polymers
Article
Viscoelastic Behavior and Phase Structure of High-Content
SBS-Modified Asphalt
Dongdong Yuan 1,2 , Chengwei Xing 1,2 , Wei Jiang 1,2, *, Jingjing Xiao 3 , Wangjie Wu 1,2 , Pengfei Li 1,2
and Yupeng Li 1,2
Citation: Yuan, D.; Xing, C.; Jiang, W.;
Xiao, J.; Wu, W.; Li, P.; Li, Y.
Viscoelastic Behavior and Phase
Structure of High-Content
SBS-Modified Asphalt. Polymers 2022,
14, 2476. https://doi.org/10.3390/
polym14122476
Academic Editor: Alexander Malkin
Received: 21 May 2022
Accepted: 16 June 2022
Published: 17 June 2022
Publisher’s Note: MDPI stays neutral
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iations.
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Polymers 2022, 14, 2476. https://doi.org/10.3390/polym14122476
1 Key Laboratory for Special Area Highway Engineering of Ministry of Education, Chang’an University,
Xi’an 710064, China; ddy@chd.edu.cn (D.Y.); xingcw@chd.edu.cn (C.X.); wwj@chd.edu.cn (W.W.);
2020021080@chd.edu.cn (P.L.); liyupeng@chd.edu.cn (Y.L.)
2 School of Highway, Chang’an University, South 2nd Ring Road Middle Section, Xi’an 710064, China
3 School of Civil Engineering, Chang’an University, Xi’an 710064, China; xiaojj029@sina.com
* Correspondence: jiangwei@chd.edu.cn
Abstract: To investigate the effect of styrene-butadiene-styrene (SBS) modifier content on the vis-
coelastic behavior of SBS-modified asphalt (SBSMA) at different temperatures and phase structures,
the star SBS modifier was chosen to fabricate seven types of SBSMA with different contents. Multiple
stress creep recovery (MSCR), linear amplitude sweep (LAS), and low-temperature frequency sweep
tests were adopted to study the influence of SBS modifier content on the viscoelastic performance of
SBSMA at high to low temperatures. The SBSMA’s microstructure with different contents was inves-
tigated using a fluorescence microscope. The results indicated that the change in non-recoverable
creep compliance and creep recovery rate was bounded by 4.5% content at high temperatures, with
an apparent turning point. The changing slope of content at less than 4.5% was much higher than
that of the content greater than 4.5%. At medium temperatures, the fatigue life of SBSMA increased
exponentially with the rising modifier content. The rate of increase in fatigue life was the largest
as the content increased from 4.5% to 6.0%. At low temperatures, the low-temperature viscoelastic
property index G (60 s) of SBSMA decreased logarithmically as the modifier content increased. In
terms of the microscopic phase structure, the SBS modifier gradually changed from the dispersed to
the continuous phase state with the increasing SBS modifier content.
Keywords: high-content polymer modified asphalt; SBS; viscoelastic behavior; phase structure
1. Introduction
Asphalt pavement consists of aggregates, fillers, and asphalt binders; the design
of asphalt binders and research on its related properties remain at the core of asphalt
pavement [1,2]. Using an asphalt binder with excellent properties can remarkably improve
the quality of asphalt pavement [3,4]. With the increasing traffic load, a neat asphalt
binder will not be enough to fulfill the requirements of traffic development [5,6]. Styrene-
butadiene-styrene (SBS)–modified asphalt (SBSMA) is universally applied because of its
properties such as excellent durability, anti-ageing, fatigue resistance, and water damage
resistance [7,8]. SBSMA has been utilized extensively on national highways in China [9,10].
SBS is a block copolymer created from the anionic polymerization of 1,3-butadiene, styrene
(monomer), tetrahydrofuran (activator), and n-butyllithium (initiator) in the cyclohexane
solvent [11]. According to the different contents of polystyrene and polybutadiene, as
well as the difference in the molecular structure, SBS can be divided into the linear and
star structures, as shown in Figure 1 [12]. In general, the molecular weight of the star
structure is higher than that of the linear structure. Previous research and applications
have suggested that the SBSMA content in many countries is 3.0–6.0%, considering the
limitations of asphalt pavement construction costs and construction technologies [13,14].
Yet, no in-depth investigation has been conducted on the higher dosage of this material.
https://www.mdpi.com/journal/polymers
 Polymers
Polymers 2022,
2022, 14,14, 2476
2476 22 ofof1616

dosage ofporous
However, this material.
asphaltHowever, porous
concrete has beenasphalt concrete
more and morehas been
used more and materials
in pavement more used
in pavement materials with the advancements in pavement green technology
with the advancements in pavement green technology [15,16]. Therefore, modified asphalt [15,16].
Therefore, modified asphalt with high viscosity is commonly applied in porous
with high viscosity is commonly applied in porous asphalt concrete [17,18]. At present, asphalt
concreteasphalt
modified [17,18].with
At present, modified
high viscosity asphalt
is mainly with high
fabricated viscosity
using a highiscontent
mainlyoffabricated
SBSMA
using a high
(6.0–12.0%) content of SBSMA (6.0–12.0%) [19].
[19].

Figure1.1.Linear
Figure LinearSBS
SBSand
andStar
StarSBS.
SBS.

Zhang
Zhangetetal.al.examined
examinedthe therheological
rheologicalbehavior
behaviorofofhigh-content
high-contentSBSMA SBSMAafter afterthe
the
addition of a plasticizer (fural exact oil) and a crosslinker (sulfur). Their results
addition of a plasticizer (fural exact oil) and a crosslinker (sulfur). Their results illustrated illustrated
that
thatthe
theplasticizer
plasticizerreduced
reducedthe theanti-rutting
anti-ruttingperformance
performanceofofSBSMA. SBSMA.The Theinclusion
inclusionofofa a
crosslinker created a polymer network, a network structure
crosslinker created a polymer network, a network structure with better ageing, with better ageing, which in-
which
creased SBSMA’s ageing resistance [20]. This is because the ageing
increased SBSMA’s ageing resistance [20]. This is because the ageing of the polymer of the polymer depends
on the actual
depends on3Dthestructure
actual 3D (more chaotic(more
structure or more structured)
chaotic or more andstructured)
the type ofand crosslinks
the type[21].of
However, the SBS modifier content in their study was just 6.0%, remarkably lower than
crosslinks [21]. However, the SBS modifier content in their study was just 6.0%,
what is used in practice. Yan et al. evaluated the ageing properties of high-content SBSMA,
remarkably lower than what is used in practice. Yan et al. evaluated the ageing properties
whose findings revealed that the SBS modifier breakdown occurs during the early stages
of high-content SBSMA, whose findings revealed that the SBS modifier breakdown occurs
of ageing. In addition, short-term ageing at elevated temperatures can severely degrade
during the early stages of ageing. In addition, short-term ageing at elevated temperatures
high-content SBSMA’s anti-rutting capabilities [22]. Lin et al. investigated the rheologi-
can severely degrade high-content SBSMA’s anti-rutting capabilities [22]. Lin et al.
cal properties of high-content SBSMA. Their results suggested that SBSMA with higher
investigated the rheological properties of high-content SBSMA. Their results suggested
content would possess superior rheological qualities; however, 9% is the ideal dosage for
that SBSMA with higher content would possess superior rheological qualities; however,
economic reasons [23]. Zhang et al. explored the composition of high viscosity–modified
9% is the ideal dosage for economic reasons [23]. Zhang et al. explored the composition of
asphalt and discovered that increasing the SBS modifier concentration is one of the most
high viscosity–modified asphalt and discovered that increasing the SBS modifier
effective approaches to maintaining the physical qualities of high viscosity–modified as-
concentration is one of the most effective approaches to maintaining the physical qualities
phalt [24]. Giacomo et al. observed that a high-content SBS modifier was able to lessen the
of high viscosity–modified
ageing-induced stiffening of asphalt
SBSMA.[24]. Giacomo
Compared to et al. observed
typical SBSMA thatwithaahigh-content
lower polymer SBS
modifier was able to lessen the ageing-induced stiffening of SBSMA.
concentration, the SBS modifier network in the high-content SBSMA could present a barrier Compared to typical
toSBSMA with a lower
the oxidation of the polymer concentration,
binder, leading to betterthe SBS modifier
anti-ageing network in
performance the high-content
[3,25].
SBSMA
In a could present
nutshell, limiteda barrier
studiesto the oxidation of the
on high-content binder,
SBSMA leading
have beentoconducted
better anti-ageing
so far.
performance [3,25].
Furthermore, most research focuses on the influence of ageing on the properties of high-
contentInSBSMA.
a nutshell,At limited
present,studies
research onon high-content SBSMA
the viscoelastic have been
properties and conducted so far.
phase structure
Furthermore, most research focuses on the influence of ageing
of high-content SBSMA is not detailed enough. Therefore, to investigate the viscoelasticon the properties of high-
behavior of high-content SBSMA at high to low temperatures, we employed three newof
content SBSMA. At present, research on the viscoelastic properties and phase structure
high-content
dynamic shear SBSMA
rheometer is not
(DSR) detailed enough.That
test methods. Therefore, to investigate
is, the multiple the viscoelastic
stress creep recovery
behavior
(MSCR) of linear
test, high-content
amplitude SBSMA sweepat high
(LAS)totest,
lowandtemperatures, we employedfrequency
4 mm low-temperature three new
dynamic
sweep test.shear rheometer
Meanwhile, (DSR) test methods.
the microstructure Thatwith
of SBSMA is, the multiple
different stress creep
contents recovery
was analyzed
(MSCR) test, linear amplitude sweep (LAS) test, and 4 mm
by a fluorescence microscope. The flowchart of this study is shown in Figure 2. This low-temperature frequency
sweep
study test. Meanwhile,
clarified the viscoelastic theproperties
microstructure of SBSMA
and microscopic withstructure
phase different contents was
of high-content
analyzed by a fluorescence microscope. The flowchart of this study is shown in Figure 2.
 Polymers 2022, 14, 2476 3 of 16
Polymers 2022, 14, 2476 3 of 16

This study clarified the viscoelastic properties and microscopic phase structure of high-
content
SBS SBS modified
modified asphalt atasphalt attemperatures,
different different temperatures, whichaprovides
which provides referenceafor
reference for
the wider
application of high-content
the wider application SBS modified
of high-content asphalt.
SBS modified asphalt.

Figure2.2.Flowchart
Figure Flowchartofofthis
thisstudy.
study.

2.2.Materials
Materialsand
andMethods
Methods
2.1. Raw Materials
2.1. Raw Materials
Shell
Shell70# neat
70# asphalt
neat was utilized
asphalt to prepare
was utilized high-content
to prepare SBSMA. Its
high-content basic attributes
SBSMA. Its basic
are tabulated in Table 1. The adopted SBS modifiers were provided
attributes are tabulated in Table 1. The adopted SBS modifiers were provided by Baling Petrochemical
by Baling
Company of Sinopec
Petrochemical Group.ofTable
Company 2 listsGroup.
Sinopec the basic parameters
Table 2 lists of
thethebasic
modifier. The modifier
parameters of the
content was chosen as 3.0%, 4.5%, 6.0%, 7.5%, 9.0%, 10.5% and
modifier. The modifier content was chosen as 3.0%, 4.5%, 6.0%, 7.5%, 9.0%, 12.0% of the mass of the
10.5% and
neat
12.0%asphalt,
of the respectively. Theasphalt,
mass of the neat sulfur powder with purity
respectively. of more
The sulfur powderthanwith
99%purity
provided by
of more
Shanghai Qunkang Asphalt Technology Co., Ltd. (Shanghai, China)
than 99% provided by Shanghai Qunkang Asphalt Technology Co., Ltd. (Shanghai, was selected as the
stabilizer. The content of the stabilizer was chosen as 0.15% of the mass of the neat asphalt.
China) was selected as the stabilizer. The content of the stabilizer was chosen as 0.15% of
the mass
Table of property
1. Basic the neat of
asphalt.
neat asphalt.

Table 1. Basic property of neat asphalt.

Item Shell 70#
Penetration at 25◦ C,0.1 mm 70.8 70#
Item Shell
Softening point, ◦ C 49.2
Penetration at 25 °C, 0.1 mm
Ductility at 5 ◦ C, 5 cm min−1 , cm
70.8
74.3
Softening point, °C 49.2
Ductility at 5 °C, 5 cm min−1, cm 74.3
Table 2. Technical performance of SBS modifier.
Table 2. Technical performance
Type of SBS modifier. Star Type
Type g cm−3
Specific gravity, Star
0.94Type
Elongation at break,
Specific gravity, % −3
g cm 680
0.94
Tensile strength, MPa 21.2
Elongation at break, % 680
Melt index, g (10 min−1 ) 7.0
Tensile strength, MPa 21.2
Melt index, g (10 min−1) 7.0
2.2. Experimental Methods
2.2.1. Preparing SBSMA
2.2. Experimental Methods
SBSMA can be prepared as Figure 3. First, the corresponding quality of neat asphalt,
2.2.1. Preparing SBSMA
SBS modifier, and stabilizer was weighed. We heated the neat asphalt to the molten state
SBSMA
in an oven. canweighed
The be prepared as Figurewas
SBS modifier 3. First,
addedthe into
corresponding quality
it and stirred withof neat asphalt,
a vane stirrer
atSBS
170modifier, and stabilizer
◦ C and 1000 r/min forwas
halfweighed.
an hour. We
Theheated theneat
blended neatasphalt
asphalt and
to the molten
SBS state
modifier
were then sheared by a shear emulsifying machine at 170 C and 3000 rotations per min forat
in an oven. The weighed SBS modifier was added into it
◦ and stirred with a vane stirrer
10 min. Next, the stabilizer was added, and the mixture was sheared for an hour at 170 ◦ C
Polymers 2022, 14, 2476 4 of 16

Polymers 2022, 14, 2476 170 °C and 1000 r/min for half an hour. The blended neat asphalt and SBS modifier 4were
of 16
then sheared by a shear emulsifying machine at 170 °C and 3000 rotations per min for 10
min. Next, the stabilizer was added, and the mixture was sheared for an hour at 170 °C
and 5000 rotations per min. Finally, the sheared SBS modifier was heated at 170 °C ◦for 90
and 5000 rotations per min. Finally, the sheared SBS modifier was heated at 170 C for
min to allow the prepared SBSMA to fully develop and escape the air bubbles created
90 min to allow the prepared SBSMA to fully develop and escape the air bubbles created
during the preparation process.
during the preparation process.

Figure
Figure 3.
3. Preparation
Preparation process
process of
of SBSMA.
SBSMA.

2.2.2. MSCR
MSCR Test
The high-temperature viscoelastic behavior of SBSMA was investigated using MSCR
tests. In
In this
this test,
test, Smartpave
Smartpave 102102 DSR
DSR (Anton
(Anton Paar
Paar company,
company, Graz,Graz, Austria)
Austria) was
was utilized.
utilized.
Two round parallel plates with a diameter of 25 mm were utilized, and the gap between
them was
them was 11 mm.
mm. To To simulate
simulate the
the high
high temperature
temperature experienced
experienced by by the
the asphalt
asphalt pavement
pavement
in summer,
in summer, referring
referring to
to the
the AASHTO
AASHTO M332-19
M332-19 [26]
[26] classification
classification standard,
standard, 64 64 ◦°C
C was
was
selected for the MSCR test. The creep and recovery tests were performed
selected for the MSCR test. The creep and recovery tests were performed with the constant with the constant
stress (0.1
stress (0.1 kPa
kPa and
and 3.2
3.2 kPa),
kPa), respectively.
respectively. During
Duringthe thetest,
test,the
thestress
stresswas
wasfirst
firstloaded
loaded forfor
1
1 s. Afterward, zero stress was recovered for 9 s. First, the test was run
s. Afterward, zero stress was recovered for 9 s. First, the test was run for 20 cycles at 0.1for 20 cycles at
0.1 kPa.
kPa. Then,
Then, it ran
it ran forfor
10 10 cycles
cycles at at
3.23.2
kPa.kPa. Finally,it itran
Finally, ran3030creep
creepandandrecovery
recovery cycles
cycles for
for
300 s [27,28].
300 s [27,28].
2.2.3. LAS Test
2.2.3. LAS Test
The LAS test can assess SBSMA’s fatigue properties at medium temperatures. Smartpave
The LAS test can assess SBSMA’s fatigue properties at medium temperatures.
102 DSR (Anton Paar company, Graz, Austria) was used in this test, with an 8 mm-parallel
Smartpave 102 DSR (Anton Paar company, Graz, Austria) was used in this test, with an 8
plate die and a 2 mm-gap. The LAS test was performed in a loading mode (controlled strain)
mm-parallel plate die and a 2 mm-gap. The LAS test was performed in a loading mode
with a design test time of 300 s. During the test, the sine wave dynamic load amplitude rose
(controlled strain) with a design test time of◦300 s. During the test, the sine wave dynamic
linearly from 0.1% to 30% [29,30]. Herein, 25 C was chosen as the LAS test temperature.
load amplitude rose linearly from 0.1% to 30% [29,30]. Herein, 25 °C was chosen as the
LAS
2.2.4.test temperature. Frequency Sweep Test
Low-Temperature
The low-temperature frequency sweep test was performed by DSR, which could
2.2.4. Low-Temperature Frequency Sweep Test
overcome the disadvantages of too many materials and the long test time of the low-
The low-temperature
temperature frequency (BBR)
bending beam rheometer sweeptest.
testThe
was4 mmperformed
parallel by DSR,
plate which could
low-temperature
overcome
frequency the disadvantages
sweep of too many
test can substitute the BBR materials
test to and thethe
assess long test time
asphalt of theatlow-
property low
temperature bending beam rheometer (BBR) test. The 4 mm parallel
temperatures [31]. Therefore, a 4 mm parallel plate for the low-temperature frequency plate low-
temperature
sweep test was frequency sweeptotest
selected herein can SBSMA’s
explore substitutelow-temperature
the BBR test toviscoelastic
assess thebehavior.
asphalt
property at low
The tests used temperatures
a SmartPave Model[31].
102Therefore,
DSR with aa 44mm-parallel
mm parallel plate
plate die for the atlow-
placed the
temperature
3 mm-gap. The frequency sweep was
loading model testcontrolled
was selected
strain,herein
and theto strain
explore
wasSBSMA’s low-
1%; the sweep
temperature
frequency was viscoelastic behavior.
0.1–100 rad/s, The
and the tests
test temperature was −5 ◦ C
used a SmartPave Model
and − 15 ◦DSR
102 with a 4
C [32].
Polymers 2022, 14, 2476 5 of 16

2.2.5. Fluorescence Microscope Test

An LW300LFT fluorescence microscope (Nikon Corporation, Tokyo, Japan) was em-
ployed to determine SBSMA’s distribution and morphological characteristics in the asphalt
phase. The magnification of the eyepiece of the fluorescence microscope and that of the
objective lens was 10.

3. Results and Discussion

3.1. Viscoelastic Behavior at High Temperatures
3.1.1. Non-Recoverable Creep Compliance and Creep Recovery Rate
Generally, a high-temperature rutting phenomenon will occur on the asphalt pavement
due to the accumulation of the asphalt binder’s non-recoverable strain. Therefore, the
non-recoverable creep compliance (Jnr ) is a critical evaluation indicator of the MSCR test
(Equation (1)). Under a certain recovery time, the greater the recovery deformation and the
smaller the amount of non-deformation of asphalt, the less likely high-temperature rutting
will occur. Therefore, the creep recovery rate (R) can also represent the high-temperature
viscoelastic behavior of asphalt (Equation (2)). Jnr and R are calculated by average values
in 10 creep recovery cycles, respectively [31]. The Jnr at 0.1 kPa and 3.2 kPa are denoted as
Jnr 0.1 and Jnr 3.2. Furthermore, the R at corresponding stress levels are represented as R0.1
and R3.2.
εu
Jnr = (1)
σ
where, εu is the adjusted strain value after the recovery period, σ is the value of the applied
stress level.
ε p − εu
R= × 100% (2)
εp
where, εp is the adjusted strain value when the creep loading ends, εu is the adjusted strain
value after recovery period.
Figure 4 presents the Jnr and R of the eight kinds of asphalt at 64 ◦ C. Under different
stress levels, Jnr 3.2 > Jnr 0.1, R3.2 < R0.1. This order indicates that the increase in stress will
worsen the high-temperature viscoelastic properties of SBSMA. With the rising modifier
content, the Jnr of SBSMA dropped and the R increased, suggesting that increasing the
modifier content can improve the rheological properties of SBSMA. When the modifier
content increased by 1.5%, an obvious turning point was noticed in the change in Jnr and R,
which was bounded by 4.5% content. The changing slope of the content less than 4.5% is
much higher than that of the content greater than 4.5%, indicating that when the modifier
content exceeds 4.5%, it can enhance the SBSMA’s high-temperature viscoelastic behavior
with a limited improvement effect. This is because when the content of SBS modifier
is 4.5%, the viscosity of the asphalt phase and the elasticity of the SBS phase in SBSMA
reach an equilibrium state. Although increasing the content of the modifier can increase
the mechanical strength of the SBS phase, the effect is not obvious. Figure 5 shows that
for Shell 70# neat asphalt, the addition of the star SBS modifier to 3.0% content caused a
decrease in Jnr 0.1 and Jnr 3.2 by 82.44% and 78.91%. R0.1 and R3.2 rose by 955.00% and
8690.90%. It is shown that adding the SBS modifier can considerably boost the neat asphalt’s
high-temperature viscoelastic performance. For SBSMA, when it rises from 3.0% to 4.5%,
the change rate of Jnr and R is the largest, followed by the change rate when the content
increases from 4.5% to 6.0%. Thereafter, with the increasing content, the change rate of Jnr
and R becomes smaller, which may be related to the microstructure of SBSMA.
 Polymers
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16
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Figure
Figure4.4.
Figure Non-recoverable creep
Non-recoverablecreep
4.Non-recoverable compliance
creepcompliance and
complianceand creep
andcreep recoveryrate
creeprecovery rateof
ofasphalt.
asphalt.

(a)
(a)

(b)
(b)
Figure
Figure5.5.
Figure The
5.The change
Thechange rate
changerate of
rateof JJnrand
ofJnr andR.
R.(a)
(a)non-recoverable
non-recoverablecreep
creepcompliance;
compliance;(b)
(b)Creep
Creeprecovery
recoveryrate.
rate.
nr and R. (a) non-recoverable creep compliance; (b) Creep recovery rate.

3.1.2.Stress
3.1.2
3.1.2 StressSensitivity
Stress Sensitivity
Sensitivity
TheSBSMA’s
The
The SBSMA’ssensitivity
SBSMA’s sensitivityto
sensitivity tostress
to stresscan
stress canbe
can beexpressed
be expressedby
expressed bythe
thedifference
differencein theJJnrnr
inthe under
under
nrunder

3.2
3.2 kPa
kPa and
and 0.1
0.1 kPa,
kPa, which
which is
is calculated according to Equation
3.2 kPa and 0.1 kPa, which is calculated according to Equation (3). (3).

Jnr-diJJnr-diff
fnr-diff
= JJ3.2
f = =[( Jnr
3.2−JJnr
3.2−J
nrnr − nr
0.1
0.1)/J/J
nr0.1
0.1 ××100%
0.1 100%
nrnrnr 0.1] × 100%
/J (3)
(3)
(3)
where,
where,JJnr-diff
where, Jnr-diff isisthe
thestress
stresssensitivity,
sensitivity,JJnrnr0.1
0.1and
andJJnrnr3.2
3.2are
arethe
thevalues
valuesofofJJnrnrof
ofasphalt
asphaltatat0.1
0.1
nr-diff is the stress sensitivity, Jnr 0.1 and Jnr 3.2 are the values of Jnr of asphalt at
kPa
kPa and3.2
0.1 and
kPa 3.2kPa.
and kPa. TheJThe
The
3.2 kPa. Jnr-diff J ofeight
nr-diffof eight typestypes
types
of eight ofasphalt
of asphalt at64
at
of asphalt 64°C
°C64
at are
are plotted
plotted
◦C ininFigure
are plotted Figure 6.6. 6.
in Figure
nr-diff
 Polymers2022,
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2476 77 of
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16

Figure6.6.JJnr-diff
Figure of eight
nr-diff of eight types
types of
of asphalt.
asphalt.

Figure
Figure66shows
showsthat theJnr-diff
thatthe of the
Jnr-diff of the neat
neat asphalt
asphalt is
is the
the smallest
smallest among
amongthe theeight
eighttypes
types
of the J
of asphalt, and the Jnr-diff of SBSMA is much larger than that of the neat asphalt. For SBSMA,
asphalt, and nr-diff of SBSMA is much larger than that of the neat asphalt. For SBSMA,
JJnr-diff has no evident change rule with the rising star SBS modifier content. The J of 3.0%
nr-diff has no evident change rule with the rising star SBS modifier content. The Jnr-diffnr-diff
of
3.0% content is the smallest, and the
content is the smallest, and the Jnr-diff of nr-diff J of 6.0% content is the largest. This may
6.0% content is the largest. This may be attributed be
attributed to a large
to a large number ofnumber
polymerofchainpolymer chaininside
segments segments inside the
the SBSMA SBSMA
with complexwith complex
mechanical
mechanical behavior and different phase structures. The literature
behavior and different phase structures. The literature has shown that the viscoelastic has shown that the
viscoelastic performance of modified asphalt could be determined according to the notion
performance of modified asphalt could be determined according to the notion of whether
of whether the Jnr-diff of the modified asphalt is greater than 5% [30]. When Jnr-diff is greater
the Jnr-diff of the modified asphalt is greater than 5% [30]. When Jnr-diff is greater than 5%, it
than 5%, it is a nonlinear viscoelastic state. Similarly, when Jnr-diff is less than 5%, it is a
is a nonlinear viscoelastic state. Similarly, when Jnr-diff is less than 5%, it is a linear
linear viscoelastic state. At 3.2 kPa and 64 ◦ C, the viscoelastic performance of star SBSMA
viscoelastic state. At 3.2 kPa and 64 °C, the viscoelastic performance of star SBSMA with
with a content of more than 3.0% is all nonlinear.
a content of more than 3.0% is all nonlinear.
3.2. Viscoelastic Properties at Medium Temperatures
3.2. Viscoelastic
3.2.1. Properties
Stress–Strain Responseat Medium Temperatures
3.2.1.Asphalt
Stress–Strain Response
undergoes elastic and plastic deformations in the LAS test under repeated
Asphalt
loading. undergoes
The shear stress elastic
graduallyanddecreases
plastic deformations
when the appliedin the load
LAS reaches
test under repeated
a particular
loading.
point; The shear
however, the stress gradually
shear strain decreases
increases when
in that case.the A applied
peak valueloadofreaches
the sheara particular
stress is
point; however,
observed in the LASthetest’s
shearstress–strain
strain increases
curve.inThe
thatAASHTO
case. A peak value specification
TP 101-12 of the shear stress
definesis
observed
this in theasLAS
peak value test’s stress–strain
the asphalt yield stress, curve.
and itsThe shearAASHTO
strain theTPyield
101-12 specification
strain. Figure 7
defines the
presents thisstress–strain
peak value curvesas the ofasphalt yield
LAS tests ofstress, and its
eight kinds shear strain
of asphalt. the yield
The neat asphalt strain.
has
Figure
the 7 presents
highest the stress–strain
yield stress and the smallestcurves of strain.
yield LAS tests Only ofthe
eight kindswith
SBSMA of asphalt. The and
3.0%, 4.5% neat
asphalt
6.0% has the
contents highest yield
demonstrated stressinand
a peak the the smallest yield
stress–strain curvestrain.
for theOnly
SBSMA.the The
SBSMA orderwith
of
yield
3.0%,stress
4.5%wasand3.0%6.0%> contents
6.0% > 4.5%, and the order
demonstrated of yield
a peak strain
in the was 6.0% >curve
stress–strain 4.5% >for 3.0%.
the
The ranking
SBSMA. Theoforder
yieldofstress
yieldand yield
stress wasstrain
3.0% >is6.0%
inconsistent.
> 4.5%, and Whenthe the content
order of yieldwas greater
strain was
than 6.0%, the stress increases relatively slowly in the loading process.
6.0% > 4.5% > 3.0%. The ranking of yield stress and yield strain is inconsistent. When the With the increase
in strain,was
content the greater
stress gradually
than 6.0%,becomes
the stressflat and the
increases stress–strain
relatively slowly curve
in thedoes not process.
loading show a
peak. Thisincrease
With the findinginindicated that
strain, the the gradually
stress yield stress or yieldflat
becomes strain
and can only characterize
the stress–strain curve
the stress–strain
does not show aresponse
peak. This of finding
asphalt under medium
indicated that thetemperature
yield stressconditions and repeated
or yield strain can only
loadings but cannot
characterize characterize
the stress–strain the fatigue
response properties
of asphalt under of medium
asphalt. temperature conditions
and repeated loadings but cannot characterize the fatigue properties of asphalt.
Polymers 2022,
Polymers 14, 2476
2022, 14, 2476 8 8of
of 16
16

Figure
Figure 7.
7. Stress–strain
Stress–strain response
response of
of asphalt.
asphalt.

Fatigue Life
3.2.2. Fatigue Life
The results of the
The results of the LAS
LAS tests
tests were
were further
further analyzed
analyzed using
using the
the Viscoelastic
Viscoelastic Continuous
Continuous
Damage Mechanics
Damage Mechanics theoretical
theoretical model
model [31].
[31]. Notably,
Notably, the
the LAS
LAS test
test is
is composed
composed ofof frequency
frequency
sweep and
sweep and amplitude
amplitude sweep.
sweep. First,
First, the
the parameter
parameter αα isis acquired
acquired via
via the
the frequency
frequency sweep
sweep
test and is calculated according to Equations (4)–(6) [32,33].
test and is calculated according to Equations (4)–(6) [32,33].
∗ * × cos δ
G0 =
G =| GG| × cos δ (4)
lg 0G==mm(lgω
lgG lg )ω+ +b b (5)
(5)
11 (6)
a a== m (6)
m
where G 0 is the storage modulus (MPa), G*∗ is the complex
is the complex shear
shear modulus
modulus (MPa),
(MPa), δδ is
(◦ ), m
the phase angle (°), m and
and bb are the fitting parameters, a is a parameter for asphalt’s
viscoelastic behavior.
Secondly,
Secondly, the damage variable (D) is calculated, as shown in Equation (7) [34].
N N
a/(a/(1+a)
1+ a )
∼D∑(t)[πγ 2
−i−1 t 1/(1+a) 1/(1+ a)
D (t) = C i−21(C
≅ 0 ([πγ 0
C−Ci )] i )] i−
(ti −t
(t i−1 )i −1 )
(7)
i =1 i=1

where t is the test

test time
time (s), is the
(s), ttii is the current
current test
test time,
time,tti i−1
−1 is
isthe
the previous
previous test
test time,
time, N
N is
is the
total number of tests, C(t) is the integrity parameters, which is calculated by Equation (8).
*
C (C
t) (t)
=|=G ∗G|(t(t)/
)/| GG∗*| initial (8)
(8)
initial

where, G∗* |((t)t) is

where, | G is the
the complex
complex shear
shear modulus
modulus with
with test
test time
time inin the amplitude sweep
the amplitude sweep test
test
*
(MPa), G∗ |initial is
(MPa), | G is the
the complex
complex shear
shear modulus
modulus when
when the
the test
test starts
starts (MPa),
(MPa), γγ0 is
is the
the test
test
initial 0
strain (%).
For
For the
the loss
loss variable
variable (D
(D (t))
(t)) and
and integrity
integrity parameter
parameter (C (C (t)),
(t)), there
there is the following
relationship, as shown in Equation (9).

C (tC) (t)
=C = C−−C [D (t)]CC22 (9)
0 0 C11 [ D ( t )] (9)
where, C0 = 1, C1 and C2 are the fitting parameters.
where, C0 = 1, C1 and C2 are the fitting parameters.
Finally, the fatigue life is calculated, as shown in Equation (10).
Nf = A (γmax )-B (10)
Polymers 2022, 14, 2476 9 of 16

Polymers 2022, 14, 2476 Finally, the fatigue life is calculated, as shown in Equation (10). 9 of 16
Polymers 2022, 14, 2476 9 of 16
N f = A (γmax )− B (10)

where, γγmax isis theexpected

expected maximum strain strain (%) and and A and and B are the
the fatigue correlation
correlation
where,
where, γmax
max
isthe
the expectedmaximum
maximum strain (%) (%) and A A and BB are
are the fatigue
fatigue correlation
coefficients, which
coefficients, which areare calculated
calculated according
according to to Equation
Equation(11) (11)to
toEquation
Equation(12).
(12).
coefficients, which are calculated according to Equation (11) to Equation (12).
[1+(1-C
[f1)+(
 f (D 2 )a]
1− C ) a ]
A = f Df (Df f
)[1+(1-C22)a] a (11)
(11)
A = A = [1+(1-C
[1+(1-C 2 )a](πC1 C2 )a
2))a](πC 1 CC2) )a
(11)
[ 1 + ( 1 − C 2 a ]( πC 1 2
C0 -Cpeak 1/C2
where, f = 10 Hz, Df = ( C0 -Cpeak )1/C2 .
where, f = 10 Hz, D = ( CC0 1−C ) .
where, f = 10 Hz, D ff = ( C1 C peak )1/C2 .
1
B = 2a (12)
B=B =2a2a (12)
(12)
The above calculation results present the damage characteristic curves and fatigue
The above calculation results present the damage characteristic curves and fatigue
life curves of eight
The above kinds ofresults
calculation asphalt (Figures
present the8 and 9). characteristic curves and fatigue life
life curves of eight kinds of asphalt (Figures 8damage
and 9).
curves of eight kinds of asphalt (Figures 8 and 9).

Figure 8.
8. Damage characteristic
characteristic curves of
of asphalt.
Figure 8. Damage
Figure Damage characteristic curves
curves of asphalt.
asphalt.

Figure 9. Fatigue life of asphalt.

Figure 9. Fatigue life of asphalt.
Figure 8 shows that C represents the integrity parameter of asphalt and D represents
Figure 8 shows thatparameter.
C represents the integrity parameter of asphalt and D represents
the cumulative damage expression C
parameter. The expression C = 1 denotes that the asphalt is intact,
the cumulative damage parameter. The expression C = 1 denotes that the asphalt is intact,
expression C
and the expression C == 0 denotes
denotes that
that itit has
has been
been completely
completely damaged.
damaged. Figure 8 shows
shows
and the expression C = 0 denotes that it has been completely damaged. Figure 8 shows
that when the cumulative damage parameter has a certain value, the asphalt’s integrity
that when the cumulative damage parameter has a certain value, the asphalt’s integrity
improves with the rising modifier content. Among them, the neat asphalt’s integrity is the
improves with the rising modifier content. Among them, the neat asphalt’s integrity is the
worst, and the integrity of the 12.0% SBSMA is the best. However, the damage
worst, and the integrity of the 12.0% SBSMA is the best. However, the damage
characteristic curves of 12.0% and 10.5% SBSMA appear staggered, suggesting that with
characteristic curves of 12.0% and 10.5% SBSMA appear staggered, suggesting that with
Polymers 2022, 14, 2476 10 of 16
Polymers 2022, 14, 2476 10 of 16

that when the cumulative damage parameter has a certain value, the asphalt’s integrity
the increase in the damage intensity, the damage resistance of 10.5% SBSMA is higher
improves with the rising modifier content. Among them, the neat asphalt’s integrity is the
than
worst, that
andofthe
12.0%.
integrity of the 12.0% SBSMA is the best. However, the damage characteristic
Figure
curves of 12.0% 9 shows
anddifferent asphalts’
10.5% SBSMA fatigue
appear life at 2.5%
staggered, strain. The
suggesting fatigue
that life of
with the SBSMA
increase in
increases exponentially with the increasing modifier content. This is
the damage intensity, the damage resistance of 10.5% SBSMA is higher than that of 12.0%. because with the
increase in SBS
Figure modifier
9 shows content,
different the distribution
asphalts’ fatigue life atof2.5%
the SBS phase
strain. The in asphalt
fatigue life gradually
of SBSMA
forms
increases exponentially with the increasing modifier content. This is because 70#
a cross-linking state, which increases the fatigue life. Specifically, for Shell withneat
the
asphalt, N f increased by 47.3% after adding 3.0% of the star SBS modifier. For SBSMA,
increase in SBS modifier content, the distribution of the SBS phase in asphalt gradually
when
formsthe content risesstate,
a cross-linking fromwhich
4.5% increases
to 6.0%, the
the fatigue
change life.
rateSpecifically,
of Nf is thefor largest
Shell (63.9%),
70# neat
followed by the change rate from 10.5% to 12.0%, and the change rate
asphalt, Nf increased by 47.3% after adding 3.0% of the star SBS modifier. For SBSMA, from 6.0% to when
7.5%
isthe
thecontent
smallest (2.8%).
rises from 4.5% to 6.0%, the change rate of Nf is the largest (63.9%), followed
by the change rate from 10.5% to 12.0%, and the change rate from 6.0% to 7.5% is the
3.3. Viscoelastic
smalles (2.8%).Properties at Low Temperatures
3.3.1. Modulus and Phase Angle
3.3. Viscoelastic Properties at Low Temperatures
Figures 10 and 11 show the variations in G* and δ, with eight kinds of asphalt
3.3.1. Modulus and Phase Angle
frequencies at −5 °C and −15 °C. The G* of eight types of asphalt increased when the
Figures
frequency was10 gradually
and 11 show the variations
augmented G* rad/s
fromin0.1 and δ,to
with100eight kinds
rad/s, whichof asphalt frequen-
conformed to
cies at − 5 ◦ C and −15 ◦ C. The G* of eight types of asphalt increased when the frequency
Generalized Maxwell model [35]. However, the phase angle change is more complicated.
was
At −5gradually augmented
°C, the phase angle offrom 0.1 rad/s
SBSMA to 100with
decreases rad/s,
thewhich conformed
increasing to Generalized
frequency when the
Maxwell model [35]. However, the phase angle change is more complicated.
content of SBSMA is less than 10.5%. Although the SBSMA with contents of 10.5% At − 5 ◦ C,and
the
phase angle of SBSMA decreases with the increasing frequency when
12.0%, the phase angle decreased and the phenomenon of “first increase and then the content of SBSMA
is less thanwill
decrease” 10.5%. Although
appear the SBSMA
in the change withAt
process. contents
−15 °C,ofthe10.5% and
phase 12.0%,
angle the phase
of SBSMA hasangle
no
decreased and the phenomenon of “first increase and then decrease”
obvious pattern when the◦frequency enlarges. With the rising modifier content, the G* andwill appear in the
change process. At −
δ of SBSMA had little change. The order of the G* and δ of the eight types of asphalt at the
15 C, the phase angle of SBSMA has no obvious pattern when −5
frequency enlarges. With the rising modifier content, the
°C and −15 °C was inconsistent. This may be because in the preparation G* and δ of SBSMA had
of high-contentlittle
change. The order of the G* and δ of the eight types of asphalt at −5 ◦ C and −15 ◦ C was
SBSMA, the same shear time as the low-content SBSMA was used, resulting in a portion
inconsistent. This may be because in the preparation of high-content SBSMA, the same
of the SBS of the high-content SBSMA being too late to swell and cross-link. Additionally,
shear time as the low-content SBSMA was used, resulting in a portion of the SBS of the
each high-content SBSMA is too late to swell and the cross-link of the SBS is different, so
high-content SBSMA being too late to swell and cross-link. Additionally, each high-content
the SBSMA with the increase in the amount of low-temperature viscoelastic properties is
SBSMA is too late to swell and the cross-link of the SBS is different, so the SBSMA with the
also different.
increase in the amount of low-temperature viscoelastic properties is also different.

Figure
Figure10.
10.Modulus
Modulusand
andphase
phaseangle
angleof
ofasphalt
asphaltat
at−5 ◦ C.
−5°C.
Polymers 2022,14,
Polymers2022, 14,2476
2476 11
11 of 16
16

Figure 11. Modulus and phase angle of asphalt at −15 ◦ C.

Figure 11. Modulus and phase angle of asphalt at −15 °C.
3.3.2. Evaluating Index
3.3.2. Evaluating Index
Sui et al. [36] compared the relaxation modulus G (t) master curve according to
the 4Sui mmetDSR
al. [36] compared
test with thethe relaxation
creep stiffnessmodulus
modulus G (t) master
S (t) mastercurve
curveaccording
based on to the
BBR4
mm DSR test with the creep stiffness modulus S (t) master curve based
tests. They showed that G (60 s) and mr (60 s) had an excellent linear correlation with on BBR tests. They
Sshowed thatmGc (60
(60 s) and (60 s).
s) and mr (60 s)Ghad
Therefore, (60 an excellent
s) and mr (60linear
s) arecorrelation
recommended with forS (60 s) and
4 mm DSRmc
(60 s). Therefore, G (60 s) and m (60 s) are recommended for 4 mm
as the evaluation indicator of low-temperature viscoelastic properties of asphalt. While
r DSR as the evaluation
indicator ofGlow-temperature
calculating (60 s) and mr (60viscoelastic properties
s), the primary curveofofasphalt.
storageWhile
modulus (G0 ) of asphalt
calculating G (60 s)
was mr (60
and first s), the by
derived primary
fittingcurve of storage modulus
the time-temperature (G′) of asphalt
equivalence was first
principle. derived(13)
Equation by
fitting the
describes time-temperature
the transformation equivalence
between the primary principle. the G 0 (ω )(13)
curves ofEquation describes
and the the
G (t). Then,
transformation
Equation (14) was between
adopted the
to primary curves
fit the master of the
curve G′ (ω)
of the G (t).and the GG(t).
Finally, (60Then,
s) andEquation
mr (60 s)
(14) was adopted to fit the master curve of the
were counted according to Equations (15) and (16), respectively.G (t). Finally, G (60 s) and mr (60 s) were
counted according to Equations (15) and (16), respectively.
G (t) ≈ G 0 (ω ) ω =2/πt (13)
G (t) ≈ G′ (ω) |ω=2/πt (13)
0
where, G (t) is the relaxation modulus (Pa), G (ω ) is the storage modulus (Pa), t is the test
where, G (t) is the relaxation modulus (Pa), G′ (ω) is the storage modulus (Pa), t is the
time (s), ω is the angular frequency (rad/s).
test time (s), ω is the angular frequency (rad/s).
y = ax2 + bx + c (14)
y = ax2 + bx + c (14)
where,a,a,b,b,and
where, andccare
areparameters
parametersfor
forfitting.
fitting.
G (60
G (60 s) =s) ax 2 2
= ax+bx + +c c| x|=x=1.78
+ bx 1.78 (15)
(15)

mr (m60
r (60 s) 2ax
s) = + +b b| x|=x=1.78
= 2ax
1.78
(16)
(16)
Using −−15
Using 15 ◦°C
C asasthethe reference
reference temperature,
temperature, the master
the master curve ofcurve of the relaxation
the relaxation modulus
of eight kinds of asphalt is drawn in this study (Figure 12). Next, G (60 s) and mr (60s)s)and
modulus of eight kinds of asphalt is drawn in this study (Figure 12). Next, G (60 mr
were
(60 s) were counted (Figures
counted (Figures 13 and 14). 13 and 14).
Polymers 2022, 14, 2476 12 of 16
Polymers
Polymers2022,
Polymers 2022,14,
2022, 14,2476
14, 2476
2476 1212ofof
12 of16
16

Figure 12. Main curve of relaxation modulus of asphalt at low temperatures (−15 °C).
◦ C).
Figure
Figure12.
12.Main
Maincurve
curveof
ofrelaxation
relaxationmodulus
modulusof
modulus ofasphalt
of asphaltat
asphalt atlow
at lowtemperatures
low temperatures(−15
temperatures −15°C).
((−15 °C).

Figure 13. Evaluation index G (60 s) of asphalt at low temperatures.

Figure
Figure 13.
Figure13. Evaluation
13.Evaluation indexGG
index
Evaluationindex (60
(60s)s)
G(60 of
s)of asphalt
ofasphalt at
asphaltat low
atlow temperatures.
lowtemperatures.
temperatures.

Figure
Figure 14.
14. Evaluation
Evaluation index mrr(60
index m (60s)s)of
ofasphalt
asphaltat
atlow
lowtemperatures.
temperatures.
Figure
Figure14.
14.Evaluation indexmmr r(60
Evaluationindex (60s)s)ofofasphalt
asphaltatatlow
lowtemperatures.
temperatures.
Polymers 2022, 14, 2476 13 of 16

Polymers 2022, 14, 2476 13 of 16

Figure 12 plots that the relaxation modulus level of neat asphalt is obviously higher
than that of SBSMA, whereas the relaxation modulus of 3.0% is the largest and that of 12.0%
is Figure 12 plotsFurthermore,
the smallest. that the relaxation modulus
the SBS levelreduced
modifier of neat asphalt is obviously
the asphalt’s highermodulus
relaxation
than that of SBSMA, whereas the relaxation modulus of 3.0% is the largest
level, lowering the temperature stress accumulation inside the asphalt and improving and that of its
12.0% is the smallest. Furthermore, the SBS modifier reduced the asphalt’s relaxation
cracking resistance at low temperatures.
modulus level, lowering the temperature stress accumulation inside the asphalt and
Figure 13 shows the low-temperature property evaluation index G (60 s) of asphalt. It
improving its cracking resistance at low temperatures.
is shown that the G (60 s) of SBSMA decreased logarithmically with the increasing modifier
Figure 13 shows the low-temperature property evaluation index G (60 s) of asphalt.
content. For Shell 70# neat asphalt, G (60 s) decreased by 39.5% after adding 3.0% content.
It is shown that the G (60 s) of SBSMA decreased logarithmically with the increasing
For SBSMA,
modifier content.when it rises
For Shell from
70# neat 9.0% G
asphalt, to(60
10.5%, the change
s) decreased of Gadding
rateafter
by 39.5% (60 s) 3.0%
is the largest.
content. For SBSMA, when it rises from 9.0% to 10.5%, the change rate of G (60 s) is4.5%
In contrast, the change rate is the smallest when the content increases from the to 6.0%.
Figure 14 shows the asphalt’s low-temperature property evaluation
largest. In contrast, the change rate is the smallest when the content increases from 4.5% index m r (60 s). With
the increasing SBS modifier content,
to 6.0%. Figure 14 shows the asphalt’s low-temperature m r (60 s) shows
property evaluation index mr (60 which is
no apparent change law,
s). With the increasing SBS modifier content, mr (60 s) showscurves
attributed to the different slopes of relaxation modulus of different
no apparent changetypes
law,of asphalt
in 60
which is s. Importantly,
attributed to theusing mr (60
different s) to
slopes ofdetermine the low-temperature
relaxation modulus property
curves of different types of SBSMA
is still worthy
of asphalt of in-depth discussion
in 60 s. Importantly, using mr (60ands) toresearch.
determine the low-temperature property
of SBSMA is still worthy of in-depth discussion and research.
3.4. Phase Structure of SBSMA
3.4. PhaseFigure
Structure of SBSMA the microscopic phase structures of the eight kinds of asphalt
15 illustrates
Figure
under 15 illustrates
a 100-fold the microscopic
fluorescence phase structures of the eight kinds of asphalt
microscope.
under a The
100-fold fluorescence
microscopic microscope.
phase structure of SBSMA is a two-phase (SBS phase and asphalt
The microscopic
phase) coexistencephase of thestructure
co-blended of SBSMA is a system
structural two-phase (SBS phase
compared andneat
to the asphalt
asphalt. The
phase)
phase structure varies with the SBS modifier content. When the SBS modifier The
coexistence of the co-blended structural system compared to the neat asphalt. content rises
phase
fromstructure
3.0% tovaries
12.0%, with
thethe SBS modifier
distribution content.
state of SBSWhen
phase theinSBS modifier
asphalt phasecontent rises forms a
gradually
from 3.0% to 12.0%, the distribution state of SBS phase in asphalt phase
cross-linking state; that is, the SBS modifier gradually changes from the dispersed to thegradually forms
a cross-linking
continuous state;
phasethat is, the
state. ThisSBS modifieras
is because gradually changes
the modifier from thethe
increases, dispersed
numbertoofthe particles of
continuous phase state. This is because as the modifier increases, the number of particles
the modifier increases, and its specific surface area increases significantly. Under the action
of the modifier increases, and its specific surface area increases significantly. Under the
of surface tension, the modifier particles are more likely to agglomerate. Specifically, when
action of surface tension, the modifier particles are more likely to agglomerate.
this content is 3.0% and 4.5%, the SBS modifier is in the dispersed phase state, whereas
Specifically, when this content is 3.0% and 4.5%, the SBS modifier is in the dispersed phase
the neat asphalt is in the continuous phase state. The 4.5% content of the SBS modifier
state, whereas the neat asphalt is in the continuous phase state. The 4.5% content of the
SBSdispersion is more uniform
modifier dispersion than the
is more uniform 3.0%
than the content of the
3.0% content of SBS modifier.
the SBS modifier. When
Whenit reaches
6.0%, the SBS modifier is also present in the dispersed
it reaches 6.0%, the SBS modifier is also present in the dispersed phase. Moreover, phase. Moreover, a aparticular
network structure appears and the SBS modifier gradually
particular network structure appears and the SBS modifier gradually changes from the changes from the dispersed to
the continuous phase state. When the SBS modifier content is
dispersed to the continuous phase state. When the SBS modifier content is 7.5% and 9.0%,7.5% and 9.0%, the two phases
theof the
two blendofare
phases the continuous, and the and
blend are continuous, modifier-formed
the modifier-formednetwork structure
network is intertwined
structure is
intertwined with each other. Compared with the 7.5% content of the SBS modifier, thestructure
with each other. Compared with the 7.5% content of the SBS modifier, the mesh
meshformed by the
structure 9.0%by
formed content
the 9.0% is content
more closely
is moreintertwined. When this
closely intertwined. When content reaches 10.5%
this content
and 12.0%,
reaches 10.5% andthe12.0%,
SBS modifier becomesbecomes
the SBS modifier a continuous phase phase
a continuous state, state,
whereas the neat
whereas the asphalt
neat asphalt abecomes
becomes dispersed a dispersed
phase state, phaseandstate, and the network
the formed formed network
structure structure
exhibitsexhibits
a rough surface
a rough surface
and large and large interwoven
interwoven “leaf”. In“leaf”. In contrast,
contrast, the 12.0% the SBSMA
12.0% SBSMA had ahad a rougher
rougher surface and
surface
largerand larger interwoven
interwoven “blade”“blade”
than the than the 10.5%
10.5% SBSMA. SBSMA.

(a) (b)

Figure 15. Cont.

Polymers 2022, 14, 2476 14 of 16
Polymers 2022, 14, 2476 14 of 16

(c) (d)

(e) (f)

(g) (h)
Figure 15.15.
Figure Fluorescent microscopic
Fluorescent images
microscopic of asphalt.
images (a) Neat(a)
of asphalt. asphalt, (b) 3.0% SBSMA,
Neat asphalt, (b) 3.0%(c)SBSMA,
4.5% (c) 4.5%
SBSMA, (d) 6.0% SBSMA, (e) 7.5% SBSMA, (f) 9.0% SBSMA, (g) 10.5% SBSMA, (h) 12.0% SBSMA.
SBSMA, (d) 6.0% SBSMA, (e) 7.5% SBSMA, (f) 9.0% SBSMA, (g) 10.5% SBSMA, (h) 12.0% SBSMA.
4.4.
Conclusions
Conclusions
(1)(1) With
Withthetheincreasing
increasingSBS
SBSmodifier
modifier content
content(3.0–12.0%),
(3.0–12.0%), thethe
non-recoverable creep
non-recoverable creep com-
compliance of SBSMA drops with the growing creep recovery rate. The
pliance of SBSMA drops with the growing creep recovery rate. The modifier content modifier
content increases
increases the high-temperature
the high-temperature viscoelastic
viscoelastic performance
performance of SBSMA.
of SBSMA. An turn-
An obvious
obvious turning point was observed in the change in non-recoverable creep
ing point was observed in the change in non-recoverable creep compliance and creep
compliance and creep recovery rate, which is bounded by the 4.5% content. The
recovery rate, which is bounded by the 4.5% content. The changing slope of the
changing slope of the content less than 4.5% is much higher than that of the content
content less than 4.5% is much higher than that of the content greater than 4.5%.
greater than 4.5%.
(2) The fatigue life of SBSMA increases exponentially with the increasing modifier content.
(2) The fatigue life of SBSMA increases exponentially with the increasing modifier
Moreover,
content. the growth
Moreover, rate rate
the growth of fatigue life life
of fatigue is the largest
is the (63.9%)
largest (63.9%)when
whenthe
the content
increases from 4.5% to 6.0%.
content increases from 4.5% to 6.0%.
(3) The 4 mm DSR test can evaluate the viscoelastic performance of SBSMA at low
temperatures. G (60 s) and mr (60 s) were selected as evaluation indicators. The
G (60 s) of SBSMA decreases logarithmically with the increasing modifier content
Polymers 2022, 14, 2476 15 of 16

(3.0–12.0%). However, mr (60 s) has no noticeable change with the rising content. The
SBS modifier cut down the low-temperature relaxation modulus of asphalt.
(4) In terms of the microscopic phase structure, the microscopic phase structure of SBSMA
is a two-phase (SBS modifier and neat asphalt) coexistence of the co-blended structural
system. With the increasing SBS modifier content, the SBS modifier gradually changes
from a dispersed to a continuous phase state. When the modifier amount is less than
6.0%, the SBS modifier is present in a dispersed phase. Similarly, when the modifier is
more than 6.0%, the SBS modifier is present in the continuous phase.
(5) The viscoelastic properties of high-content SBS modified asphalt at different temper-
ature were investigated, and the phase structure of different content SBS modified
asphalt were clarified. The chemical composition of high-content SBS modified asphalt
and its aging characteristics will be studied in the next step.

Author Contributions: Conceptualization, W.J. and J.X.; methodology, D.Y.; software, C.X.; valida-
tion, D.Y., C.X. and J.X.; formal analysis, D.Y.; investigation, D.Y.; resources, W.J.; data curation, P.L.;
writing—original draft preparation, D.Y.; writing—review and editing, Y.L. and W.W.; visualization,
W.W.; supervision, C.X. and W.J.; project administration, W.J.; funding acquisition, W.J. All authors
have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China, grant
number 52122809 and 52038001, the Fok Ying-Tong Education Foundation, grant number 161072, the
Youth Top-notch Talent Support Program of Shaanxi Province, the Fundamental Research Funds for
the Central Universities-Excellent doctoral cultivation project of Chang’an University, grant number
300203211215, the China Scholarship Council (CSC), grant number 202006560054.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Access to any other materials can be requested by writing to the
corresponding authors.
Conflicts of Interest: The authors declare no conflict of interest.

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