The reduced frequency could be calculated
with time-temperature shift factor aðTÞ. aðTÞ with a form of
quadratic function was used here as follows (Witczak, 2005):

logwr ¼ logw þ log aðTÞ (1)

log aðTÞ ¼ aT 2 þ bT þ c (2)

Where wr is the reduced frequency, w is the actual angular fre-

quency, T is the temperature and a,b,c are model constants. The
aðTÞ is obtained by fitting at least squares principle with Excel Fig. 1. FTIR spectra of (a) the bio-rejuvenator during aging process; (b) the original and
solver. unaged bio-rejuvenated asphalts.
1234 X. Cai et al. / Journal of Cleaner Production 220 (2019) 1231e1238

stretching vibration of carbonyl (C¼O) in the carboxylic acid is re- of SBS, indicating that oxidation aging reactions were faster in
flected at the peak around 1701 cm-1. 1032 cm1 shows the Pen70 than in SBS. It was due to the fact that SBS polymers had
stretching vibration of sulphoxide (S¼O) (Feng et al., 2016). Besides, positive effect on restraining the aging of base asphalt (Zhu et al.,
the peak at 967 cm1 is unique for SBS modified asphalt, which 2018). There was little change in the growth rates of the CAIs
represents the flexural vibration of the double bond of carbon before and after rejuvenation for both asphalts. It demonstrates
(C¼C) (Xiong et al., 2017). that bio-rejuvenation was just a process of physical blending.
As Fig. 1(b), it follows that the bio-rejuvenated asphalts display Additionally, the CCI reflects the competitive chain of degradation
the quite similar FTIR spectrum to the original asphalts’, except that and crosslinking reactions in SBS, which influences the mechanical
there is a spectral band at around 1734 cm1 in the bio-rejuvenated properties of SBS significantly (Xu et al., 2007). There was a slight
asphalts. This indicates that after bio-rejuvenation, there generated increase in the CCI of the original SBS asphalt from5h to 15 h due to
just a new carbonyl functional group in the saturated fatty the crosslinking reaction. But after rejuvenation the network
aldehyde. structure was mainly destroyed and the CCI kept decreasing. In
The carbonyl and sulphoxide functional groups are the aging addition, the higher CIR in SBSr than in Pen70r resulted from the
products of asphalts (Feng et al., 2016). The changes of the carbonyl larger dosage of bio-rejuvenator in SBSr. The faster decline of the
in the saturated fatty aldehyde are due to the aging of the bio- CIR in SBSr than in Pen70r indicated the bio-rejuvenator in SBS was
rejuvenator. And the carbon-carbon double bond (967 cm1) can more susceptible to aging than in Pen70.
reflect the changes of the SBS polymers. Thus to evaluate the aging
extent, the carbonyl indexes (1701 cm1 and 1734 cm1), the
sulphoxide index (1032 cm1) and the double bond of carbon index 4.2. Analysis of viscosity and activation energy
(967 cm1) were calculated as follows:
The viscosity can characterize the asphalts’ ability of resisting
Chemical Aging Index ¼ Carbonyl index ðCIÞ þ Sulphoxide index ðSIÞ shear deformation. The viscosity at 135
C is an index for rejuve-
nated asphalts to judge if eligible in EN 12595. The change of vis-
A1701 A1032
¼P  þP   cosity at 135
C, named the viscosity aging index (VAI), is often
1
A 200  600cm A 200  600cm1 utilized to evaluate the aging extent (Zhu et al., 2018). The defini-
tion of the VAI is as Equation (6) and the VAIs of the four specimens
(3)
during aging process are as Fig. 3(a).

A1734 viscosity after aging  original viscosity at 0h

Carbonyl index of rejuvenator ðCIRÞ ¼ P   (4) VAI ¼ (6)
A 200  600cm1 original viscosity at 0h
The VAI of Pen70r and SBSr were even lower than the original,
A967 demonstrating that the bio-rejuvenator could restore the viscosity
Double bond of carbon index ðCCIÞ ¼ P   (5)
A 200  600cm1 of both asphalts. Besides, SBS had a steadier VAI than Pen70 as
aging, owing to its better aging resistance. While for both asphalts,
Where A is the area of the related spectral band. the increasing gradient of the VAI after rejuvenation kept similar
The areas under the spectra were calculated by the Nicolet with that of the original, which was not compliance with the pre-
omnic8.2 Software (Zhang et al., 2013). The results of the three vious research that bio-rejuvenated asphalt was more susceptible
indexes are in Fig. 2. According to Fig. 2, the chemical aging indexes to aging (Ongel and Hugener, 2015). It is because the VAI reflects
(CAI) of Pen70 and SBS increased after rejuvenation. It was owing to the aging extent through the change of viscosity at only a constant
the adding of carbonyl from the bio-rejuvenator as Fig. 1(a). Be- temperature. But asphalt is susceptible to temperature as well as
sides, the growth rate of the CAI of Pen70 was much larger than that

Fig. 3. (a) VAI of four asphalts; (b) Arrhenius Equation of the unaged Pen70; (c)
Fig. 2. Comparison of the FTIR indexes of Pen70 and SBS asphalts. Activation energy of four asphalts; (d) AI of four asphalts.
 X. Cai et al. / Journal of Cleaner Production 220 (2019) 1231e1238 1235

loading frequency. The sensitivity is varied for different asphalts the glassy modulus associated with the behavior at high fre-
thus the VAI can rank asphalts at the specific temperature but is quencies and low temperatures, w is the angular frequency, m is a
unable to rank their aging extent under a broad temperature range. calibration constant, i is the complex number, t0 is the character-
The activation energy of viscosity is introduced here to repre- istic relaxation time. k and h are constants and 0 < k < h < 1. b is a
sent the internal property of asphalt. The flow of asphalt is essen- constant that depends on the viscosity of the dashpot.
tially the movement of molecules in the asphalt to overcome the The model calibration process was accomplished by utilizing the
energy barrier from the original position to the adjacent ‘hole’. The Global Optimization in MATLAB software and the model parame-
activation energy is the minimum work to overcome the barrier. It ters are shown in Table 2. The reference temperature is 30
C.
can characterize the fluidity or temperature sensitivity of asphalt
and can be calculated through the Arrhenius Equation (in logs) as
below (Delmar Salomon, 2002). 4.3.2. Rheological analysis
The tested and modeled modulus and phase angle master
Ef curves for two asphalts are shown in Fig. 4. The dynamic modulus
lnh ¼ þ lnA (7)
RT and phase angles of Pen70 both changed obviously after aging and
rejuvenation. The bio-rejuvenator had little effect on the modulus
Where hðPa,sÞ is the viscosity under different temperatures. TðKÞ is of Pen70. But the phase angles of Pen70 decreased a lot at low
the Kelvin temperature. A is a constant. Rð8:314 J=mol,KÞ is the frequencies, meaning high temperatures, corresponding to the re-
general gas constant. And Ef ðkJ=molÞ is the activation energy. The sults of the VAI. For SBS, tiny difference was found on the modulus
relationship between the viscosity and the temperature of the after aging and rejuvenation. It is because the stiffening effect of
unaged Pen70 is plotted in Fig. 3(b) as an example. The activation aging and the softening effect of degradation of SBS polymers
energy equals the gradient of the line multiplying the general gas formed a competitive system (Naderi et al., 2014). On the other
constant. The calculation results of the four asphalts are shown in hand, the phase angles were susceptible to aging and rejuvenation.
Fig. 3(c). For both asphalts, the activation energy decreased after There was a distinct decrease in the phase angle master curves after
rejuvenation, indicating that the asphalts were softened. The acti- aging. And comparing to the phase angle master curves of bio-
vation energy of SBS had a decrease trend from 5 h to 15 h. It might rejuvenated SBS, the imitative effect of the 2S2P1D model for the
result from transiently more crosslinking reactions in SBS reflected phase angles of original SBS during aging was worse. Similar results
in the CCI in Fig. 2. Sun also found that the activation energy of SBS could be found in previous research because of the highly non-
has a decreasing process (Sun et al., 2016). The activation energy linear viscoelasticity of modified asphalts (Yusoff et al., 2013). Af-
index (AI) was defined according to Equation (8), showing in ter rejuvenation, the fitting results of the phase angles were good
Fig. 3(d). during aging, which indicated that the cross-linked structure in SBS
had been destroyed and the behavior of the bio-rejuvenated SBS
activation energy after aging  original activation energy at 0h
AI ¼ was closer to base asphalt.
original activation energy at 0h
(8)
As Fig. 3(d), different from the similar gradients of the VAIs 4.3.3. The viscosity of the dashpot
before and after rejuvenation, a larger gradient was found in the AI An aging index independent of frequencies needs to be
of Pen70r comparing with Pen70, consistent with the phenomenon extracted to characterize aging extent of asphalts before and after
that bio-rejuvenated Pen70 asphalt was more susceptible to aging. rejuvenation. In previous study, the area between the two
Another difference was the inflection point at 5 h in the AI of SBS, modulus master curves of unaged and aged asphalts was once
which was in line with the change of cross-linked structure content employed as the index (Cavalli et al., 2018b). If then the change in
(as showed in Fig. 2, SBS-CCI). Similar conclusion was obtained by viscous portion was neglected. So parameters from the 2S2P1D
Sun that activation energy of SBS has close correlation with model, which had physical meanings were considered to be the
colloidal structure (Wang et al., 2015). index here. The previous research demonstrated that for mixtures
with base asphalt, the model parameters k, h, the glassy modulus
Eg and the representative relaxation time t0 were approximately
4.3. Dynamic mechanical analysis linear to the change of the CI (Alavi et al., 2013). Similar results
would be obtained here. However when it came to SBS modified
The influence of aging on viscoelastic behavior of asphalts can asphalt, the glassy modulus, Eg , was relatively stable during aging.
be reflected on both viscous part and elastic part. As aging deepens, While t0 , was susceptible to aging. Lager t0 meant less viscous
the viscosity, as well as the elastic stiffness increases. To search for proportion in the behavior with aging deepening. Thus, to consider
an internal aging index representing the influence on both elastic both the elasticity and viscosity portions, the viscosity of the
and viscous part over a broad range of temperature, dynamic shear dashpot in the 2S2P1D model was chosen here to be the aging
modulus test was employed. A physical constitutive model, the two index.
springs, two parabolic elements, and one dashpot (2S2P1D) model, The viscosity of the dashpot index (HAI) was defined according
was introduced to characterize the viscoelastic behavior of the as- to the form of Equation (10). The results are shown in Fig. 5. Higher
phalts at different aging stages (Sun et al., 2016). HAI means higher stiffness. As Fig. 6, the HAI of Pen70r increased
faster than that of Pen70 during aging, in accordance with the
4.3.1. Model fitting and parameters change of AI. It indicated that bio-rejuvenated Pen70 asphalt was
For sinusoidal signals (eiwt ), the response equation of the more susceptive to age. The HAI of Pen70r at 5 h was higher than
2S2P1D model at a reference temperature is: Pen70. It was due to the fact that the viscosity proportion of Pen70r
at high temperatures decreased a lot due to the bio-rejuvenator (as
Eg  Ee in Fig. 4(b)). The HAI curves were more steady when it referred to
E* ðwÞ ¼ Ee þ (9)
1 þ mðiwt0 Þk þ ðiwt0 Þh þ ðiwbt0 Þ1 SBS and SBSr, due to the better aging resistance. A turning point was
found at 5 h in SBS, which might be the effect of the increasing
Where Ee is the equilibrium modulus, which is 0 for asphalts. Eg is cross-linked structures (the CCI) reflected in Fig. 2.
1236 X. Cai et al. / Journal of Cleaner Production 220 (2019) 1231e1238

viscosity of the dashpot after aging  viscosity of the dashpot at 0h

HAI ¼ (10)
viscosity of the dashpot at 0h

4.4. Correlation analysis among three indexes

viscosity of the dashpot ¼ Eg bt0 (11)
Three aging indexes were calculated to evaluate the aging extent
of asphalts in this research: the CAI and the CCI, representing rates

Table 2
Optimized 2S2P1D model parameters.

Type Aging Time/h Eg /MPa m k h b t0 /104 a/104 b c

Pen70 0 319.10 2.339 0.360 0.669 19.687 1.288 6 0.138 3.589

5 344.42 2.365 0.333 0.646 55.993 1.300 4 0.134 3.566
15 536.83 4.306 0.312 0.635 102.975 2.395 2 0.120 3.366
Pen70r 0 262.31 3.189 0.378 0.694 54.759 3.315 4 0.134 3.619
5 315.05 6.297 0.408 0.766 48.601 4.684 3 0.126 3.538
15 345.65 3.300 0.343 0.602 178.433 5.010 3 0.128 3.487
SBS 0 834.23 5.933 0.306 0.693 8453.34 0.241 4 0.134 3.576
5 834.26 17.025 0.392 0.737 8451.93 0.949 8 0.150 3.881
15 1914.58 20.925 0.298 0.711 9750.92 0.207 7 0.151 3.849
SBSr 0 731.94 5.674 0.292 0.698 10002.87 0.200 5 0.134 3.463
5 735.00 7.864 0.354 0.740 10000.04 0.471 6 0.133 3.405
15 736.63 7.309 0.309 0.709 23046.77 0.465 4 0.122 3.268

Fig. 4. (a) Modulus and (b) Phase angle master curves for Pen70 asphalts; (c) Modulus and (d) Phase angle master curves for SBS modified asphalts.
 X. Cai et al. / Journal of Cleaner Production 220 (2019) 1231e1238 1237

more severe aging extent in Pen70r. Thus after rejuvenation, the

time period before the intersection is an advantage period for the
bio-rejuvenated Pen70 and the original Pen70 is better during the
period behind the intersection. According to the above ideal model,
a total benefit of rejuvenation can be calculated to decide whether
the regeneration is profitable.
As for SBS modified asphalt, the AI and the HAI change much
less than Pen70 after aging. And the susceptibility to the aging
functional groups is relatively stable after rejuvenation. There is a
decrease in the AI & HAI of SBS from 5 h to 15 h because of the
momentary increase of the CCI (cross-linking of SBS polymers).
While the linear relationship is not influenced by the fluctuation
of the CCI. More tests in the future need to be conducted to verify
the correlation here. As currently envisaged, the bio-rejuvenator
can restore the physical property (the AI and the HAI) of aged
SBS modified asphalt to original extent. And the aging rate of bio-
rejuvenated SBS asphalt has little difference with the original
one. But after rejuvenation, the momentary cross-linking of SBS
polymers during the initial aging stage is prevented, which
makes no fluctuation in the AI/HAI of SBSr. In conclusion,
although the bio-rejuvenator cannot restore the crosslinking
Fig. 5. HAI of the two asphalts during aging and rejuvenation. structures in SBS, the bio-regeneration of aged SBS is still cost-
effective.

5. Conclusions

Bio-rejuvenator is a promising material for aged asphalt binder.

A lot of investigations have been conducted on performance
improvement of bio-rejuvenated asphalts while the re-aging effect
is always neglected. However, the re-aging effect does influence the
service life of reclaimed asphalt pavement. Thus this paper aims to
evaluate aging behavior of two bio-rejuvenated asphalts. Compar-
Fig. 6. (a) Linear regression between AI and CAI/CCI; (b) HAI and CAI/CCI.
ison was also made between the aging development of original
asphalt and bio-rejuvenated asphalt. Conclusions are displayed as
follows:
of the oxidation aging reaction and the crosslinking or degradation
reactions, respectively; the AI representing the change of flow (1) Bio-rejuvenation was a process of physical blending, which
ability or shear deformation resistance and the HAI representing made no change in chemical functional groups. As the CAI,
the change of complex modulus after aging and rejuvenation. As an the rates of oxidation aging reaction for two asphalts stayed
internal aging index, it should have an excellent correlation with basically unchanged after rejuvenation. And for SBS modified
the change of related chemical functional groups. Thus, linear asphalt, the crosslinking structures couldn't be restored by
regression was implemented in the CAI & CCI versus the AI and the the bio-rejuvenator.
HAI separately. The results are as Fig. 6. (2) In rheological analysis, the effect of bio-rejuvenation on
For Pen70 and Pen70r, the CAI was chosen to demonstrate the Pen70 obviously reflected on the decrease of phase angle at
chemical aging extent. While for SBS and SBSr, there were cross- low frequencies. As for SBS, the modelling of phase angle was
linking and degradation reactions during aging that would seri- more susceptible to rejuvenation and aging than modulus,
ously influence the mechanical behavior of asphalt. Taking this since nonlinear viscoelastic was weakened after aging and
CAI
effect into consideration, a mathematical formula, eCCI , was found rejuvenation.
efficient for linear regression. Appropriate fitting results were ac- (3) The aging rates of physical properties of Pen70 increased
quired among the three aging indexes as the figure shows, which after rejuvenation, according to the AI and the HAI. However,
indicates that the AI and the HAI are potential internal aging in- a much lower AI and HAI were found in SBS, indicating its
dexes to characterize effect of aging on the physical property of excellent aging resistance. And the curves of AI and HAI were
different asphalts. similar with the CCI's, suggesting that the crosslinking
Specifically, in Fig. 6, it suggests that the AI and the HAI of structures dominated in the properties of SBS.
Pen70r are both more susceptible to the change of the CAI than (4) The AI and HAI had a good linear correlation with the CAI in
those of Pen70. The AI & HAI lines of Pen70r and Pen70 have a point CAI
Pen70, as well as the eCCI in SBS, which demonstrated that the
of intersection. If the CAI increases little after rejuvenation and the two indexes were potential internal aging indexes indepen-
CAI point of Pen70 is in front of the intersection, the AI & HAI of the dent of test conditions, reflecting the aging extent of asphalt
asphalt will decrease after rejuvenation, indicating that the phys- physical properties.
ical property of the aged asphalt will be improved. However, with (5) Compared with aged original Pen70, there was a benefit
aging deepening, the CAI increases (it can be concluded from Fig. 3 period for bio-rejuvenated Pen70, during which bio-
that bio-rejuvenation barely changes the increasing rate of the CAI). rejuvenation was profitable. While for SBS, rejuvenation
When the CAI point is behind the intersection, the AI & HAI of was cost-effective all the time, although the crosslinking
Pen70r will be higher than the contemporary Pen70, indicating a structures couldn't be restored.
1238 X. Cai et al. / Journal of Cleaner Production 220 (2019) 1231e1238

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