Construction and Building Materials 293 (2021) 123480

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Construction and Building Materials

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

Dynamic chemistry based self-healing of asphalt modified by diselenide-

crosslinked polyurethane elastomer
Lei Lyu a, Dong Li a, Yuxian Chen b, Yefei Tian a,c,⇑, Jianzhong Pei a,⇑
a
School of Highway, Chang’an University, Xi’an, Shaanxi 710064, China
b
School of Management, Xi’an Polytechnic University, Xi’an, Shaanxi 710048, China
c
School of Materials Science and Engineering, Chang’an University, Xi’an, Shaanxi 7100614, China

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

Dynamic covalent chemistry is

inventively used to enhance self-
healing property of asphalt.

The self-healing of polyurethane
elastomer at ambient temperature
without light is achieved.

Covalent bond reorganization has
great efficacy in resisting cracks in
asphalt pavement.

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

Article history: Asphalt with self-healing property prevents the formation and propagation of cracks in asphalt pave-
Received 6 December 2020 ments, while rejuvenation encapsulation and induction heating suffer from unsustainable nature and
Received in revised form 19 April 2021 energy consumption. Herein, dynamic covalent chemistry was used to endow asphalt binder with self-
Accepted 24 April 2021
healing property via modifying the asphalt with diselenide-crosslinked polyurethane elastomer.
Available online 8 May 2021
Fourier-transform infrared spectrometer and thermal-gravimetry results indicate that diselenide-bonds
were stably introduced into the asphalt binder. The results from healing tests illustrated that diselenide
Keywords:
bonds enhance the self-healing capability of polyurethane elastomer and asphalt binder, especially at the
Self-healing
Asphalt binder
early stage after a fracture. This study opens up novel perspectives for preparing asphalt with self-healing
Dynamic covalent bond property attributed to dynamic covalent chemistry.
Polyurethane elastomer Ó 2021 Published by Elsevier Ltd.

1. Introduction
Asphalt binder acting as adhesive bonding aggregates in asphalt
pavement is exposed to the continuous traffic loads and environ-
mental changes during service, resulting in the potential formation
of cracks [1]. The consequence of the accumulated cracks is serious
damage to the mechanical properties and a significant decrease in
⇑ Corresponding authors at: School of Highway, Chang’an University, Xi’an,
Shaanxi 710064, China.
E-mail addresses: yftian@chd.edu.cn (Y. Tian), peijianzhong@126.com (J. Pei).
the service life of asphalt pavement [2]. Fortunately, asphalt pave-
ments were found to have the capability for repairing its microc-
rack damages and restoring its functionality to some extent [3].
The healing potential of asphalt mixtures comes from the vis-
coelastic component asphalt binder, achieving by its diffusion at
the fracture surfaces [4]. As a viscoelastic material, asphalt binder
tends to flow into the weakened area spontaneously and even fill
some micro-cracks, referred to as the self-healing behavior [5].
It’s also proven that the self-healing capability largely depends
on the chemical composition and mechanical properties of asphalt
binders [6]. Nevertheless, the limited self-healing properties of

https://doi.org/10.1016/j.conbuildmat.2021.123480
0950-0618/Ó 2021 Published by Elsevier Ltd.
L. Lyu, D. Li, Y. Chen et al.
asphalt binders contribute little to resist the generation and prop-
agation of cracks in asphalt pavement [7]. Self-healing asphalt aims
to produce a sustainable asphalt pavement using self-healing tech-
nology to facilitate and improve the healing capability of asphalt
binder [8,9]. Rejuvenation encapsulation and induction heating
are the two main pathways to accelerate the self-healing efficiency
of asphalt binder by adding rejuvenator and heating, respectively,
which are limited by their unsustainable nature and energy con-
sumption in practical use [10–12]. There is still a research niche
on motivating the intrinsic self-healing capability of asphalt
binder.
Nowadays, polymer modifiers have been widely used to
improve the physicochemical properties of asphalt binders, includ-
ing elastomers, plastomers, and polymeric materials with reactive
groups [13–15]. Polyurethane, which features dual advantages of
rubber and plastic that originate from its soft and hard segment
phases, can lead to higher consistency, strength, low-temperature
toughness, and permanent deformation resistance of asphalt bin-
der when used as a polymeric modifier [16–18]. Designing a new
type of polyurethane elastomer with intrinsic self-healing property
shows an appealing prospect in developing sustainable pavement.
Dynamic covalent bonds are reversibly formed covalent bonds
that can undergo formation, cleavage, or metathesis under defined
conditions, which are extensively employed in self-healing materi-
als [19,20]. The endless bond reorganization caused by the
dynamic covalent bonds allows recovering the network integrity
of materials following mechanical damage timely and repeatedly
[21]. The metathesis reaction of disulfide bonds is widely used,
while this self-healing process requires catalysis or irradiation
under ultraviolet (UV) light [22–24]. Our prior studies have inves-
tigated the modification of asphalt by a disulfide-crosslinked poly-
urethane elastomer, demonstrating the self-healing properties
under UV irradiation after multiple damages [25]. Nevertheless,
ultraviolet irradiation, in turn, contributes to the potential acceler-
ated aging of asphalt binder [26]. In comparison to disulfide bonds,
diselenide bonds (Se-Se) owns lower bond energies (172 kJ mol1,
while disulfide bonds: 240 kJ mol1), indicating that diselenide
bonds are more dynamic, and that metathesis may occur under
milder conditions [27,28]. It’s also reported that a diselenide bond
containing polyurethane elastomer was developed to achieve
effectively self-healing (almost 100% recovery of Young’s modulus)
under merely visible light [29,30].
This study developed a novel self-healing asphalt based on
diselenide-crosslinked polyurethane elastomer. Diselenide-
crosslinked polyurethane elastomer was synthesized by two-step
copolymerization of polypropylene glycol, isophorone diiso-
cyanate, and selenocystamine as a crosslinker used to modify the
asphalt binder to obtain the PU-modified asphalt. The chemical
properties, microscopic morphology, and self-healing capability
of diselenide-crosslinked polyurethane elastomer and polyur-
ethane modified asphalt were evaluated in this study. The objec-
tive of this study is to exploit the dynamic covalent chemistry to
develop an intrinsic self-healing asphalt, for the purpose to
improve the long-term cracking resistance of asphalt pavement.
2. Materials and experiments
2.1. Raw materials
Polypropylene glycol (Aladdin Industries, average molecular
weight: 2000 and 6000 g/mol) and isophorone diisocyanate (Alad-
din Industries, purity  98%) were adopted to prepare the prepoly-
mer with the aid of dibutyltin dilaurate catalyst (Alfa Aesar,
purity  95%). Selenocystamine hydrochloride (Bidepharm,
purity  97%) and dimethyl sulfoxide (Aladdin Industries) were
used to obtain the diselenide-crosslinked polyurethane elastomer
2
Construction and Building Materials 293 (2021) 123480
by chain extension reaction with the prepolymer. The asphalt bin-
der used in this study was SK-70# produced by SK Holdings
(Table 1).
2.2. The preparation of polyurethane elastomer and modified asphalt
binder
The polyurethane modified asphalt was obtained by modifying
the original asphalt binder with the diselenide-crosslinked polyur-
ethane elastomer. The diselenide bonds of selenocystamine
hydrochloride are the source of dynamic covalent bonds in the
polyurethane modified asphalt.
The diselenide-crosslinked polyurethane elastomer was pre-
pared using the two-step copolymerization as shown in Fig. 1
[10,25,26]: the isophorone diisocyanate (IPDI) was mixed with
the polypropylene glycol (PPG-2000, molecular weight:
2000 g/mol) at the molar ratio of 5:1 in a flask at the temperature
of 60 °C, continuously stirred at the spend of 240 r/min for 30 min.
The dibutyltin dilaurate catalyst was then poured into the flask and
stirred for 60 min to obtain the prepolymer-1. The prepolymer-2
was prepared using the isophorone diisocyanate and polypropy-
lene glycol (PPG-6000, molecular weight: 6000 g/mol) at the molar
ratio of 2:1 by the same process with a higher temperature (65 °C)
and shorter mixing time (30 min) after adding dibutyltin dilaurate
catalyst. Two prepolymers and the selenocystamine hydrochloride
(crosslinker) were mixed at the molar ratio of 2:1.2:3 with the
addition of dimethyl sulfoxide as solvent. Then the mixture was
cured at 180 °C for 20 h under vacuum pressure to obtain the
diselenide-crosslinked polyurethane elastomer (DCP) according
to Supplementary Material Section 1.
To prepare the polyurethane modified asphalt, the 3%, 5%, 7%,
and 9% diselenide-crosslinked polyurethane elastomer (by the
weight of asphalt) was added into original asphalt at the tempera-
ture of 140 °C and blended by a high-speed shearer at the speed of
3500r/min for 45 min. The obtained polyurethane modified
asphalts are denoted as PMA-3, PMA-5, PMA-7, PMA-9 for the var-
ious diselenide-crosslinked polyurethane elastomer feeding ratio
of 3%, 5%, 7%, and 9%.
2.3. Characterization methods
The chemical properties of diselenide-crosslinked polyurethane
elastomer and polyurethane modified asphalt were characterized
by Fourier transform infrared (FT-IR) spectrometer and thermal-
gravimetry differential scanning calorimetry. A Fourier infrared
spectrometer (Nicolet Is10, Thermo Fisher Scientific) was used to
observe the diselenide bonds of the diselenide-crosslinked polyur-
ethane elastomer and polyurethane modified asphalt. Thermal-
gravimetry (TG) was conducted to test the thermal stability of
the diselenide-crosslinked polyurethane elastomer at the tempera-
ture ranging from 30 °C to 700 °C with the heating rate of 10 °C/
min under nitrogen condition. The prepolymer was characterized
using gel permeation chromatography (GPC, PL-GPC50, Polymer
Laboratories) at a rate of 1 mL/min at a temperature of 35 °C and
1
H NMR (Bruker AV400 spectrometers) with deuterated chloro-
form (CDCl3) as the solvent in Supplementary Material Section 2
and 3.
Table 1
The properties of the original asphalt binder.
Property SK-70#
Penetration at 25 °C 89.9 mm
Softening Point 45.1 °C
Ductility at 5 °C ＞100 cm
L. Lyu, D. Li, Y. Chen et al.
Fig. 1. Synthetic routes of the diselenide-crosslinked polyurethane elastomer.
2.4. Healing capability experiments
Various methods have been developed to characterize the self-
healing capability of asphalt materials at different scales. Never-
theless, there are still no universal test methods to evaluate the
healing capability of asphalt due to its unclear damage and healing
mechanisms [4]. Fracture-based healing tests and fatigue-based
healing tests are widely adopted to evaluate the healing capability
of asphalt binders, demonstrating excellent consistent and accu-
racy with the results from asphalt mixtures [31,32]. The healing
capabilities of DCP and PMA against macroscopic cracks and fati-
gue cracking were evaluated using fracture-healing-fracture test
and fatigue-healing-fatigue test as shown in Fig. 2, respectively.
2.4.1. Fracture-healing-fracture test
The fracture-healing-fracture test was conducted using the uni-
versal testing machine (CMT5105, MTS Systems Corporation) to
evaluate the healing capability of DCP and PMA against the macro-
scopic cracks, respectively [33].
Fig. 2. Scheme of the healing capability testing.
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Construction and Building Materials 293 (2021) 123480
The strip specimens of polyurethane elastomer
(80 mm*20 mm* 2 mm) were prepared to conduct the fracture-
healing-fracture test as shown in Fig. 3. The specimens were cut
using a blade in the middle of the original specimens and subjected
to different healing conditions to create the healed specimens as
shown in Table 2. The direct tension test was then conducted on
original and healed specimens with a tensile rate of 100 mm/min
at ambient temperature. Herein, the tensile strength and deforma-
tion were used to evaluate the effect of healing duration, temper-
ature, and lighting condition on the healing capability of DCP.
The healing rate (HR) were calculated as Eq.1:
Rmh
HR ¼  100% ð1Þ
Rmo
Where HR is the healing rate of specimens; Rmh is the tensile
strength (MPa) of healed specimens; Rmo is the tensile strength
(MPa) of original specimens.
The fracture-healing-fracture test was conducted on PMA-3,
PMA-5, PMA-7, and PMA-9 according to the ductility tests in JTG
L. Lyu, D. Li, Y. Chen et al. Construction and Building Materials 293 (2021) 123480

Fig. 3. Fracture-healing-fracture test of DCP: (a) original specimens, (b) original specimens in the direct tension test, and (c) healed specimens in the direct tension test.

Table 2
The healing condition of the fractured DCP. Where HIM is the healing index of specimens against the
Specimens Healing duration (h) Temperature (℃) Lighting condition macroscopic cracks; Sh is the maximum stress (N) of healed speci-
mens during the direct tension test; So is the maximum stress (N)
DCP 0.5, 1, 4, 8, 12, 24 20℃ Visible light
DCP 0.5, 12 20℃, 60 ℃ Visible light
of original specimens during the direct tension test.
DCP 0.5, 12 20℃ Visible light, no light
PMA 0.5, 1, 4, 8, 12 20℃ Visible light
2.4.2. Fatigue-healing-fatigue test
The Fatigue-healing-fatigue test was adopted using a dynamic
E20-2019 as shown in Fig. 4 [34]. The specimens were kept at the shear rheometer (DSR, Smartpave-102 produced by Anton Parr)
temperature of 5 °C for 2 h and cut in the middle section. The to evaluate the healing capability of PMA-3, PMA-5, PMA-7, and
fractured specimens healed in an incubator at the temperature of PMA-9 against the fatigue cracking process [4]. An 8 mm plate with
20 °C for different healing duration as shown in Table 2. The orig- a 2 mm gap was used in the fatigue-healing-fatigue test with a
inal and healed specimens were immersed in the water at the tem- strain level of 3% and a frequency of 10 Hz at the temperature of
perature of 5 °C for 2 h and then subjected to the direct tension test 20 °C. The loading of the fatigue-healing-fatigue test stopped when
in the universal testing machine with a tensile rate of 100 mm/min the initial modulus of specimens drops to 70% of the initial value.
at 5 °C. Three duplicate specimens for each asphalt binder are After 1 h and 2 h healing, the loading was conducted on the spec-
tested to obtain the average maximum stress. The coefficient of imens again [6]. The healing index of asphalt against the fatigue
variation (the ratio of the standard deviation to the mean) was also cracking process (HIF) was calculated as Eq.3. Three duplicate spec-
calculated to evaluate the statistical dispersion of results from the imens for each asphalt binder are adopted to obtain the average
fracture-healing-fracture test. A rule of thumb for transportation healing index.
materials is that the coefficient of variation of mechanical proper-
ties must be below 15% to ensure the precision and repeatability of Gh  Gi
experiments [35,36]. The healing capability of asphalt was evalu- HIF ¼  100% ð3Þ
Gi
ated using the healing index against macroscopic cracks (HIM) as
Eq. (2): Where HIF is the healing index of specimens against the fatigue
cracking process; Gh is the complex modulus of specimens after
Sh
HIM ¼  100% ð2Þ healing; Gi is the complex modulus of specimens at the fatigue fail-
So ure control point of the first loading test.

Fig. 4. The direct tension test of PMA: (a) original specimens, (b) fractured specimens, (c) healed specimens, and (d) refractured specimens.

4
L. Lyu, D. Li, Y. Chen et al.
3. Results and discussions
3.1. Chemical characterization analysis
The chemical properties of selenocystamine hydrochloride,
DCP, original asphalt, and PMA were characterized using FT-IR
spectrum and TG-DSC as shown in Fig. 5 and Fig. 6.
It can be seen in Fig. 5 that there are absorption peaks at
2921 cm1 and 1630 cm1 in the curve of DCP, related to the
stretching vibration of carbon-hydrogen bonds and carbon–oxygen
bonds, respectively. These are the characteristic absorption peaks
of polyurethane elastomer, indicating that the polyurethane elas-
tomer has been obtained using the two-step copolymerization
[37]. Meanwhile, the characteristic absorption peak of 3431 cm1
related to the amino groups in the curve of selenocystamine
hydrochloride disappears in the curve of DCP [38]. The reason
behind this is related to the chain-extension reaction between
selenocystamine hydrochloride from the selenocystamine
hydrochloride and isocyanate groups from the prepolymer during
the preparation of DCP. There is also no characteristic absorption
peak of isocyanate groups at 2264 cm1 in the curve of DCP, indi-
cating that the isocyanate groups from prepolymer have been fully
reacted with selenocystamine hydrochloride in the chain-
extension reaction [39]. Furthermore, amine groups containing dis-
elenide bonds were obtained in the chain-extension reaction,
forming an obvious absorption peak at 1092 cm1 in the curve of
DCP. The amine groups containing diselenide bonds also result in
a characteristic absorption peak in the curve of PMA, indicating
that the diselenide bonds from selenocystamine hydrochloride
have been introduced to the asphalt. Similarly, the peak at
1240 cm1 related to C-N bonds in the curves of DCP also appears
at the corresponding position in the curve of PMA [40]. Neverthe-
less, another obvious peak at 1540 cm1 related to the typical
amide I band of DCP disappears at the curve of PMA [41]. It may
attribute to the abundant aromatic hydrocarbons from asphalt bin-
der [42]. Previous research reports that this peak is easily covered
by the skeleton vibrates of aromatic hydrocarbons [43,44]. As the
characteristic absorption peaks of asphalt, no obvious changes
are observed at 2919 cm1 (the asymmetric stretch of carbon-
hydrogen bonds), 2850 cm1 (the symmetric stretch of carbon-
hydrogen bonds), 1456 cm1 (asymmetric bending of carbon-
hydrogen bonds), and 1376 cm1 (symmetrical bending of methyl)
[45,46]. This in turn suggests that there is no chemical reaction
between DCP and asphalt during the preparation process.
Fig. 5. FT-IR spectrum of polyurethane elastomer, DCP, original asphalt, and PMA.
5
Construction and Building Materials 293 (2021) 123480
Fig. 6. TG and DTG curves of DCP.
The mixing temperature for modified asphalt usually ranges
from 160 °C to 180 °C. Therefore, the thermal stability of DCP is
of great importance as an asphalt modifier. The thermal stability
of DCP is characterized by the TG and DTG curves as shown in
Fig. 6. Only one stage can be observed in the TG curve of DCP at
the temperature ranging from 230 °C to 400 °C. This indicates that
no chemical reaction is observed under the temperature of 230 °C,
which is significantly higher than the mixing temperature of mod-
ified asphalt. The mass loss in this stage accounted for 95.53%,
related to the decomposition of the organic long chain of the
DCP. The DTG curve demonstrates the maximum mass-loss rate
of polyurethane elastomer containing diselenide bonds appears
at the temperature of 381 °C. It’s obvious that the DCP can be stable
in the mixing process of asphalt. This may attribute to the cross-
linked structure of DCP, which has been proved to efficacy enhance
the thermal stability of polyurethane elastomer [47–49].
3.2. The healing capability of DCP
The fractured-healing-fractured test was conducted on the DCP
to evaluate the healing capability by applying the direct tensile
force. The self-healing mechanism and process of DCP were
demonstrated in Fig. 7. After specimens fractured, the dynamic
bond reorganization of diselenide bonds appeared at the fractured
surface promptly, achieving the initial healing of polyurethane
elastomer. The intrinsic self-healing of polyurethane elastomer
was then facilitated and cured the weakened area spontaneously.
The fractured specimens were subjected to the different healing
conditions to discuss the effect on the healing capability of DCP
as shown in Fig. 8, Fig. 9, and Fig. 10.
The tensile strength and healing rate of DCP at different healing
duration were shown in Fig. 8. The maximum tensile strength of
original specimens is 0.232 MPa in the direct tensile test, selected
as the initial tensile strength to calculate the healing rate. It’s obvi-
ous that the increasing healing duration significantly enhances the
tensile strength and healing rate of DCP, indicating better healing
at the fractured surface. Remarkably, the healing rate of 53% was
achieved after only 0.5 h healing of fractured specimens, demon-
strating a superior healing capability at the early stage after a frac-
ture. This is related to the dynamic reorganization of diselenide
bonds at the fractured surface. The endless dynamic covalent bond
reorganization of diselenide bonds timely recoveries the fractured
network of polyurethane elastomer. Furthermore, the healing rates
of 88% and 93% were observed after 12 h and 24 h healing, respec-
tively. Similar results prove that the intrinsic healing of DCP almost
L. Lyu, D. Li, Y. Chen et al.
Fig. 7. Schematic of the self-healing mechanism of DCP.
finished in 12 h after it fractured, resulting in less than 5% improve-
ment in the following healing time. Therefore, the tensile strength
of specimens after 0.5 h and 12 h healing was used to evaluate the
short-term and long-term self-healing capability of DCP,
respectively.
The tensile strength and healing rate of specimens after 0.5 h
and 12 h healing were shown in Fig. 9, discussing the effect of tem-
perature and lighting conditions on the healing capability of DCP,
respectively. As shown in Fig. 8, the healing rate of specimens after
0.5 and 12 h healing at the temperature of 60 °C is 62.93% and
92.67%, indicating a 10.99% and 5.17% increasing in that of speci-
mens healing at the temperature of 20 °C. It suggests that the
higher temperature significantly benefits the self-healing of DCP,
especially at the early stage after a fracture. Similarly, the tensile
strength of specimens after 0.5 h and 12 h healing at the tempera-
ture of 60 °C is also enhanced by 25% and 10% compared to that of
specimens healing at the temperature of 20 °C. The higher healing
temperature may provide the necessary energy for dynamic bond
reorganization between diselenide bonds and facilitate the interac-
tion between molecules at the fractured surface to enhance the
intrinsic healing capability of specimens.
It can be seen from Fig. 10 that the healing rate and tensile
strength of specimens under visible light were improved by less
than 2% and 5% compared to that of specimens without any light.
Fig. 8. (a) Strength-strain curves and (b) tensile strength and healing rate of DCP at different healing duration.
6
Construction and Building Materials 293 (2021) 123480
This suggests that the dynamic reorganization of diselenide bonds
can react without any light. This may be related to the low bond
energy of diselenide covalent bonds, which results in the low
energy necessary for dynamic reorganization. Relevant studies also
report the similar dynamic reorganization of diselenide bonds in
the presence of heat alone without light [28]. It can be conducted
that lighting condition has little effect on the healing capability of
DCP. It is of great significance for the potential application in the
self-healing asphalt, due to the lack of light inside the asphalt
pavement.
3.3. The healing capability of PMA for macroscopic cracks
The fracture-healing-fracture test was conducted on the PMA to
measure the maximum stress of specimens after healing for the
visible cracks. The maximum stress and HIM of original and healed
specimens were obtained and shown in Table 3 and Fig. 11,
respectively.
It’s can be seen from Table 3 that all fractured specimens
achieved self-healing and recovered the maximum stress to vary-
ing degrees compared to the unfractured specimens. All coeffi-
cients of variation are below 15%, indicating that the averaged
maximum stress largely depends on the specimens, rather than
experimental errors [35]. The healing duration demonstrates a sig-
nificant effect on the maximum stress of specimens in the fracture-
healing-fracture test. The maximum stress of fractured original
asphalt increases from 32.57 N after 0.5 h healing to 62.57 N after
12 h healing, demonstrating the intrinsic healing capability of the
original asphalt binder. It’s also remarkable that the maximum
stress of PMA after 0.5 h healing is 21% higher than that of the orig-
inal asphalt averagely. The dynamic covalent bond reorganization
timely recovery the network integrity at the fractured surface, sig-
nificantly enhancing the prompt healing capability of asphalt bin-
der. It may have great efficacy in resisting the propagation of cracks
in asphalt pavement [50,51].
The HIM was calculated to further discuss the effects of polyur-
ethane elastomer contents on the healing capability of PMA against
the macroscopic cracks. Generally, the PMA demonstrates the
higher HIM compared to the original asphalt binder after the same
healing duration, demonstrating the obvious improvement in the
healing capability during the whole healing process after fractured.
The HIM of PMA-5 increased to 77.5% and 131.3% after 0.5 h and
L. Lyu, D. Li, Y. Chen et al. Construction and Building Materials 293 (2021) 123480

Fig. 9. (a) Strength-strain curves and (b) tensile strength and healing rate of DCP at different healing temperatures.

Fig. 10. (a) Strength-strain curves and (b) tensile strength and healing rate of DCP at different healing lights.

Table 3
Maximum stress of PMA at various polyurethane elastomer contents.

Healing duration Original asphalt PMA-3 PMA-5 PMA-7 PMA-9

Unfractured MS (N) 63.21 67.21 60.35 65.13 52.78
CV (%) 4.31 2.75 4.28 2.43 6.29
0.5 h MS (N) 32.57 44.65 46.77 37.63 29.34
CV (%) 3.91 4.46 5.19 4.91 3.21
1h MS (N) 44.56 49.34 50.51 46.27 33.97
CV (%) 5.31 4.51 7.34 2.73 3.42
4h MS (N) 47.63 52.67 59.22 55.43 46.25
CV (%) 6.38 1.97 3.79 4.18 2.87
8h MS (N) 53.24 59.35 66.31 65.07 48.51
CV (%) 2.57 2.58 4.79 3.94 2.18

MS: Averaged maximum stress; CV: Coefficient of Variation.

7
L. Lyu, D. Li, Y. Chen et al.
Fig. 11. HIM of PMA at various polyurethane elastomer contents.
12 h, which is 50.4% and 32.7% higher than that of original asphalt,
respectively. Nevertheless, the excessive polyurethane elastomer
content contributes to an obvious decrease in the healing capabil-
ity as shown in the curves of PMA-7 and PMA-9. It may be related
to the effects of DCP on the mechanical properties of asphalt bin-
der, which also demonstrated in the unstable maximum stress of
unfractured specimens as shown in Table 3. It’s remarkable that
the HIM of some specimens is higher than 1, indicating that the
maximum stress of healing specimens after fractured is even
improved compared to the unfractured specimens. This may be
related to the second cross-link among multiple polymers inside
PMA caused by abundant hydrogen bonds from polyurethane elas-
tomer [52]. The healing temperature and duration provide the nec-
essary energy and time to strengthen the topological polymer
network inside the PMA. Therefore, a dual-dynamic three-
dimensional crosslinked network of hydrogen bonds and dynamic
diselenide bonds further enhances the mechanical properties of
PMA [53].
3.4. The healing capability of PMA for fatigue cracking
It’s reported that the fatigue cracking caused by the repeated
vehicular loading is the main damage form of asphalt pavements
[6]. In the fatigue-healing-fatigue test, a similar repeated loading
was conducted on the specimens using DSR to obtain the fatigue
damage. The complex modulus and HIF of specimens after 1 h
and 2 h healing were calculated to evaluate the healing capability
for fatigue cracking as shown in Fig. 12.
It can be seen from the results that the complex modulus of
specimens decreases synchronously with the increasing polyur-
ethane elastomer content, indicating the lower stiffness of PMA
than the original asphalt. Obviously, the decrease in the stiffness
of specimens is the consequence of the addition of polyurethane
elastomer with different mechanical properties compared to the
asphalt binder and the potential interaction of compositions. The
complex modulus of specimens after 2 h healing is higher than that
of specimens after 1 h healing, indicating that increasing healing
duration benefits in a better recovery of the fatigue damage. The
curves of HIF show the changes in the healing capability of PMA
containing different polyurethane elastomer contents. The maxi-
mum HIF of 58.88% and 78.63% after 1 h and 2 h healing appear
8
Construction and Building Materials 293 (2021) 123480
Fig. 12. Complex modulus (G*) and HIF of PMA at various polyurethane elastomer
contents after 1 h and 2 h healing.
Table 4
Increasing rate in HIF of PMA at various polyurethane elastomer contents.
Healing Increasing rate in HIF
duration
PMA-3 PMA-5 PMA-7 PMA-9 Average
1h 52.08% 111.41% 77.52% 76.43% 76.43%
2h 60.30% 125.37% 84.81% 83.90% 83.90%
at the curve of PMA-5, which is improved by 111.41% and
125.36% compared to that of original asphalt, respectively. The
higher polyurethane elastomer contents in turn weaken the heal-
ing capability of PMA, which is consistent with the results from
fractured-healing-fractured of PMA. This may be due to the violent
dynamic bond reorganization caused by the excessive diselenide
bonds, decreasing stability of the healing area near the fractured
surface.
To further evaluate the effect of polyurethane elastomer on the
PMA, the increasing rate in HIF is calculated by subtracting HIF of
original asphalt from HIF of self-healing asphalt divided by HIF of
original asphalt after the same healing duration as shown in
Table 4. It’s obvious that the increasing rate in HIF of 2 h is higher
than that of 1 h, indicating that the efficacy of polyurethane elas-
tomer on the healing capability of specimens during the second
healing hour is even more significant than that of specimens dur-
ing the first hour of healing. Nevertheless, the healing efficiency
of DCP continuously decreases with the increased healing duration
according to results from the fracture-heal-fracture test, which is
inconsistent with the increasing rate in HIF. This may be related
to the promotion effect of polyurethane elastomer on the intrinsic
self-healing capability of asphalt binder. The reorganization of
dynamic covalent bonds results in a better healing capability at
the initial stage, partly recovering the network integrity of asphalt
at the fractured surface. The asphalt binder is then easier to flow
into the weakened area spontaneously along with the restored net-
work, achieving the synergistic healing of PMA.
4. Conclusions
This preliminary study proves the great potential of diselenide
bonds in the self-healing asphalt, motivating the intrinsic self-
healing capability of asphalt binder and achieving synergistic heal-
ing. The following conclusions were drawn from this study:
L. Lyu, D. Li, Y. Chen et al.
(1) FT-IR indicates that the diselenide bonds were introduced to
polyurethane elastomer using the two-step copolymeriza-
tion and modifying the original asphalt to obtain the PMA.
The thermal stability of DCP is proved to be satisfied as the
asphalt modifier using TG-DSC analysis.
(2) The diselenide bond significantly enhances the self-healing
capability of DCP, especially at the early stage after a frac-
ture. The increasing temperature has an obvious promotion
on the healing efficiency, while the lighting condition has lit-
tle effect on the self-healing of DCP.
(3) PMA demonstrates a superior healing capability for macro-
scopic and fatigue cracks. The intrinsic self-healing capabil-
ity of asphalt binder is promoted by the diselenide
dynamic covalent bonds, achieving synergistic healing.
(4) The synergistic of dynamic bond reorganization and asphalt
binder on self-healing has been proved in this study. Future
research should focus on the mechanism of synergistic heal-
ing in diselenide-crosslinked polyurethane elastomer modi-
fied asphalt to further motivate the healing capability. The
healing capability of diselenide-crosslinked polyurethane
elastomer modified asphalt mixtures also should be investi-
gated for its future deployment in the self-healing asphalt
pavement.
CRediT authorship contribution statement
Lei Lyu: Conceptualization, Data curation, Formal analysis,
Investigation, Methodology, Resources, Validation, Visualization,
Writing - original draft. Dong Li: Conceptualization, Data curation,
Formal analysis, Investigation, Methodology, Validation. Yuxian
Chen: Resources, Conceptualization, Validation, Investigation.
Yefei Tian: Resources, Validation, Visualization, Funding acquisi-
tion, Supervision. Jianzhong Pei: Resources, Software, Validation,
Visualization, Funding acquisition, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This research was sponsored by the National Key R&D Program
of China (Grant No. 2018YFE0103800), the National Science Foun-
dation of China (Grant No. 51703010), the China Postdoctoral
Science Foundation (Grant No. 2017 M623092 and
2018 T111008), the Association of Science and Technology Youth
Talents Invitation Project of Shaanxi Universities (20190407), and
the Fundamental Research Funds for the Central Universities,
CHD (Grant No. 300102210402 and 300102319206). The authors
gratefully acknowledge their financial support.
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