Science of the Total Environment 695 (2019) 133943

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Science of the Total Environment

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

Flow-induced crystallization of biochar in bio-asphalt under various

aging conditions
Xinxing Zhou a,b,c,⁎, Sanjeev Adhikari d
a
State Key Laboratory of Silicate Building Materials, Wuhan University of Technology, Wuhan 430070, China
b
Centre for Pavement and Transportation Technology, University of Waterloo, Ontario N2L 3G1, Canada
c
Key Laboratory of Highway Construction and Maintenance Technology in Loess Region, Shanxi Transportation Technology Research & Development Co., Ltd, Taiyuan 030032, China
d
Kennesaw State University, 1100 South Marietta Park, Marietta, GA 30060, USA

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Bio-char and bio-oil are main

pyrolysised products of waste wood.
• Eco-friendly bio-asphalt system: bio-
char and bio-oil rejuvenated aging
asphalt was built.
• A new perspective: flow-induced crys-
tallization of biochar in bio-asphalt was
provided.

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

Article history: Flow-induced crystallization (FIC) in polymers is an important problem that occurs on a very rapid time scale.
Received 4 July 2019 This study aims to evaluate the flow-induced crystallization of bio-asphalt modified with different contents of
Received in revised form 13 August 2019 biochar under various aging conditions. Small angle X-ray scattering and molecular dynamic simulations were
Accepted 14 August 2019
performed to impose extensional deformation and the nucleation process. The rheological properties were mea-
Available online 15 August 2019
sured using the dynamic shear rheometer (DSR) and the morphology of biochar modified bio-asphalt (BMBA)
Editor: Daniel CW Tsang was measured using an optical microscope. The relative scattering intensity during crystallization appeared to
peak at four strain rates: 13.2 s−1, 19.6 s−1, 25.4 s−1, and 27.3 s−1. The results showed that the addition of biochar
Keywords: could improve the flow-induced crystallization and enhance the high-temperature properties of bio-asphalt.
Flow-induced crystallization Moreover, crystallization status of BMBA is lamellar crystals. Ultraviolet and pressure aging vessel aging could re-
Biochar markably affect the crystallization status of BMBA and promote the formation of crystals.
Bio-asphalt © 2019 Elsevier B.V. All rights reserved.
Rheological properties
Molecular dynamic simulation

1. Introduction

Understanding the flow-induced crystallization of polymers is im-

⁎ Corresponding author at: Room 218, 27 Wuluo Street, Xiaodian District, Taiyuan,
portant to both fundamental polymer science and polymer processing
China. (Liu et al., 2011). Within this topic semicrystalline polymer is a very im-
E-mail address: zxx09432338@whut.edu.cn (X. Zhou). portant subset of polymers. Unlike simple crystalline and amorphous

https://doi.org/10.1016/j.scitotenv.2019.133943
0048-9697/© 2019 Elsevier B.V. All rights reserved.
2 X. Zhou, S. Adhikari / Science of the Total Environment 695 (2019) 133943
polymer, the semicrystalline polymer has a composite structure of both
crystalline and amorphous regions. The morphology of the crystalline
structures strongly influences all properties of the polymer. Moreover,
flow-induction significantly enhances the rate of polymer crystalliza-
tion. The flow breaks down kinetic barriers to crystallization and directs
the resulting morphology by distorting the polymer chains. Flow-
induced crystallization (FIC) in polymers is an externally-driven, non-
equilibrium phase transition which is controlled by kinetics. The crystal-
lization of wax on the surface of asphalt has been investigated (Pizzorno
et al., 2014), however, there is no report on the FIC rheological proper-
ties of asphalt itself.
The consumption of asphalt cement (AC) in road construction and
maintenance practices has led to increases in both the cost and price
of petroleum asphalt (Chen and Wang, 2018). The high demands for
AC have encouraged the development of alternative binders to modify
or even replace ordinary AC. Recently, significant developments have
been made toward converting renewable resources into bio-oil and
great efforts have been made toward building an eco-friendly bio-
asphalt system (Guarin et al., 2016; Zeng et al., 2018). Bio-oil is a dark
organic liquid, which consists of various highly oxygenated compounds
(Zhang et al., 2013). It can be produced from various raw materials, such
as swine manure, corn straw, waste wood, and sawdust ash (Ott et al.,
2008; Pittman et al., 2012; Wang et al., 2016; Yang et al., 2014; Salehi
et al., 2013). In China, waste wood, which can cause serious social and
environmental problems, has been converted into biochar, bio-oil, and
gas (Kim et al., 2014). Wang et al. (2017) investigated the transforming
wood waste into water-resistant magnesia-phosphate cement and took
full use of the wood waste products.
Bio-oil could be used to rejuvenate the aging asphalt and it is an ef-
fective way to reduce consumption of asphalt by softening asphalt
binders and contributing to the improvement of their low-
temperature performance (Chen et al., 2014). Fini et al. (2012) investi-
gated the poly-phosphoric acid modified pig manure based bio-asphalt.
The pavement properties and durability of styrene-butadiene styrene
(SBS) modified bio-asphalt were also studied (Yang et al., 2014;
Williams et al., 2011) and it was indicated that the rejuvenation effects
are different depending on the kinds of raw materials. Overall, there
have been limited studies on restoring rejuvenators effect on reclaimed
aged asphalt by using a bio-oil derived from waste wood, which benefits
the environment-friendly and sustainable development. The one main
component of pyrolysis products of waste wood is biochar that its
main component is carbon that could shield the ultraviolet light of the
asphalt surface, prevent asphalt from photo-oxidation aging, and im-
prove the high-temperature stability of asphalt. Tsang and his team
made outstanding achievements about waste-wood based environment
materials (Wang et al., 2018; O'Connor et al., 2018; Tsang et al., 2007).
This study is aimed to take full advantage of the pyrolysis products of
waste wood: bio-oil and biochar. There are many research achieve-
ments of waste-wood-based bio-asphalt. Metwally (2010) prepared as-
phalt modified bio-oil derived from red oaks, willow, and corn stalk. 10%
and 15% rubber particles were added into the bio-oil derived from red
oaks (Peralta et al., 2012). Ran Zhang et al. (2017) investigated the
high-temperature performance of SBS modified bio-asphalt. Gao et al.
(2018b) studied the high-temperature performance of wood chips
based bio-asphalt binder. Lei Zhang et al. (2015) investigated the effect
of woody plant liquid of low-temperature performance of asphalt. Gao
et al. (2018a) investigated the properties of bio-asphalt based on the
time-temperature superposition principle. Research found that the
compatibility between petroleum asphalt and bio-oil would decrease
with an increase in the fraction of bio-oil (Yang et al., 2017). Lei et al.
(2018) studied the effect of bio-oil derived from corn stover waste on
the high-temperature performance of rubber modified asphalt. Yang
and You (2015) investigated the high-temperature performance of
waste-wood-based bio-asphalt. Yang et al. (2014) investigated the me-
chanical performance of asphalt mixtures modified by bio-oil derived
from waste wood. Han et al. (2017) studied waste wood pellet-based
bio-asphalt. Wang et al. (2019) investigated the biochar as green ad-
mixture for construction products. Xiong et al. (2017) came up with a
review of biochar based catalysts for chemical synthesis, biofuel produc-
tion, and pollution control. Considering the amount of research into bio-
char, there is little research about flow-induced crystallization of
biochar modified bio-asphalt under various aging conditions.
In this study, in order to understand the FIC, rheological properties,
structure and morphology of biochar modified bio-asphalt (BMBA),
the X-ray scattering, dynamic shear rheometer (DSR), molecular dy-
namic simulation, Fourier transform infrared spectroscopy and optical
microscope were used. The relationships between structure and mor-
phology were utilized to analyze the FIC mechanism of biochar modified
bio-asphalt.
2. Materials and experiments
2.1. Materials
The raw material size of waste-wood is smaller than 75 μm. Bio-oil
and biochar were derived from waste wood and the pyrolysis tempera-
ture is 500 °C with N2. The preparation process included the waste
wood, wood chips, pyrolysis equipment and bio-oil. The pyrolysis
speed of raw materials in the splitting furnace is 2.0 g/s during the py-
rolysis process.
The base asphalt used in this study was a performance graded as-
phalt PG58–28. The bio-asphalt was prepared by adding 10% bio-oil
into base asphalt. The mixing of bio-oil and asphalt was achieved
using a high-speed shear mixer at the speed of 2000 rpm for 30 min
at 120 °C. Then, the biochar was added into the liquid bio-asphalt and
the BMBA was achieved using a high-speed shear mixer at the speed
of 2000 rpm for 1 h at 135 °C. Biochar dosages of 0%, 2%, 4%, 6%, and
8% were used together with rolling thin film oven (RTFO, short-term
aging) aging bio-asphalt and it was marked by S1, S2, S3, S4 and S5, re-
spectively. BMBA aging was carried out through the rolling thin film
oven (RTFO, short-term aging), ultraviolet (UV) aging and pressure
aging vessel (PAV, long-term aging) procedures. The short-term aging
and long-term aging were performed in accordance with AASHTO
T240 and AASHTO R28, respectively. The long-term aging is assumed
to simulate 10 years of aging and it is marked by S7. UV aging is in accor-
dance with the UV radiation conditions of Taiyuan city using UV aging
tester under 65w/m2 at 60 °C for 7 days and it is marked by S6. The mix-
ture combinations of the seven different asphalt binders within this
study are summarized in Fig. 1.
PAV asphalt
UV asphalt
100 RTFO asphalt
bio-oil
biochar
80
60
Mass ratio(%)
40
20
0
S1 S2 S3 S4 S5 S6 S7
Specimen number
Fig. 1. The fundamental composition of BMBA.
 X. Zhou, S. Adhikari / Science of the Total Environment 695 (2019) 133943 3

2.2. Experiments
2.2.1. X-ray scattering experiments
In order to meet the measurement requirements for X-ray scatter-
ing, a thin-plate polymer sample with a cross-section dimension of
width 20 mm and thickness 1 mm was used.
2.2.2. DSR experiments
Master curves and creep curves of BMBA were measured using the
DSR. Creep tests were performed to measure the rheological properties
using 8 mm parallel plates at −5 °C.
2.2.3. Molecular dynamic simulation
The general asphalt molecular model is expressed as four compo-
nents: resins, aromatics, asphaltenes, and saturates (Sun and Zhou,
2018; Zhou et al., 2019). According to the results of previous experi-
ments, a three-component model of bio-oil was used, the biochar is rep-
resented by carbon, and the composition of each component was based
on the test results (Yang et al., 2018). The molecular model of BMBA was
built according to the actual composition. Firstly, geometry optimiza-
tion was used to induce the system energy then, isobaric-isothermal en-
semble (NPT) was used to get state equilibrium. Finally, Canonical
ensemble (NVT) was used to calculate the dynamic parameters. The
step size of the simulation is 1 fs and the total time step is 100 ps. The
crystal structure and crystallization kinetics were obtained by using a
molecular dynamics simulation with the stress or strain control mode.
The main components of bio-oil extracted from waste wood are ace-
tic acid, 1-carboxy-2-propanone and methanol (Zhang, 2004). The fun-
damental components of each of the mixtures used in molecular
dynamic simulation are shown in Fig. 2. The components of bio-oil are
found in mixtures S1–S7. The mass fraction of bio-oil in these mixtures
is 10%.
Fig. 3 shows the asphalt molecular model and BMBA (S5, 8% biochar
modified 10% bio-oil based asphalt) molecular model built according to
all components compositions (Fig. 2). The mass ratio could be reversed
the molecular numbers. Bio-oil and biochar molecules within the BMBA
are denoted with color.
2.2.4. Fourier transform infrared spectroscopy experiments
Fourier transform infrared spectroscopy (FT-IR) (Nicolet IS5, USA)
was used to obtain the infrared spectroscopy of BMBA. The wave-
number ranged from 400 cm−1 to 4000 cm−1. Aromatic, aliphatic and
branched aliphatic indexes were measured by the peak areas.
2.2.5. Microscope experiments
An optical microscope was employed to investigate the morphology
of BMBA. A pressing method was used to prepare the sample: a small
amount of binder was dropped on a glass substrate; by warming the
bottom of the substrate on a heating plate, the binder can spread to
form a thin film; then, this film was covered by a glass slide for the mor-
phology observation.
3. Results and discussions
3.1. The effects of biochar on FIC
Fig. 4(a) shows the transient extensional viscosity of BMBA (S5)
melts under from different strain rates and linear viscoelastic behavior
(LVE) obtained from small amplitude shear strain. The viscosity of
BMBA (S5) increased with increases in the test-time. Moreover, the vis-
cosity curves were observed to be close to linear in shape. So, the flow
direction of a semicrystalline polymer is transverse. It indicates that
the test-time of shear strain could affect the FIC and rheological proper-
ties of BMBA. Shear strain would induce the polymer crystallization to
flow the designated direction. Furthermore, the FIC has directivity and
the initial nucleation does not require large deformations. The content
of biochar could also affect the FIC, when the content of biochar is
high especially. As shown in Fig. 4(b), tests were measured at four dif-
ferent shear strain rates (13.2 s−1, 19.6 s−1, 25.4 s−1, 27.3 s−1), the X-
ray scattering characteristic peaks of BMBA (S5) became sharply and
narrower with the increased shear strain, which indicated that the
BMBA system exhibited the flow-induced crystallization (FIC). More-
over, the grain size became smaller with the increased shear strain.
The low shear strain rates couldn't promote the polymer completed
crystallization, while the increased shear strain rates could accelerate
the flow-induced crystallization of polymers. Research found that
shear strain may also change the shapes of polymer crystallization.
Fig. 5 shows the X-ray scattering curves for selecting mixtures (S1,
S2 and S5). The characteristic peaks at 0.2 nm−1 were observed for
the X-ray scattering curves of biochar and appeared obviously with
the increased content of biochar in the BMBA (S1(0% biochar), S2(2%
biochar) and S5(8% biochar)). There were no sharp peaks observed for

100%
9.43 26.90 21.65 16.48 5.50 2.30 1.20
90% 8.00

9.76 27.96 22.80

80%
16.65
5.50 2.30 1.20
70% 11.15 28.86
24.60 8.00
17.38
60% 5.50 2.30 1.20
29.57
Mass ratio

11.42
25.20
50%
17.81
30.27 8.00
11.70 5.50 2.30 1.20
40% 25.80

30% 30.98 18.23

11.97 5.50 2.30 1.20 6.00
26.40
20%
18.66
52.70 4.00
10% 14.20 27.90 5.50 2.30 1.20
5.20 2.00
0%
1 2 3 4 5 6 7 8

saturate aromatic resin asphaltene acetic acid 1-carboxy-2-propanone methanol

Fig. 2. The fundamental components of BMBA used in molecular dynamic simulation.

4 X. Zhou, S. Adhikari / Science of the Total Environment 695 (2019) 133943

Fig. 3. Molecular model: (a) asphalt molecular model and (b) BMBA molecular model.

the bio-asphalt (S1) instead the characteristic peaks of bio-asphalt (S1)
are more gradual and flat-topped. This indicates that bio-asphalt could
be classified as non-crystal polymer, while the BMBA was semicrystal-
line polymer. Furthermore, biochar could improve the flow-induced
crystallization ability of BMBA. The characteristic peaks of BMBA (S2
and S5) were higher than that of bio-asphalt (S1) and the biochar
content could affect the crystal structure of BMBA. The reason is that
biochar itself is crystal and its internal has many pores structure,
which can adsorb the polymer and create the FIC.
Fig. 6(a) displays the X-ray scattering intensity curves of BMBA (S5)
during crystallization at 135 °C with different scattering time. The thick-
ness of BMBA (S5) after the extension was ensured to be 0.50–0.60 mm.
The intensity curves of X-ray scattering indicate that no signal of lamel-
lar crystals appearing after extensional loading. It takes about 180 s for
the peak of lamellar crystals to be visible, whose intensity further in-
creases with time and finally reaches a plateau. It demonstrates that
the critical time point is 180 s that is the time of FIC appeared. The ex-
tensional loading could accelerate the creation of FIC. The FIC appears
the 0.2 nm−1. It indicates that the FIC occurs in the surface layer of
BMBA and the crystalline domains are small. Fig. 6(b) gives crystalliza-
tion kinetic data quantitatively. As for the induction time, it can be con-
cluded that the high strain rate accelerates the crystallization. The
relative intensity of BMBA increased with the increase of the induction
time and shear strain rates, which indicated that the induction time
and shear strain rates would affect the structure of the polymer and
FIC. The relative intensity of BMBA changed obvious in the initial induc-
tion time, while the relative intensity of BMBA changed slightly in the
final induction time. It shows that the change of the relative intensity
has the time selectivity. So, the FIC of BMBA has also the time selectivity.
Owing to their sensitivity to both temperature and frequency, mas-
ter curve sweeps have become very useful for asphalt characterization.
As shown in Fig. 7, the complex modulus and phase angle of bio-asphalt
(S1) and BMBA (S5) show that the complex modulus of BMBA (S5) is

260
asphalt
240
bio-asphalt(S1)
220 2% BMBA(S2)
200 8% BMBA(S5)
180
Intensity(arb.unit)

160
140
120
100
80
60
40
20
0
0.0 0.2 0.4 0.6 0.8 1.0
-1
q(nm )
Fig. 4. Extensional viscosity and scattering characteristic peaks curves of BMBA (S5) with
different strain rate: (a) extensional viscosity curves, (b) scattering characteristic peaks
curves. Fig. 5. X-ray scattering curves of asphalt systems.
 X. Zhou, S. Adhikari / Science of the Total Environment 695 (2019) 133943 5

a 0s much higher than that of bio-asphalt (S1), while the phase angle of
60 s
250 BMBA (S5) is much lower than that of bio-asphalt (S1). Moreover, the
120 s
180 s complex modulus decreased with the frequency. This indicates that
240 s BMBA is more elastic and stiffer than bio-asphalt. Therefore, biochar
200 300 s could improve the high-temperature stability and enhance the FIC. It
360 s
shows that FIC may also have the sensitivity to both temperature and
Intensity(arb.unit)

420 s
150 frequency.
420 s
As shown in Fig. 8, the complex modulus of BMBA (S2 an S5) are
more than that of bio-asphalt (S1) and the complex modulus of BMBA
100
(S2 and S5) increased with the content of biochar. The higher levels of
strain maintained under creep condition are due to the polymer of FIC.
50 Moreover, this effect increased with the increased content of biochar.
That is to say. The biochar could induce the formation of crystal and im-
prove the ability of FIC to bio-asphalt (S1). The addition of biochar could
0 0s
0.0 0.2 0.4 0.6 0.8 1.0 reduce the creep time of BMBA (S2 and S5). It indicates that the biochar
-1
q(nm ) improve the complex modulus of bio-asphalt, while decrease the ability
of elastic recovery. The biochar could change the structure of bio-
b asphalt and lead to the FIC and low creep time.
1.4
-1 Fig. 9(a) shows the microstructure of the various mixtures (S1, S2,
13.2 s
1.2 -1
S3, S4 and S5). BMBA was found to have aggregate regions which may
19.6 s be the crystallization of the polymer. The aggregate regions became big-
-1
25.4 s ger with increasing content of biochar. The flat black regions within the
1.0 27.3 s
-1
images are bio-asphalt. The results shows that the higher biochar con-
tent could improve the crystallization ability for polymer and make
relative intensity

0.8 bio-asphalt undergo the FIC phenomenon. This phenomenon shows

that bio-oil could agglomerate or aggregate easily in asphalt, while the
0.6 biochar could appear a uniform distribution of points or fill into the net-
work of asphalt and bio-oil in BMBA.
0.4
3.2. The effects of aging conditions on FIC
0.2
Fig. 9(b) shows the morphology of the different BMBA (S5, S6 and
S7) under aging conditions. The microscope shows that the aggregate
0.0
0 200 400 600 800 1000 regions of BMBA become darker and larger with aging, which indicates
that aging could affect the rate of crystallization and create FIC. Aggre-
time (s)
gate regions of BMBA after UV aging (S6) are darker than those after
PAV aging (S7), while these regions are the lightest in un-aged BMBA.
Fig. 6. X-ray scattering curves: (a) the intensity curves of X-ray scattering during flow-
The FIC effects in decreasing order are UV aging (S6), PAV aging (S7),
induced crystallization at 135 °C and (b) the relative intensity evolution of X-ray
scattering at different strain rates. and RTFO aging BMBA (S5), respectively. The results show that aging
could affect highly the crystallization morphology of BMBA. The UV
aging affect mainly the morphology or structure of bio-asphalt in

80
1.00E+010 bio-asphalt(S1)
BMBA(S5) 70
9.00E+009
60

8.00E+009
Complex modulus(Pa)

50
Phase angle( )
o

7.00E+009
40

6.00E+009
30

5.00E+009 20

4.00E+009 10

3.00E+009 0
0 20000 40000 60000 80000 100000
Frequency(Hz)

Fig. 7. Master curves of asphalt system.

6 X. Zhou, S. Adhikari / Science of the Total Environment 695 (2019) 133943
Fig. 8. The creep curves of bio-asphalt and BMBA (S1, S2, and S5).
BMBA, while the PAV aging affect the morphology of bio-oil and biochar
in BMBA. The results show that biochar could shield the ultraviolet light
of the asphalt surface and prevent asphalt from photo-oxidation aging.
Fig. 9. The morphology of asphalt: (a) asphalt, (b) bio-asphalt (S1), (c) 2% BMBA (S2), (d) 4% BMBA (S3), (e) 6% BMBA (S4), (f) 8% BMBA (S5), (g) short-term aging BMBA (S5), (h) UV
aging BMBA (S6), and (i) PAV aging BMBA (S7).
FT-IR data are shown in Fig. 10. Peaks at 2880 cm−1 and 1452 cm−1
is due to the stretching vibration peaks of -CH3, while the peaks at
2731 cm−1 and 1302 cm−1 are caused by the bending vibration peaks
of -CH2-. The 1711 cm−1 peak is due to C_O bonds, which come from
the aging process of BMBA. The 1572 cm−1 peak is due to the vibration
peak of -COOH that comes from the oxygen functional groups of bio-
char. The 500 cm−1-1200 cm−1 range belongs to the crystallization of
the polymer. The aging degree is different from the characteristic peak
of the C_O and crystallization of the polymer. Moreover, the peak
height of PAV aging BMBA (S7) is higher than that of UV aging BMBA
(S6), and the peak height of UV aging BMBA (S6) is higher than that
of RTFO aging BMBA (S5) and RTFO aging bio-asphalt (S1). It indicates
that aging could increase the content of C_O and decrease the content
of -CH3. Aging will make the characteristic peak of crystallization of the
polymer increase, which shows that the aging could make the polymer
create the FIC. The FIC effects of UV aging are more severe than that of
PAV aging.
3.3. The effects of shear stress on FIC
As shown in Fig. 11, in general, the strain of BMBA (S5) increased
with the loading shear stress and time during the initial step of creep,
while the strain of BMBA (25 Pa) is higher that the strain of BMBA
(30 Pa). Furthermore, the strain of BMBA (S5) is higher than that of

4
biochar modifieed PAV aging bio-asphalt(S7)
biochar modified UV aging bio-asphalt(S6)
biochar modified RTFO aging bio-asphalt(S5)
3 RTFO aging bio-asphalt(S1)
Absorbance(arb.unit)
2
0
500 1000 1500 2000 2500
Wavenumber(cm )
Fig. 10. FT-IR of BMBA.
bio-asphalt (S1). It shows that shear stress could improve the strain and
the FIC of BMBA. The strain change of BMBA is slight with the increase of
shear stress. While the strain change of BMBA is sharply with the in-
crease of shear time in the initial shear time. The strain decreased
sharply when the shear time is 100 s. The decreased degree of strain
changed obviously with the increase of shear stress. It showed that
the shear stress and shear time could affect the strain and FIC of BMBA.
Fig. 12 shows the difference of the FT-IR spectrum under different
shear stress levels for BMBA (S5) appeared at 500 cm−1-1200 cm−1. Re-
search found that the 500 cm−1–1200 cm−1 range belongs to the crys-
tallization of the polymer. The characteristic peaks at 1370 cm−1-
1450 cm−1 changed obviously with the increase of biochar and shear
stress. So, it indicated that biochar could change the functional group
and FIC of BMBA. Moreover, the shear stress would also change the
functional group and FIC of BMBA. The characteristic peak areas of crys-
tal decreased with increases of the shear stress. It indicated that the
crystallinity of the polymer decreased with the increasing of the shear
stress. Moreover, the shear stress could weaken the FIC of BMBA.
As shown in Fig. 13, the microscope showed that the aggregate re-
gions of BMBA (S5) changed remarkably and became smaller with the
increasing of shear stress, which indicated that shear could affect the
rate of crystallization and weaken the FIC. The results showed that
shear stress could affect the crystallization morphology of BMBA. The
0.6
0.5
0.4
strain
0.3
0.2
0.1
0.0
0 100 200
Time (s)
Fig. 11. Creep curves of BMBA (S5) at different stress.
X. Zhou, S. Adhikari / Science of the Total Environment 695 (2019) 133943 7
30 Pa BMBA(S5)
25 Pa BMBA(S5)
20 Pa BMBA(S5)
bio-asphalt(S1)
Intensity(arb.unit)
1000 2000 3000 4000
3000 3500 4000
-1
-1 Wavenumber(cm )
Fig. 12. FT-IR of BMBA at different stress.
morphology of BMBA is different with the change of shear stress. The
main reason is that the morphology of BMBA has the shear stress selec-
tivity. The shear stress would improve the morphology of FIC to some
extent.
3.4. The effects of simulation condition on FIC
Fig. 14 shows the characteristic peaks of bio-asphalt (S1), including
the four peaks of 1.0 Å, 1.5 Å, 1.7 Å, and 2.2 Å. The first characteristic
peak of the radical distribution function for biochar appeared at 4.0 Å–
5.4 Å. Research found that 1.0 Å peak represents spherocrystal, the 4.1
Å peak represents filamentous crystals, and the 11.2 Å peak represents
lamellar crystals, the radical distribution function without peaks repre-
sent amorphous. Furthermore, the first characteristic peak of BMBA in-
creased with the increasing content of biochar. It showed that the main
crystal orientation of 0%, 2%, 4%, 6%, and 8% biochar modified bio-asphalt
(S1, S2, S3, S4, and S5) is amorphous, spherocrystal, and part lamellar
crystals, respectively. The results showed that the filamentous crystals
are more likely to appear with the addition of biochar. The reason for
the formation of filamentous crystals is the tropism action along the
shear direction. Moreover, the results showed that biochar could in-
crease the amount of filamentous crystals.
The initial crystallization time of biochar modified bio-asphalt (S5) is
35 ps, 31 ps, 28 ps, 25 ps, 23 ps, respectively, when the shear stress is
20 Pa, 25 Pa, 30 Pa, 35 Pa, and 40 Pa. The initial crystallization time de-
creased with the increased shear stress. In addition, the direction of
20 Pa crystallization and the initial crystallization time is affected by shear
25 Pa stress. The higher that the shear rate is, the more tropism there is. The
30 Pa orientation energy could indicate the energy difference of all orientation
stress and evaluate the change of FIC. Research found that the biggest orienta-
tion energy of FIC was the main driving force of FIC. The orientation en-
ergy of biochar modified bio-asphalt is shown in Table 1. The potential
energy is the biggest energy during potential energy, kinetic energy,
and non-bond energy. So, we analyze mainly the potential energy. At
temperatures of 273 K, 298 K, 333 K, 353 K, and 408 K, the potential en-
ergy is 7362.0 kJ/mol, 9625.0 kJ/mol, 10,317.2 kJ/mol, 12,225.0 kJ/mol,
and 15,025.5 kJ/mol, respectively. The potential energy increased with
the increase of temperature. It shows that temperature can improve
the potential energy or orientation energy. We can conclude that the
orientation energy of BMBA is the biggest acting force and it is the
main driving force of FIC. Moreover, Angle energy is the main energy
300 400 500 in valence energy (diag.terms), and stretch-torsion energy is the main
energy in the valence energy (cross.terms), which show that the main
driving force is angle and stretch-torsion energy in valence energy.
Zhou et al. (2019) thought that the valence energy (diag. terms) is the
8 X. Zhou, S. Adhikari / Science of the Total Environment 695 (2019) 133943

Fig. 13. Morphology of BMBA (S5) at different shear stress: (a) 20 Pa shear stress, (b) 25 Pa shear stress, (c) 30 Pa shear stress.

major factor involved in the potential energy. We could get the same
conclusion. In this study, the valence energy (diag.terms) is bigger
than valence energy (cross.terms), and the valence energy is a part of
potential energy.
4. Conclusions
Flow-induced crystallization of biochar in bio-asphalt was measured
by X-ray scattering, FT-IR, DSR, optical microscopy and molecular dy-
namic simulation.
Biochar could improve the flow-induced crystallization ability of
bio-asphalt. Moreover, the biochar content could affect the crystal struc-
ture of bio-asphalt. Biochar could improve the high-temperature
stability and enhance the FIC. Aging could highly affect the crystalliza-
tion morphology of BMBA. Moreover, FIC effects of UV aging are more
severe than that of PAV aging.
BMBA exhibited the flow-induced crystallization, and the morphol-
ogy of the crystallization changed with increased shear stress. Shear
stress could improve the complex modulus of bio-asphalt. Furthermore,
the crystallinity of the polymer decreased with increases in the shear
stress.
The filamentous crystals appeared at the addition of biochar and the
reason for the formation of filamentous crystals is the tropism action
along the shear direction. Moreover, the BMBA could be forming fila-
mentous crystals with the increase of biochar.
Acknowledgments

This work was supported by the National Natural Science Founda-

40 tion of China (grant number 51808329), the Special Project of Commer-
8% BMBA(S5)
cialization of Shanxi Province Research Foundation (grant number
6% BMBA(S4)
4% BMBA(S3)
201804D131034), Science and Technology Project of Shanxi Transpor-
2% BMBA(S2) tation Holdings Group Co., LTD (grant number 18-JKKJ-13), Open Foun-
30
bio-asphalt(S1) dation of Key Laboratory of Transport Industry of Road Structure and
Material, Research Institute of Highway, Ministry of Transport (grant
number KF201906), and Science and Technology Department of Shanxi
20 Province International Cooperation (grant number 201603D421027).
g(r)

Declaration of competing interest

10 The authors declare no conflict of interest.

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