Journal of Cleaner Production 237 (2019) 117725

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Journal of Cleaner Production

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

Enhancing effect of microalgae biodiesel incorporation on the

performance of crumb Rubber/SBS modified asphalt
Shaochan Duan a, Yaseen Muhammad a, b, Jing Li a, *, Sahibzada Maria b, Fei Meng a,
Yunhao Wei a, Zhibin Su a, Hongquan Yang a
a
Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University, Nanning, 530004, China
b
Institute of Chemical Sciences, University of Peshawar, 25120, KP, Pakistan

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

Article history: In this study, microalgae biodiesel (MB) was prepared by chemically modifying microalgae acidified oil,
Received 17 April 2019 which was in turn added as a modifier to a pre-synthesized crumb rubber-styrene-butadiene-styrene
Received in revised form (CR/SBS) modified asphalt to prepare MBCR/SBS composite modified asphalt. Rotational viscosity mea-
21 June 2019
surement showed that viscosity of MBCR/SBS-2 asphalt meets the requirements of Superpave specifi-
Accepted 20 July 2019
Available online 22 July 2019
cations. Dynamic shear rheometer and multiple stress creep recovery tests revealed that MBCR/SBS-2
asphalt exhibited the largest complex modulus (G*), smallest phase angle (d) in high frequency range,
Handling editor. Zhen Leng and higher average recovery rate (R) after rotating thin film oven test. The fatigue cracking analysis
revealed that higher content of MB results in better resistance to fatigue cracking under intermediate
Keywords: temperature. Separation analysis showed that MBCR/SBS-2 asphalt possessed softening point difference
Microalgae biodiesel modifier of 2.9
C. Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy
Crumb rubber/SBS modified asphalt analyses confirmed more unsaturated groups in the MB than in the base asphalt, and amide groups
DSR and MSCR analysis bonded to the free radicals of CR which promoted the development of network structure resulting in
FT-IR analysis
1
enhanced mechanical properties of MBCR/SBS modified asphalt than pristine CR/SBS asphalt. In addition,
H-NMR analysis
a proposed synthesis and performance mechanism of MBCR/SBS asphalt was elaborated. This study
based on simplified preparation and enhanced performance of MBCR/SBS asphalt composite modified
asphalt, could be of potential interest for practical applications in construction and highway industries.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
With the development of global economy, the construction of
asphalt based roads is increasing in parallel. Under heavy traffic
load and harsh environmental conditions, conventional asphalt
pavements on highways face damage problems such as rutting,
cracking and stripping. Among these, stripping of asphalt and
aggregate caused by water accumulation concomitantly causes
asphalt pavement damages and serious environmental pollution
(Zhang et al., 2018b). Thus, advocating global environmental pro-
tection regulations, road construction engineers and researchers
are consistently striving for designing new materials which can
concurrently ensure the structural integrity of asphalt pavement
and environmental safety (Xu et al., 2017).
At present, some environment friendly modified asphalt
* Corresponding author.
E-mail address: lijingsophia1234@163.com (J. Li).
materials for roads construction have been explored such as waste
tire rubber modified asphalt (Fakhri and Farshad, 2016; Oliveira
et al., 2013), low emission warm mix asphalt (Almeida-Costa and
Benta, 2016; Sol-Sa nchez et al., 2016), and recycled asphalt (Xiang
et al., 2012). In addition, the potential application of bio-oil in the
preparation of bio-asphalt as pavement material has also been re-
ported with promising results (Fini et al., 2011).
There are many studies reported on the preparation of bio-
materials modified asphalt. For example, Mogawer et al. (2012)
prepared modified asphalt by adding pig manure extracted bio-
adhesives with reclaimed asphalt pavement and shingles, which
exhibited enhanced low temperature properties. EH Fini's (Fini
et al., 2017) reported the enhanced low-temperature performance
and processability of bio-binder extracted from pig manure incor-
poration rubber-modified asphalt. In addition, the surface activa-
tion of rubber particles with bio-modifiers rich in amide groups can
enhance the interaction between rubber and base asphalt, and ul-
timately increased increase resistance to water damage. Similarly,

https://doi.org/10.1016/j.jclepro.2019.117725
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
2 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725
Hill et al. (2016) reported that awn grass and corn straw-based bio-
oil modified bio-asphalt mixture realized excellent fracture resis-
tance and creep compliance. Garcia et al. (2016) proved that addi-
tion of sunflower seed oil capsule can enhance the regeneration
and prolongation of life of asphalt mixture. Podolsky et al. (2016)
found that the addition of corn biomass extracted biological addi-
tive as warm mixing agents can reduce the mixing and compacting
temperature by 30
C.
Accredited to the variety and wide range of sources and easy
regeneration, bio-oil extracted from biomass are considered envi-
ronment friendly. Bio-oil can be extracted from biomass materials
such as animal manure (You et al., 2011), waste wood (Yang et al.,
2014), agricultural waste (Roauf, 2010), microalgae and waste
edible oil (Chailleux et al., 2012). The properties of bio-asphalt
prepared from the incorporation of different biomass materials
vary largely. For example, Raouf and Williams et al. (Roauf, 2010)
found that waste wood added modified bio-asphalt exhibited
improved high temperature performance than conventional
asphalt, but greatly compromised on the low temperature prop-
erties. On the contrary, the bio-asphalts prepared by the addition of
bio-oil extracted from pig manure and waste cooking oil revealed
weaker high temperature and better low temperature performance
respectively (Fini et al., 2011; Wen et al., 2012).
Research on the microalgae industry has received increasing
attention recently. Compared with its crops, microalgae have faster
growth rate, higher rate of photosynthesis and oil content
(Chailleux et al., 2012). In addition, aquatic mode of reproduction
and growth saves considerable extent of land resources. Rational
use of the by-products from microalgae industry e.g. microalgae
acidified oil, can concomitantly save renewable resources and
contribute to the economic benefits. Furthermore, induction of
additional additives like nano-materials and polymers to bio-
asphalt can further improve the road performance of original
road pavement (Onochie et al., 2013). Therefore, it is worth
studying the addition of polymers to the modified microalgae
acidified oil bio-asphalt to produce a road construction material
that can simultaneously improve road performance and alleviate
environmental pollution.
Thus, in this study, microalgae biodiesel (MB) was prepared by
transesterification and vacuum distillation using microalgae acidi-
fied oil. 2 wt%, 4 wt%, and 6 wt% MB was mixed with crumb rubber/
styrene-butadiene-styrene (CR/SBS) asphalt for the synthesizing
MBCR/SBS composite added asphalt. The road performance under
high and medium temperature and stability during storage of
MBCR/SBS asphalt were analyzed by physical properties, rotational
viscosity (RV), dynamic shear rheometer (DSR), multiple stress
creep recovery (MSCR), anti-fatigue cracking property after pres-
sure aging vessel (PAV) and phase separation tests. Chemical
structure of MB was analyzed by Fourier transform infrared (FT-IR)
spectroscopy and proton nuclear magnetic resonance (1H-NMR)
spectroscopy. In addition, the microscopic morphology and thermal
stability of MBCR/SBS asphalt were analyzed by fluorescence mi-
croscope (FM) and thermogravimetric analysis (TGA) respectively,
and a proposed synthesis and performance mechanism of MBCR/
SBS asphalt was elaborated.
2. Experimental
2.1. Materials
Analytica grade reagents were used in this project. CR (particle
size of 100 mesh) was purchased from Changzhou Rongao chemical
new materials Co., Ltd. Microalgae acidified oil (oil content of 40 wt
%) was purchased from Henan Jimei chemical products Co., Ltd.
Methanol was provided by Guangdong Guanghua technology Co.,
Ltd. Concentrated sulphuric acid (AR, 98%) was provided by
Chengdu cologne chemicals Co., Ltd. SBS (Linear YH 791) was ob-
tained from Shandong Chongjiao road and bridge engineering Co.,
Ltd. SK 70A base asphalt was provided by Shandong boheng
economy and trade Co., Ltd. Table 1 compiles some physical prop-
erties of base asphalt while those of SBS have been reported in our
previous study (Han et al., 2018).
2.2. Preparation of asphalt
2.2.1. Preparation of MB
60 ml of microalgae acidified oil and 240 ml of methanol were
poured into a 500 ml round bottom flask and 13 ml of concentrated
sulfuric acid (as catalyst) were slowly added to it. The mixed so-
lution was stirred on a collecting thermal type constant tempera-
ture heating magnetic stirrer at 65
C for 5 h. After this, the mixture
was distilled by a rotary evaporator (Hei-VAP Valu, Germany) at
30 rpm under vacuum of 0.08 MPa. Distillation was performed at
85
C, 95
C, 105
C, 110
C, 115
C and 120
C with each distillation
covering 20 min. The MB sample after distillation was collected.
This synthesis procedure is summarized in Fig. 1.
2.2.2. Synthesis of MBCR/SBS modified asphalt
The base asphalt was heated to 165
C in an iron vessel till
fluidity. Pre-weighed 4 wt% SBS and 10 wt% CR were added to the
molten asphalt and sheared in a high-speed shearer at 5000 rpm
for 30 min to completely pulverize CR and SBS. 0 wt%, 2 wt%, 4 wt%
and 6 wt% of MB were separately added to the above mixed system,
and stirred at 400 rpm for 1 h, and the sample was developed in
oven by keeping static at 170
C 2.5 h. The prepared asphalts were
labeled as CR/SBS, MBCR/SBS-2, MBCR/SBS-4 and MBCR/SBS-6
corresponding to 0 wt%, 2 wt%, 4 wt% and 6 wt% MB contents
added modified asphalt, respectively. A similar procedure was
adopted to prepare 5 wt% SBS modified asphalt as a control sample.
This preparation process is summarized in Fig. 2.
2.3. Performance evaluation
2.3.1. Physical properties evaluation
Penetration is a measure of vertical distance (in 0.1 mm)
through an asphalt sample covered by a standard needle under
known temperature, time and load conditions following standards
of ASTM D5 (ASTM, 2013a). Softening point is the temperature at
which a substance reaches a certain degree of softening under
specified conditions, which was performed using ASTM D36 (ASTM,
2014) via ring and ball method. The ductility was measured by
molding the asphalt into 8-shaped standard test piece and
stretching each at a constant speed of 5 cm/min till breakage at 5
C
following ASTM D113 (ASTM, 2017). Each experiment was per-
formed in triplicates and average values were reported along-with
the standard deviation.
2.3.2. RV measurement
The viscosity was measured using a Brookfield viscometer (RV-
DVIII Ultra) according to ASTM D4402 (ASTM, 2013b). The viscosity
of asphalt sample at a specific temperature was obtained by
applying rotational shear. 10.5 g of each modified asphalt was taken
using No. 27 rotor. Three replicates were taken at 1 min intervals for
each test and the average viscosity values were recorded at a
specified temperature and speed.
2.3.3. DSR test
According to AASHTO T315 (AASHTO, 2012), DSR (CVO 100D
ADS, Bohlin Instrument) having parallel plate geometry was
applied for the evaluation of viscoelastic properties of various
 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725 3

Table 1
Conventional properties of the base asphalt (SK 70A).

Test Type SK 70A Experimental methoda

Measured value Standard value

Penetration 25 C (0.1 mm) 71 60e80 T0604
Penetration index (PI) 1.25 1.0e1.5 T0604
Softening Point (oC) 47.0 46 T0606
Ductility (5 cm/min 10
C) (cm) 52 15 T0605
60
C dynamic viscosity (Pa$s) 185 180 T0620
Density 15
C (g/cm3) e Actual observed value T0603
a
Experimental method is from Technical Specification for Construction of Highway Asphalt Pavements (JTG F40-2004).

Fig. 1. Schematic representation of preparation of MB.

Fig. 2. Schematic representation of the preparation of MBCR/SBS modified asphalt.

groups of modified asphalts. This study used a parallel plate of
25 mm with a gap of 1 mm between two consecutive plates. The
frequency sweep test was performed in a temperature range of
16e82
C.
2.3.4. Aging procedure of asphalt
Aging of asphalt was performed by volatilization, polymeriza-
tion and oxidation by atmospheric oxygen during mixing and
agitation. The rotating thin film oven test (RTFOT) is used to
simulate the short-term aging of asphalt during construction. PAV
can simulate aging during prolonged use of 3e5 year. The asphalt
samples were used RTFOT for 85 min at 163
C (ASTM, 2004) and
PAV for 20 h at 100
C (ASTM, 2009).
2.3.5. MSCR test
In previous studies, the rutting factor (G*/sin d) discussed in
terms of performance grade (PG) was used to evaluate the rutting
resistance of polymer modified asphalt. However, there are several
reports on the weak relation between G*/sin d and real field
(Behnood et al., 2016; Soenen et al., 2013), and hence MSCR test can
better evaluate the rutting resistance of polymer modified asphalt
as compared to G*/sind. Therefore, this study used MSCR test for
evaluate anti-rutting performance at 64
C according to AASHTO TP
70 (AASHTO, 2010a). In this test, shear stress levels of 0.1 kPa and
3.2 kPa were applied to the asphalt samples after RTFOT for 1 s,
followed by a rest period of 9 s.
2.3.6. Fatigue cracking test
Fatigue cracking tests were performed on PAV residual binders
according to AASHTO M320 (AASHTO). The complex modulus (G*)
and phase angle (d) at 25
C were measured by DSR to calculate the
fatigue factor (G*$sind). The smaller value of G*$sind of PAV-aged
4 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725
asphalt binder at intermediate temperature suggests its better
resistance to fatigue cracking. In this test, a parallel plate of 8 mm
diameter with a gap of 2 mm was used with an angular frequency of
1.59 Hz.
2.3.7. Phase separation analysis
Phase separation analyses were conducted in accordance with
T0661-2011 (T0661-2011, 2011). 50 g of modified asphalt was
placed in aluminum sample tubes with a diameter and length of
25 mm and 140 mm, respectively. After closing, the port was
vertically placed and heated in an oven at 163
C for 48 h. The
sample tube was then removed from the oven, cooled to room
temperature, and was horizontally cut into three equal parts. The
storage stability of each group of modified asphalt was evaluated by
measuring the difference in softening point between the top and
bottom layers. If the difference in softening point is less than 3.5
C,
the modified asphalt is considered to have good storage stability
(T0661-2011, 2011).
2.4. Microanalysis
2.4.1. FT-IR analysis
The chemical structure of various asphalts was characterized by
FTIR attenuated total reflectance spectrometer (FTIR-ATR) (Nicolet,
USA). The spectrum was obtained by dropping a thin layer of water
on a zinc selenide (ZnSe) prism. The contact between the adsorbent
and the prism surface attenuated the internal reflected light and
provided the FTIR absorption spectrum, which is identical to the
spectrum recorded when the light passes through the surface layer
of material under study.
2.4.2. 1H-NMR analysis
1
H-NMR was performed via Bruker 600 MHz NMR using
deuterium chloroform (CDCl3) as the solvent while tetramethylsi-
lane was used as a reference material.
2.4.3. FM analysis
The microscopic morphology of modified asphalt was observed
by electric fluorescence microscope (IMAGER. Z2). In sample
preparation, a drop of asphalt was heated and dripped onto the
slide, which was covered and pressed into thin sheets (Zhang et al.,
2018a).
2.4.4. TGA
Before performance test, MB and base asphalt were thoroughly
mixed at high temperature, and were then tested for thermal sta-
bility via TGA and derivative thermogravimetry (DTG) (Hou et al.,
2018). The samples were heated from 30 to 800
C at a heating
rate of 10
C/min by a thermogravimetric analyzer (Shimadzu TG-
50).
3. Results and discussion
3.1. Evaluation of various performance indicators
3.1.1. Physical properties of various modified asphalts
Fig. 3 shows that the addition of MB proportionally improves the
penetration of SBS modified asphalt, which suggests that asphalt
viscosity decreases to a certain extent. Compared with 5% SBS
modified asphalt, the ductility of CR/SBS modified asphalt
decreased by 33%, however it increases for each group of MBCR/SBS
asphalt with increasing MB contents. This further suggests that the
addition of MB improves the resistance of modified asphalt to
cracking, which may be related to the rich light components in MB
(Xu et al., 2017). At more than 2% MB content, the softening point of
MBCR/SBS modified asphalt was significantly reduced, attributed to
the high contents of light components provided by MB. These facts
of ductility, penetration and softening point of MBCR/SBS added
asphalt were far superior than some reported studies and hence
scores in favor of MBCR/SBS modified asphalt for practical appli-
cations (Moreno and Rubio, 2013).
3.1.2. RV measurement
Fig. 4 shows that the viscosity of each sample decreases with
increasing temperature, while MB addition pronouncedly
decreased the viscosity of CR/SBS modified asphalt. The sharper
decrease in viscosity upon the addition of 2% MB could be attrib-
uted to the lubricating effect of MB on CR and SBS. Upon increasing
the amount of MB from 4% to 6%, a milder decrease in viscosity is
observed, which is due the adsorption of MB on the surface of CR
and SBS, hence establishing bonds between the disulfide and sty-
rene butadiene polymer with the free radicals of CR (Baeta et al.,
2009).
According to ASTM D4402 (ASTM, 2013b), 135
C is the test
temperature in accordance with Superpave specifications. It can be
seen from Fig. 4 that the viscosities (at 135
C) of both, 5% SBS and
CR/SBS modified asphalts, were higher than the Superpave speci-
fications (3 Pa s). However, those of all MBCR/SBS asphalts were
lower than 3 Pa s, which conforms to Superpave specifications.
3.1.3. DSR analysis
Due to the functional limitations of DSR, it is not possible to
measure the complex modulus (G*) and phase angle (d) of asphalt
samples at low temperatures (<10
C). Therefore, the master curve
is used for analysis. The master curve test applies a specific load to
the asphalt sample at different temperatures and frequencies to
test the stiffness of the asphalt to infer a smooth curve under a wide
range of conditions. Asphalt behaves stiffer when it is loaded at
high frequencies and lower temperatures (Ericson et al., 2016).
Fig. 5 shows the results of master curve analysis of G* of different
modified asphalts. The procedure and methodology for obtaining
master curve is described in supporting information as Fig. S1.
It can be seen from Fig. 5 that in the high frequency region, G* of
MBCR/SBS modified asphalt is higher than 5% SBS modified asphalt,
while MBCR/SBS-2 modified asphalt realized the highest G* value.
This enhancement in viscoelastic properties by the addition of 2%
MB could be due to the fact that this amount of MB can supplement
the light components in the mixed system, which can be fully
absorbed by CR and SBS reaching saturation, thus promoting
swelling and development of asphalt (Xu et al., 2017). The filling
effect of CR is obvious, which enhances the development of SBS
network structure (Liang et al., 2015b). In addition, some of the
polymer chains in CR enter into the base asphalt, thereby increasing
the interaction of asphalt with rubber (Baeta et al., 2009). On the
contrary, higher MB content results in smaller G* value which is due
to the supersaturation of CR and SBS and rupturing of CR (Moreno
and Rubio, 2013). This dilutes the effect of MB, thus decreasing the
elasticity of modified asphalt.
Fig. 6 suggests that G* of various modified asphalts gradually
decreases with increasing temperature, among which those of CR/
SBS modified asphalt was the largest at 60
C, followed by MBCR/
SBS-2 modified asphalt, which suggested enhanced high temper-
ature viscoelastic properties of these two samples than those of 5%
SBS modified asphalt. However, G* gradually decreased with
increasing MB content. At more than 2% MB content, the absorption
of light components by CR and SBS reaches supersaturation and CR
ruptures, resulting in significantly decreased high temperature
performance (Fini, 2016) which was even lower than that of control
asphalt.
Viscoelastic properties of various modified asphalts were
 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725 5

Fig. 3. Test results of physical properties of different modified asphalts.

Fig. 5. Master curve of complex modulus of different original asphalts.

Fig. 4. Viscosity of different original asphalts at variable temperatures.

and the elastic properties are correspondingly decreased. This is

determined by calculating their d at 1.6 Hz frequency using DSR at
different temperatures and the test results are shown in Fig. 7.
Fig. 7(a) suggests that d increases with increasing temperature and
below 30
C, the d of MBCR/SBS-2 modified asphalt was the
smallest suggesting its best elastic properties among all the sam-
ples. Upon increasing MB amount from 2% to 6%, the d is increased
attributed to the fact that 2% MB can facilitate the absorption of
light components by CR and SBS, while further increasing its con-
tents results in the dilution of asphalt (Fini, 2016).
It can be seen from Fig. 7(b) that d of 5% SBS modified asphalt is
much larger than that of CR/SBS modified asphalt at a temperature
below 76
C, which indicates improved elastic properties of the
6 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725

latter. When approaching the actual pavement temperature (64
C),

the d increases with increasing MB content. However, d of MBCR/
SBS-2 modified asphalt was much smaller as compared to 5% SBS
modified asphalt, suggesting better elastic properties of MBCR/SBS-
2 modified asphalt at elevated temperature than the latter. This
makes the proposed MBCR/SBS-2 modified asphalt of potential
value than conventional SBS modified asphalt for practical appli-
cation in areas exposed to high temperatures in hot summer.

3.1.4. MSCR analysis

MSCR test is conducted using DSR for SBS, CR/SBS and MBCR/
SBS asphalts according to AASHTO TP 70 (AASHTO, 2010b) speci-
fication at 64
C. The average recovery rate (R) and non-recoverable
creep compliance (Jnr) calculated from the MSCR test results can
evaluate the rutting sensitivity of asphalt pavement.
Table 2 shows that at both, 0.1 kPa and 3.2 kPa stresses, MBCR/
SBS-2 and CR/SBS modified asphalts exhibited closely similar R
which were much larger than that of 5% SBS modified asphalt. By
increasing stress from 0.1 kPa to 3.2 kPa, the R of 5% SBS, CR/SBS and
Fig. 6. Relationship between complex modulus and temperature of various original
MBCR/SBS-2 modified asphalts decreased by 28.3%, 17.9% and 19.9%
asphalts. respectively, suggesting the more sensitive nature of 5% SBS
modified asphalt to external stress and excellent high temperature
rutting resistance of the latter two samples. This conclusion is
consistent with the results of DSR. At different stress levels, MBCR/
SBS-2 modified asphalt has the smallest Jnr. Moreover, the R of
MBCR/SBS asphalt was still much better than reported modified
asphalt (Lei et al., 2016), which could be attributed to the better
network structure developed between MB, base asphalt and SBS in
MBCR/SBS asphalt.

3.1.5. Fatigue cracking analysis

The fatigue factors of all PAV residual asphalts were calculated
and shown in Fig. 8. The G*$sind values of all asphalt samples are
less than 5000 kPa, indicating that all modified asphalts show
excellent resistance to fatigue cracking under PAV aged state (Liu
et al., 2018). The G*$sind values of MBCR/SBS modified asphalts
are significantly lower than that of 5% SBS modified asphalt. In
addition, the G*$sind values of MBCR/SBS modified asphalts are
reduced with the increasing MB content. It can be seen that the
higher the content of MB, the better the resistance to fatigue
cracking at the intermediate temperature.
Thus, from the evaluation of physical properties, RV test, DSR,
MSCR and fatigue cracking analyses, one can conclusively infer that
MBCR/SBS-2 asphalt ranked at the top of performance among the
various asphalt samples. Thus, 5% SBS, CR/SBS, and MBCR/SBS-2
asphalts were selected for onward experiments.

3.1.6. Phase separation analysis

The segregation index can evaluate the compatibility between
modifier and base asphalt and has important reference significance
for the production, storage and transportation of modified asphalts
(Han et al., 2018). The experimental results of phase separation for
various types of modified asphalts are shown in Table 3.

Table 2
Results of MSCR test for different RTFOT asphalts at 64
C.

Sample 0.1 kPa 3.2 kPa

R (%) Jnr (kPa1) R (%) Jnr (kPa1)

5% SBS 80.1 0.122 57.4 0.271

CR/SBS 97.0 0.039 79.6 0.091
MBCR/SBS-2 95.8 0.025 78.7 0.073
Fig. 7. Curve of phase angle and temperature of different original asphalts at (a)
MBCR/SBS-4 80.9 0.115 59.1 0.244
middle temperature range and (b) high temperature range.
MBCR/SBS-6 71.9 0.145 55.8 0.302
 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725 7

Fig. 8. The fatigue factor (G*$sind) of different PAV residual asphalts at 25
C.

Fig. 9. FT-IR spectrum of CR.

It can be seen from Table 3 that the difference between the

upper and bottom layers of 5% SBS and CR/SBS modified asphalt is
unit (Ali et al., 2008). The band at 694 cm1 is due to the rocking
greater than 3.5
C, which suggests that the two modified asphalts
vibration of cis 1,3-butadiene repeating structural unit (-CH2-CH2-)
have obvious phase separation behavior, which could be attributed
(Tabassum et al., 2012). These results concluded that CR used in this
to the low compatibility of SBS and CR with asphalt (Liang et al.,
study is mainly present as natural rubber and butadiene rubber.
2015a). Under gravitational force, the swollen modifier floats up,
FT-IR analysis results of base asphalt in Fig. 10 indicate the peak
resulting in a large difference in softening point between the top
at 2924 cm1 indexed to methylene group CeH stretching vibration
and bottom layers. The softening point difference in the two layers
in cycloalkane (Marsac et al., 2014). The strong absorption band at
of MBCR/SBS-2 asphalt is less than 3.5
C, which could be due to the
2857 cm1 is credited to the methyl CeH bond stretching (Yin et al.,
fact that suitable amount of MB facilitates better expansion of CR
2018), while those at 1700 cm1 and 1600 cm1 correspond to the
and SBS and ultimately proper and packed filling of asphalt. In
characteristic absorption peak of C]O and C]C bonds in aromatic
addition, the free radicals of CR and amide groups of MB can
ring (Yao et al., 2011). The two Strong absorption peaks at
enhance the asphalt-rubber interaction and alleviate the phase
1461 cm1 and 1376 cm1 were ascribed to the bending vibration of
separation problem (Hill et al., 2016). The MBCR/SBS-2 asphalt in
this study exhibited better phase separation in terms of softening
point difference than some of the recently reported modified as-
phalts, and hence makes it superior for practical applications (Liu
et al., 2017).

3.2. Textural characterizations

3.2.1. FT-IR analysis

In Fig. 9, the peak at 2964 cm1 is due to the stretching vibration
of C]C bond, while those at 1438 cm1 and 1384 cm1 could be
indexed to the bending vibration of saturated CeH bond (Yin et al.,
2018). The peak at 960 cm1 is due to the out-of-plane bending
vibration of butadiene unit trans-substituted CeH bond, while that
at 802 cm1 is because of the cis-substituted CeH bond out-of-
plane bending vibration of isoprene unit (Narathichat et al.,
2010). The sharp peaks at 2931 cm1 and 1438 cm1 are indexed
to CeH stretching vibration and bending vibration of methylene
(-CH2-) in butadiene, respectively. The peak at 1635 cm1 is due to
the stretching vibration of C]C bond in cis 1,3-butadiene structural
unit (Ratnam et al., 2015). The peak at 883 cm1 is indexed to the
stretching vibration of CeH bond in cis 1,3-butadiene structural

Fig. 10. FT-IR spectra of base asphalt and MB.

Table 3
Softening point of different original asphalts using separation test.

Sample Upper temperature/oC Bottom temperature/oC Difference in temperature/oC

5% SBS 93.5 82.5 11.0

CR/SBS 88.0 73.9 14.1
MBCR/SBS-2 83.1 80.2 2.9
8 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725
saturated CeH, and the one at 1030 cm1 is recognized as S]O
vibration of sulfoxide group (Zhang et al., 2018c). Compared with
the substitution peaks of benzene rings, the peaks near 867 cm1,
810 cm1 and 744 cm1 are indexed to intersubstitution of benzene
rings (Ren et al., 2019). The peak at 722 cm1 is due to eCH2-
bending vibration appearing when the number of C atoms is
greater than or equal to 4 (Zhang et al., 2018b).
Fig. 10 indicates that in MB spectrum, the absorption peaks at
2924 cm1, 2857 cm1, 1700 cm1, 1460 cm1, 1376 cm1,
1030 cm1 and 722 cm1 are similar to those functional groups
mentioned for the base asphalt. The difference is that peak at
1170 cm1 is due to the stretching vibration of CeO bond in the
ester (Ge et al., 2017), and 3290 cm1 and 3160 cm1 are because of
the stretching vibration peaks of NeH bond in the amide group
(Pavia et al., 2014). From these results, it can be concluded that
amide bonds are formed in MB. Furthermore, Fig. 11 shows that
MBCR/SBS-2 asphalt has two more absorption bands at 3353 cm1
and 3187 cm1 as compared to CR/SBS modified asphalt, which are
indexed to the primary amide bond in MB.
3.2.2. 1H-NMR analysis
The abscissa of 1H-NMR spectrum in Fig. 12 represents the
chemical shift (d), and the ordinate represents the intensity of the
absorption peak. The peak at d ¼ 7.26 is awarded to CDCl3 solvent.
MB and base asphalt exhibited similar weak absorption peaks at
d ¼ 2.3, corresponding to eCH2-COO- and eC^CH (Chailleux et al.,
2012). The absorption peaks at d ¼ 1, d ¼ 1.2 and d ¼ 1.6 were
endorsed to CH3-(CH2)n-, -(CH2)n- and eCH2-CH2-COO-, respec-
tively (Zhang et al., 2018c). The difference is that the peaks of MB at
d ¼ 2.8, d ¼ 3.6 and d ¼ 5.3 awarded to ¼ CHeCH2eCH ¼ , -O-CH and
eHC]CH-, respectively, were much stronger (Habibi-Khorassani
et al., 2011). This indicates that methylene, methyl, carbonyl, C]
C, C^C and ether bonds existed in MB, which is consistent with the
FT-IR results. 1H-NMR further concluded that the chemical
composition of both, MB and base asphalt was quite similar, mainly
consisting of open chain saturated alkanes and naphthenes and
hence exhibited good mutual compatibility. In addition, MB
possessed more unsaturated groups than base asphalt.
3.2.3. FM analysis
FM results of morphological analysis of 5% SBS, CR/SBS and
MBCR/SBS-2 modified asphalts are shown in Figs. 13e15
Fig. 11. FT-IR spectra of CR/SBS and MBCR/SBS-2 modified asphalts.
respectively. The light and dark phases in all images represent
SBS/CR and the base asphalt respectively. As can be seen from
Fig. 13, SBS absorbs the light components in the asphalt and ex-
pands, and the light phase appears as a fine network structure. In
Fig. 14, after adding CR, the light spots are evenly filled, and area of
the light phase of CR/SBS increases, while that of the dark phase
decreases. This is attributed to the fact that CR is dispersed in
asphalt in granular form, and the volume is increased after
absorbing the light components, eventually forming a semi-
continuous phase. Fig. 15 shows that the size of the light phase in
MBCR/SBS-2 asphalt is increased compared to that in Fig. 14, which
is because MB increases the light component of asphalt, and the
free radicals of CR interact with the amide groups of MB to establish
a bond between the disulfide and styrene-butadiene polymer
(Baeta et al., 2009), resulting in increased size of the light phase.
3.2.4. TGA
TGA test provides a lot of important numerical information:
initial decomposition temperature (Ti), maximum weight loss rate
temperature (Tmax), and final decomposition temperature (Tf). TGA
test results (including TG and DTG curves) of MB and base asphalt
are shown in Fig. 16.
Fig. 16(a) shows continual decomposition of base asphalt with
increasing temperature. TG and DTG curves infer that Ti, Tf and Tmax
of the base asphalt are 300
C, 675
C and 443
C, respectively.
Among the two reaction zones for base asphalt, the first reaction
interval occurred at about 300e537
C with a weight loss rate of
70%, which is due to the cleavage of alkyl side chains of alkanes and
cycloalkanes (Das et al., 2018). The second reaction interval
occurred around 537e675
C with a weight loss rate of 6.6%, which
was assumed to be caused by thermal decomposition of poly-
condensation molecules of aromatic hydrocarbon polymers
(Higashihara et al., 2009).
TG and DTG curves in Fig. 16(b) infer that Ti, Tf and Tmax of MB
are 190
C, 720
C and 345
C, respectively with three reaction
zones. The first, second and third reaction intervals occurred at
about 190e415
C, 415e580
C and 580e720
C with weight loss
rate of 66%, 27% and 3%, respectively. The three reaction intervals
respectively represent the volatilization of unsaturated compo-
nents such as aldehydes and ethers, the cracking reaction of alkanes
with cycloalkanes, and the thermal decomposition of condensed
ring polymers (Mingming et al., 2012). The characteristic decom-
position temperature of MB (345
C) was though lower than that of
base asphalt, however was much higher than that of experimental
operating temperature (165
C), and hence both remained stable
during preparation process in this study.
4. Mechanism of modification
4.1. Synthesis mechanism of MB
MB has two key reactions in the synthesis process i.e. the for-
mation of amide groups and transesterification. Fig. 17 showing the
amide group formation suggests that under acidic conditions, the
fatty carboxylic ester contained in MB, undergoes substitution re-
action with the free ammonia methanol, so that the carboxyl group
in the aliphatic carboxylic ester forms an amide bond. The resulting
amide bond is a key factor in reducing the viscosity of CR/SBS
modified asphalt by MB (Fini, 2016). Fig. 18 shows the process of
acid catalyzed transesterification, where the protons first combine
with the carbonyl group of the triglyceride to form a carbocation
intermediate. The protonated methanol combines with the carbo-
cation and forms an intermediate having tetrahedral geometry,
which is then broken down into methyl and diglycerides, producing
protons which catalyze another reaction (step 1).
 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725 9

Fig. 12. 1H-NMR of MB and base asphalt.

Fig. 13. FM images of 5% SBS modified asphalt (a)  200 and (b)  400.

Fig. 14. FM images of CR/SBS modified asphalt (a)  200 and (b)  400.
10 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725

Fig. 15. FM images of MBCR/SBS-2 asphalt (a)  200 and (b)  400.

4.2. Modification mechanism of MB

The mechanism of MB modification is shown in Fig. 19.

The addition of MB to CR/SBS modified asphalt plays three roles:
(1) When a small amount of MB is added, the light components of
the system increase and MB produces a lubricating effect with CR
and SBS, so viscosity of asphalt decreases (Xu et al., 2017). (2) At an
appropriate amount of MB, CR and SBS fully absorb the light
components and swell to a saturated state, which results in proper
filling of the asphalt by CR. In addition, the free radical of CR in-
teracts with the amide group in MB to establish bonds between the
disulfide and styrene butadiene polymer, thus forming a semi-
continuous phase that enhances the development of SBS network
structure (Baeta et al., 2009). (3) When the amount of MB exceeds
certain level, CR and SBS reach supersaturation, and excess MB
causes rupturing of CR and hence MB acts as a diluent (Fini, 2016).
Therefore, MB content should be designed in such a way so as to
maximize the saturation of CR and SBS absorption while avoiding
dilution. In this study, 2% MB was the optimum amount with ideal
effect on CR and SBS in the MBCR/SBS asphalt.

5. Conclusions

In this study, the effect of MB as a modifier to prepare MBCR/SBS

modified asphalt was analyzed. The resulting modified asphalt was
tested for various performance tests and microscopic analysis and
optimum dosage of MB was determined. MBCR/SBS-2 modified
asphalt exhibited the best performance among all the samples
tested. The following generalized conclusions can be inferred from
this study.

(1) The viscosity of MBCR/SBS-2 asphalt was less than 3 Pa s at

135
C, which meets the requirements of Superpave specifi-
cations, while no phase separation was observed during
separation test.
(2) MBCR/SBS-2 asphalt realized the largest G* value in the high
frequency range and a much higher average recovery rate
than 5% SBS modified asphalt. In addition, MBCR/SBS modi-
fied asphalt realized good resistance to fatigue cracking at
intermediate temperature.
(3) The amide group formed in MB can interact with the free
radical of CR to form bonds between the disulfide and the
styrene butadiene polymer, which increase the diameter of
CR in asphalt, thereby enhancing the development of SBS
Fig. 16. TG and DTG curves (a) base asphalt (b) MB. network structure.
 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725 11

Fig. 17. Mechanism of formation of amide group in MB.

Fig. 18. Mechanism of transesterification catalyzed by sulfuric acid.

Fig. 19. Schematic representation of the mechanism of MB modified CR/SBS asphalt.

(4) 1H-NMR results showed the greatly similar composition of
MB and base asphalt which favored their mutual compati-
bility. FT-IR spectroscopy confirmed the formation of amide
bonds in MB.
(5) The characteristic decomposition temperature of MB was
higher than experimental temperature applied during the
study.
Awarded to the environmental greenness of MB, significant
enhancement in mechanical properties and comprehensive per-
formance upon compositing with CR and SBS, MBCR/SBS-2 modi-
fied asphalt could be of great interest for highway and bridge
constructions.
12 S. Duan et al. / Journal of Cleaner Production 237 (2019) 117725
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grant No. 51768007), Guangxi Natural Science
Foundation Fund, China (Grant No. 2018JJA160105).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.117725.
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