Construction and Building Materials 249 (2020) 118748

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Construction and Building Materials

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

Behaviors of asphalt under certain aging levels and effects of

rejuvenation
Tao Zhou a,b, Liping Cao a,⇑, Elham H. Fini b, Lingwen Li a, Zhiyang Liu a, Zejiao Dong a
a
School of Transportation Science and Engineering, Harbin Institute of Technology, Harbin, Heilongjiang 150090, PR China
b
School of Sustainable Engineering and the Built Environment, Arizona State University, Tempe, AZ 85287, United States

h i g h l i g h t s

RTFO time was used to control the level of asphalt aging.

Asphaltene micelles increased with aging and decreased with rejuvenation.

Physical and rheological property changes were inconsistent after rejuvenation.

Rejuvenator restored aged asphalts close to their unaged level but not completely.

Field-aged asphalt was fully restored except for asphaltene content and ductility.

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

Article history: Aging has an undesirable effect on asphalt properties, which can be restored by rejuvenation. In this
Received 22 December 2019 study, neat asphalt was aged by the standard rolling thin-film oven (RTFO) test with varying times to
Received in revised form 1 March 2020 obtain asphalts at different levels of aging; these asphalts were then rejuvenated to their original pene-
Accepted 12 March 2020
tration grade. Analysis of the asphalt fractions, Fourier-transform infrared spectroscopy (FTIR), and
atomic force microscopy (AFM) were employed to investigate the evolution of the distributions of
SARA fractions, the functional groups, and the microstructures during aging and rejuvenation. Physical
Keywords:
and rheological properties were tested to evaluate the pavement performance of the asphalts. The results
Asphalt aging
Asphalt rejuvenation
showed that aging can convert the aromatics to resins and further to asphaltenes, and increase the car-
Fraction distribution bonyl and sulfoxide contents due to oxidation. Consequently, the micelle number and proportion in the
Functional groups colloidal structure increased at the micro-scale, and the penetration and ductility decreased while the
Microstructures softening point increased at the macro-scale. These trends were more evident at increased aging levels.
A rejuvenator with a high content of aromatics can adjust the fractions and dilute the aggregated micelles
in aged asphalt, thus achieving the thermodynamically reversible process of the asphaltenes and resins
being converted to saturates and aromatics; this balances the fraction distribution and restabilizes the
colloidal structure. The performance-related properties were basically restored to their unaged levels.
Comparing the results of the aged asphalts from the laboratory and field, the ductility and asphaltene
content of the latter cannot be restored to their original level, though other properties can be, which indi-
cates the complex service conditions of asphalt in the field.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction viscosity and stiffness) in the asphalt [1]. This phenomenon is

Asphalt, like any organic matter, is affected by natural factors
like heat, oxygen, ultraviolet (UV), and so on. During its construc-
tion and long-term service life, these effects on the asphalt cause
changes in performance-related properties, which mainly result
in hardening and an increase in brittleness (that is, an increase in
⇑ Corresponding author.
E-mail address: caoliping79@163.com (L. Cao).
known as asphalt aging. Aging can change the chemical and phys-
ical properties, as well as the pavement performance, of the asphalt
irreversibly. However, aged asphalt can be partially or even fully
restored to its original state if proper measures are taken. Restora-
tion occurs by following a thermodynamically reversible process
known as rejuvenation; use of this process ensures the recycling
of non-renewable resources and the sustainable development of
pavement engineering. But, the aging and rejuvenation process is

https://doi.org/10.1016/j.conbuildmat.2020.118748
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
2 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748
very complex due to the chemical and structural complexity of
asphalt as well as the service environment of pavement.
Asphalt aging usually occurs in two stages: short-term aging
and long-term aging [2]. The former occurs during the construction
of the pavement, including mixing, paving, and compaction. It is
mainly caused by heat and oxygen acting on the asphalt thin-
film, which coats the aggregate surface and is 6 um to 9 um thick
[3], since the asphalt is usually heated to 140 °C to 165 °C to
decrease its viscosity and ensure sufficient workability for con-
struction. This aging effect is mainly manifested in the oxidation
of asphalt and loss of its lightweight molecular components, and
is usually simulated by the rolling thin-film oven (RTFO) test.
Long-term aging usually occurs throughout the entire service life
of the pavement and is caused by many factors, such as heat, oxy-
gen, UV, and even moisture [4–6], and is usually simulated by the
pressure aging vessel (PAV) test.
Regardless of whether the aging is short-term or long-term
aging, three phenomena have been reported and are commonly
accepted to interpret the aging behavior of asphalt, that is, physical
hardening, the evaporation of the light components, and oxidation.
Physical hardening, also known as steric hardening, usually
changes the viscoelastic properties without altering the chemical
composition of asphalt [7] and is reversible either by heating the
asphalt above the softening point or by prolonged mechanical
working [8]. The evaporation of the light components mainly
involves the saturates and aromatics (of which volatile compo-
nents exist), as well as the condition temperature of the asphalt
(especially during the pavement construction stage). However, it
is believed that the loss of the light components has a limited effect
on asphalt aging compared with the effect of oxidation [9], as oxi-
dation causes chemistry-related changes in the asphalt. And unlike
physical hardening, thermal reactions between oxygen from the air
and the components of asphalt can change the chemical character-
istics of the asphalt in a way that is irreversible [10].
Due to the importance of asphalt aging, which is directly related
to the longevity and durability of asphalt pavement, considerable
effort has been dedicated to research on asphalt aging behavior,
including both the process and the mechanism. This research
includes simulated tests in the laboratory, such as the thin-film
oven test (TFOT), RFTO test, PAV test, and UV test [11], and tests
in natural environment conditions [12]. Additionally, traditional
laboratory tests (of physical and rheological properties) and
advanced chemical characterization analysis by Fourier-
transform infrared spectroscopy (FTIR) [13], atomic force micro-
scopy (AFM) [14], thin-layer chromatography with flame ioniza-
tion detection (TLC-FID) [15], and so on, and molecular
simulation [2,16] were employed to analyze physical and chemical
aspects of asphalt aging at the macro and micro levels, thus provid-
ing a deeper understanding of asphalt aging.
Since asphalt aging is unavoidable, measures should be taken to
recover the performance of aged asphalt. One effective method is
asphalt rejuvenation. Rejuvenation is the inverse process of aging;
a rejuvenator is usually added into aged asphalt to restore its prop-
erties. During aging, partial aromatics convert to resins, and further
to asphaltenes [17], which increases the amount of resins and
asphaltenes and decreases the aromatics, thus causing dispropor-
tionate fractions in aged asphalt. The incorporation of a rejuvena-
tor can adjust the asphalt’s saturate, aromatic, resin and
asphaltene (SARA) fractions by adding to the fractions that lost
during aging, balancing the content of each fraction. This method
is known as fraction adjustment theory [18] and provides a base
for the research and development of an aromatics-rich asphalt
rejuvenator. Asphalt rejuvenation also requires that the content
of saturates not be too high, that the content of aromatics reach
a certain value, and that little or no asphaltene be present, for
the asphalt rejuvenator to qualify in pavement recycling.
Another theory about asphalt rejuvenation is the compatibility
theory [18]. This theory is from thermodynamics and states that
aging increases the difference in solubility parameter between
the asphalt fractions. Hence, the key point of rejuvenation is to
decrease this difference, which can be accomplished by adding
a rejuvenator that has moderate solubility parameter, thus restor-
ing the performance of the asphalt to its original level. In this
regard, several studies have investigated aged-asphalt rejuvena-
tion, such as studies on rejuvenator diffusion [19,20], asphalt
transfer between aged and fresh binders [21], and the effect of
rejuvenator components on the effectiveness of the rejuvenation
[22,23].
Researchers have devoted much effort to investigating asphalt
that has already aged, in regards to rejuvenation, and continuously
contribute new understanding in this area. However, asphalt ages
step by step, over time; hence, it’s important to explore what
action must be taken and when, before the service performance
of pavement worsens. Before we can answer that question, the
behavior of asphalt at various stages of aging (or aging levels)
should be understood more deeply, and the effects of rejuvenation
also need further investigation.
This research investigates the aging and rejuvenation behaviors
of asphalt to understand how aging and rejuvenation affect the
SARA fractions, functional groups, microstructure, and
performance-related properties of the asphalt. Neat asphalt was
aged using an RTFO under standard conditions with various aging
times to obtain asphalt samples with various aging levels. Subse-
quently, different dosages of rejuvenator (optimized) were incor-
porated into the aged asphalt to restore the aged asphalt to its
original penetration grade. The contents of the four fractions were
acquired by SARA analysis to study the fractions’ distribution
change. Specific functional groups were compared by FTIR analysis.
The evolution of the microstructure, in terms of micelle number
and proportion, was explored using AFM in tapping mode. Basic
performance-related properties were tested through physical and
rheological experiments. Recovered asphalt (RA) from reclaimed
asphalt pavement (RAP) was compared with the aged asphalt from
the laboratory simulation.
2. Materials and methods
2.1. Materials used
Conventional petroleum-based PEN 90 asphalt (P90) from Pan-
jin Petrochemical Company (Panjin, Liaoning, China) was used as
the control asphalt, and was aged to different levels in the labora-
tory. The recovered asphalt (RA) was extracted from the reclaimed
asphalt pavement (RAP) of the Hashuang expressway in the Hei-
longjiang Province of China after severing for thirteen years. RA1
rejuvenator (RE) from Jilin Jiapeng Group (Changchun, Jilin, China)
was used to rejuvenate the aged asphalts and RA; the RE is classi-
fied as an RA1 recycling agent according to the standard practice of
ASTM D4552. The fundamental properties of P90 and RE are given
in Table 1 and Table 2, respectively.
Table 1
Fundamental properties of P90.
Properties Testing value Testing methods
Specific gravity 1.028 ASTM D70
Penetration at 25 °C (0.1 mm) 87.1 ASTM D5
Softening point (°C) 45.1 ASTM D36
Ductility at 15 °C (cm) >100 ASTM D113
Viscosity at 90 °C (Pas) 4.627 ASTM D4402
Viscosity at 135 °C (Pas) 0.294 ASTM D4402
 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748
Table 2
Fundamental properties of RE.
Properties Testing Testing methods
value
Viscosity at 60 °C (cSt) 91.58 ASTM D2170
Flash point (°C) 226 ASTM D92
Saturates (wt %) 25.87 ASTM D4124
Aromatics (wt %) 33.46 ASTM D4124
Viscosity ratio of before and after TFOT 1.11 ASTM D2170, ASTM
at 60 °C D1754
Mass loss before and after TFOT (%) 3.52 ASTM D6
Density at 15 °C (g/cm3) 0.997 ASTM D70
2.2. Experimental procedure
2.2.1. Aged asphalt preparation
Aged asphalts used in this study include both laboratory-aged
asphalts and those extracted directly from samples recovered from
the field. The standard test method of ASTM D2872 recommends
85 min as the condition time for the asphalt RTFO test. To under-
stand the effect of condition time on the properties of the asphalt,
the control asphalt P90 was placed in the RTFO for 75 min, 85 min,
150 min, 180 min, 300 min, and 600 min at standard temperature
and airflow. According to the penetration at 25 °C (ASTM D5), the
laboratory-aged asphalts were characterized as three types corre-
sponding to the certain aging level: P50, P30, and P10, with pene-
trations of 50 ± 5 (0.1 mm), 30 ± 5 (0.1 mm), and 10 ± 2 (0.1 mm),
respectively. The RA was extracted from the RAP by trichloroethy-
lene according to ASTM D2172, and the recovery process was com-
pleted using a rotary evaporator according to ASTM D5404.
2.2.2. Aged asphalt rejuvenation
RE was added into the aged asphalts (P50, P30, P10, and RA)
with different contents to ensure that the rejuvenated asphalts
(P50-RE, P30-RE, P10-RE, and RA-RE) had a penetration of 90 ± 5
(0.1 mm). The rejuvenating process was implemented using a pro-
peller mixer, BME-100L (Weikang Machinery Manufacturing Com-
pany, Shanghai, China) at a speed of 1500 rpm for 15 min at
145 ± 5 °C.
2.2.3. Characterization of asphalt properties
SARA analysis (ASTM D4124) was used to evaluate the change
in asphalt fractions during the aging and rejuvenation processes.
Fourier-transform infrared spectroscopy (FTIR) with a Perkin-
Elmer LR 64912C (Perkin-Elmer, Waltham, Massachusetts, USA)
was used to determine the functional groups of the asphalts at
wavenumbers from 4000 cm1 to 650 cm1. Atomic force micro-
scopy (AFM) with a Dimension Fastscan from Bruker Corporation
(Billerica, Massachusetts, USA) was used to observe the
microstructures of the asphalts at room temperature by applying
a silicon-nitride probe in tapping mode. Penetration at 25 °C (ASTM
D5), softening point (ASTM D36), and ductility at 15 °C (ASTM
D113) were measured to evaluate the basic performance of the
asphalts. A DHR-2 rheometer from TA Instruments (New Castle,
Delaware, USA) was used to test the rheological properties; parallel
plates (10 rad/s; 8 mm diameter with 2 mm gap for 10 °C, 25 °C,
and 40 °C; 25 mm diameter with 1 mm gap for 50 °C, 60 °C, and
70 °C) were chosen in the oscillation frequency sweep, and cone
plate (25 mm diameter with 2° angle, 105 um gap at 60 °C) were
chosen in the flow sweep.
Fig. 1 summarizes the experimental procedure of this study,
and the labels, definitions, and descriptions of the asphalts, used
hereafter, are given in Table 3.
3
3. Results and Discussion
3.1. Asphalt aging and rejuvenation
Fig. 2 shows the penetration of P90 at different RTFO aging
times. A mathematical model [24] was used to produce the regres-
sion line of the penetration versus RTFO aging time; this regression
line was then used to determine the RTFO aging time needed to
obtain aged asphalts with specific penetrations (50, 30, and 10,
0.1 mm). The effect of aging time on penetration varies widely at
different stages of aging. The penetration decreases rapidly within
the first 200 min and slows after 200 min. For instance, the pene-
tration decreased from 87.1 (0.1 mm) to 30 (0.1 mm) in 170 min,
and further to 10 (0.1 mm) in about 400 min; this decrease was
far more than that observed previously for these aging times.
According to the relationship between the penetration and the
aging times of the asphalt, specific penetration grades—P50, P30,
and P10, with penetrations of 50 ± 5 (0.1 mm), 30 ± 5 (0.1 mm),
and 10 ± 2 (0.1 mm), respectively—were obtained at aging times
of 80 min, 170 min, and 600 min, respectively.
Thermo-oxidative aging can change the physical properties,
chemical components, and colloidal structure of asphalt, thus
increasing the molecular weight and viscosity, and making the
asphalt become stiff and brittle, which directly influences its pave-
ment performance. Hence, a rejuvenator with medium molecular
weight, containing high contents of saturates and aromatics that
could soften the asphalt and replenish the depleted fractions that
resulted from aging, was added into the aged asphalts (P50, P30,
P10, and RA) to restore the aged asphalts to their original state.
The significant effect of asphalt regeneration is softening and the
recovery of viscosity. Conventional methods for determining the
appropriate amount of rejuvenator are based on blending charts
of basic asphalt properties such as penetration, softening point,
ductility, and viscosity. In this study, penetration was used to
select the optimum rejuvenator content. The penetration of aged
asphalts containing different contents of RE is presented in Fig. 3.
The optimum content of RE is calculated based on its rejuvena-
tion effect. In this study, the basis for determining whether the
aged asphalt was rejuvenated was that the penetration of the
asphalt reached 90 ± 5 (0.1 mm). Accordingly, the optimum
dosages for P50, P30, P10, and RA were 6.4%, 11.4%, 26.5%, and
15.6%, respectively.
3.2. Distribution of SARA fractions
As the by-product of petroleum, asphalt contains a considerable
variety of components that make it impossible to determine the
exact chemical composition. As a result, different fractions—that
is, saturates, aromatics, resins, and asphaltenes, known as SARA
fractions—which relate to the pavement performance of asphalt
were proposed to chemically characterize asphalt and represent
its basic chemical composition, according to their polarizability
and polarity [25]. Asphalt performs well in pavement only when
these fractions have a good proportion.
Fig. 4 shows the changes in the distribution of the SARA frac-
tions during asphalt aging and rejuvenation. The figure shows that
the content of asphaltenes and resins increased after asphalt aging,
and the increase in asphaltenes was significantly higher than that
of resins. At the same time, the content of aromatics declined sig-
nificantly, and this trend was more noticeable with increasing
aging time. The saturate content changed little with aging and
shows inertia during the aging process. The four fractions of
asphalt undergo a process in which aromatics convert to resins
and further to asphaltenes, as reported in previous studies
[17,18]; the trend becomes more pronounced with increasing
4 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748

Fig. 1. Flowchart of the experimental procedures. P90 is aged at various levels, resulting in P50, P30, and P10. RAP recovery results in RA. All four materials are rejuvenated,
resulting in P50-RE, P30-RE, P10-RE, and RA-RE. These aged and rejuvenated materials are analyzed by various methods.

Table 3 After rejuvenating by adding the rejuvenator, the content of

List of the asphalts used. asphaltenes and resins decreased, and the content of aromatics
Label Definition and description increased. The content of aromatics of the rejuvenated asphalt
P90 Petroleum-based asphalt PEN 90, penetration ranges from 80 to
was even higher than that of the control asphalt P90, and the resin
100 (0.1 mm). content was even lower than that of the P90. However, the asphal-
P50 P90 aged in an RTFO for 80 mina, penetration is equal to 50 ± 5 tene content was still higher than that of the control asphalt. These
(0.1 mm). results indicate that adding the rejuvenator caused not only a
P30 P90 aged in an RTFO for 170 mina, penetration is equal to 30 ± 5
physical supplement of the depleted fractions, but also chemical
(0.1 mm).
P10 P90 aged in an RTFO for 600 mina, penetration is equal to 10 ± 2 conversion; that is, some asphaltenes and resins converted to aro-
(0.1 mm). matics and saturates during the rejuvenation process. As for the
RA Recovered asphalt from RAP, recovered using the rotary aged asphalt RA from RAP, although the rejuvenator adjusted the
evaporator. SARA fractions of the RA, bringing them closer to those of fresh
P50-RE P50 rejuvenated with a rejuvenator content of 6.4%b.
P30-RE P30 rejuvenated with a rejuvenator content of 11.4%b.
asphalt, the asphaltene content was far greater than that of the
P10-RE P10 rejuvenated with a rejuvenator content of 26.5%b. P90. This difference can affect the properties of the asphalt, as
RA-RE RA rejuvenated with a rejuvenator content of 15.6%b. asphaltenes are the most polar and largest molecule of the SARA
a,b
The basis of determining RTFO time and rejuvenator content will be presented in
fractions, and contribute to the high viscosity of asphalt [26]. This
the Results and Discussion section. was also proved by the physical properties results in a later section.

3.3. Specific functional groups studied by FTIR

Aging can affect the chemical characteristics of asphalt. These

Fig. 2. Penetration at different RTFO aging times.
aging level. Comparing the aged asphalts from the laboratory sim-
ulation and the field RAP shows that asphalt aged in a service envi-
ronment for thirteen years is equivalent to asphalt aged in the
RTFO for 300 min to 600 min. Thus, the RTFO can simulate long-
term asphalt aging in a service environment if the conditions are
chosen properly.
characteristics can be determined by changes in the functional
groups, changes that correspond to different transmittance in the
FTIR spectrum, as shown in Fig. 5. In the infrared spectrum, the dif-
ferent transmittance values among the asphalts indicated that the
functional groups changed during aging and rejuvenation. As
shown in Fig. 5, the transmittance changes occurred in the peaks
located at 1700 cm1 and 1030 cm1, corresponding to the car-
bonyl (C@O) and sulfoxide (S@O) groups, respectively. These two
functional groups are usually strengthened by the oxidation, con-
densation, and dehydrogenation reactions caused by aging, and
can be used to show the level of asphalt aging [10,15]. These
changes also align with the mechanism of free-radical reaction
[27,28]; that is, the light components volatilize, the aromatic con-
tent decreases, and the asphaltenes with their macromolecular
structure increase and agglomerate. As the level of aging increases
(from P50 to P10), the absorbance at 1700 cm1 gradually
increases. A similar result occurs at the 1030 cm1 absorption
peak, but the trend is not as obvious as it is with the peak at
1700 cm1. In addition, there is no obvious absorption peak at
1700 cm1 for the control asphalt P90 and the rejuvenator, but
the sulfoxide already existed, as shown in Fig. 5, as reported in pre-
 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748 5

Fig. 3. Penetration of aged asphalts containing different contents of RE: (a) P50; (b) P30; (c) P10; and (d) RA.

Fig. 4. Distributions of the SARA fractions of the control, aged, and rejuvenated asphalts.

vious research [29]. Hence, it is reasonable to believe that the reju-
venation cannot reduce the sulfoxide significantly, but can reduce
the carbonyl significantly. A similar phenomenon occurred in the
aged asphalt RA, as shown in Fig. 5.
To qualitatively analyze the asphalt aging and rejuvenation, the
aging indexes of carbonyl (IC=O) and sulfoxide (IS=O) were calculated
by Eqs. (1) and (2) [13] using the software PerkinElmer Spectrum,
and the results are given in Table 4.
Area of the carbonyl peak around 1700 cm1
IC ¼ O ¼
Area of the peaks between 2000 and 650 cm1
Area of the sulfoxide peak around 1030 cm1
IS ¼ O ¼
Area of the peaks between 2000 and 650 cm1
Table 4 shows that the control asphalt P90 has little carbonyl,
with IC=O almost zero, and that aging significantly affects the car-
bonyl functional group, as IC=O increases noticeably with aging
time. Comparing with the aged asphalts from the laboratory, the
RA has the highest IC=O; the reason is that the asphalt suffered
not only heat and oxygen but also UV radiation during its service
life. After rejuvenating, the IC=O decreased obviously, which indi-
cated that the rejuvenator had a positive effect on the recovery
of the chemical characteristics of the aged asphalt.
By contrast, aging did not affect IS=O as much as it did IC=O. On
ð1Þ
one hand, sulfoxide already existed in the control asphalt and reju-
venator; on the other hand, thermo-oxidative aging has a more sig-
nificant effect on carbonyl compared with sulfoxide. These two
ð2Þ
factors combined caused the change in IS=O for asphalts after aging
6 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748

Fig. 5. FTIR spectrum of the asphalts.

Table 4 the formation of micelles is related to asphaltenes; hence, the

Bond indexes of control, aged, and rejuvenated asphalts. increase in the number of micelles reflects an increase in asphal-
Asphalt IC=O IS=O tene content. This result is consistent with the SARA analysis, that
P90 0.005 0.024
aging can increase the asphaltene content in asphalt. Fig. 6(b)
P50 0.024 0.024 shows that the morphology and distribution of the micelles in
P30 0.031 0.027 the rejuvenated asphalt is basically the same as in the control
P10 0.045 0.036 asphalt P90. The softening of asphalt during regeneration is a phys-
RA 0.052 0.079
ical process, and it requires penetration and dilution; that is, the
P50-RE 0.023 0.026
P30-RE 0.019 0.030 rejuvenator diffuses into the asphaltene micelles and achieves
P10-RE 0.027 0.037 the inverse process, that the asphaltenes convert to resins and fur-
RA-RE 0.035 0.081 ther to aromatics. The same is true for the RA; both the number
and size of the micelles were reduced after rejuvenating, as shown
in Fig. 6(c).
To better analyze and compare the AFM microstructures of the
and rejuvenating to be not significant. RA had the highest IC=O and control, aged, and rejuvenated asphalts, Image Pro-Plus software
IS=O either before or after rejuvenating, which also demonstrates was used to calculate the number and area of the micelles (dark
the complexity of asphalt aging in a service environment. area) in the phase images at the scale of 20 um  20 um. These
results are shown in Table 5.
As shown in Table 5, the micelle number after aging decreased
3.4. Microstructures analyzed by AFM
while the average micelle area and its proportion increased; this
trend negatively and positively correlated with time, respectively.
Aging and rejuvenation can significantly affect the distribution
This is because aging induced the aggregation of the micelles (cor-
of SARA fractions and the chemical characteristics of asphalt, and
responding to the increase in single-micelle area), which was
these effects will induce changes in microstructure. This research
related to the increase in asphaltene content, thus leading to the
analyzes the microstructure of the aged and rejuvenated asphalts
decrease of micelle number at the same observation scale (20
using AFM. This study proposes a phase image that refers to the
um  20 um). The results concluded from the AFM analysis were
phase lag between the signal that drives the cantilever oscillation
consistent with those of the SARA analysis. After aging, the content
and its output signal; changes in the phase lag reflect variations
of asphaltenes and resins increased significantly; the proportion of
in the mechanical properties of the sample surface, such as compo-
dark area in the AFM phase images gradually increased, which
sition, adhesion, friction, and viscoelasticity, as well as other fac-
indicates that AFM phase images can reflect the evolution of the
tors. The AFM phase images of the control, aged, and rejuvenated
asphalt aging process. In addition, the AFM phase images of P10
asphalts are shown in Fig. 6. Traditionally, the colloidal model of
differ significantly from those of the other aged asphalts, which
asphalt has micelles (an asphaltene core encircled by resins) with
confirms the technical specification for asphalt pavement recycling
high viscosity, with a radius of a few nanometers, dispersed in an
(JTG FG41-2008) that aged asphalt penetration should not be less
oily liquid phase (saturates and aromatics) with low viscosity
than 20 (0.1 mm). Fig. 6 and Table 5 also show that the micelle pro-
[30]; asphalt can be divided into three types: sol structure, gel
portion of RA is higher than that of P30, which is consistent with
structure, and sol-gel structure, determined by the relative amount
the results of the SARA analysis, that the asphaltene and resin con-
of asphaltenes and maltenes [31,32].
tent in the RA is higher than the content in the P30.
As shown in Fig. 6, there are two distinct areas in the phase
After rejuvenating, the phase images of P50-RE and P30-RE are
images: the light area with a high phase angle and the dark area
very close to those of the control asphalt P90, while the micelle
with a low phase angle, which correspond to the harder asphaltene
proportions are slightly lower than that of the P90 due to the con-
micelles with higher viscosity and the softer, oily liquid maltenes
tent of asphaltene and resin in the rejuvenated asphalts being low.
with lower viscosity, respectively. In Fig. 6(a), the number of
Therefore, the average area of the micelles declined, indicating that
micelles increases gradually with increasing aging time at both
the rejuvenator can dissolve big micelles into small micelles. As for
scales, 20 um  20 um and 5 um  5 um. As mentioned above,
 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748 7

Fig. 6. AFM phase images of the asphalts: (a) control and aged asphalts (top: 20 um  20 um; bottom: 5 um  5 um); (b) control and rejuvenated asphalts (top: 20 um  20
um; bottom: 5 um  5 um); and (c) RA before and after rejuvenating (left two: 20 um  20 um; right two: 5 um  5 um).

P10-RE, the micelle number and proportion are significantly less that in the other rejuvenated asphalts; the excessive rejuvenator
than those of the other rejuvenated asphalts. The reason relates diluted the micelles so that the micelle area in the phase images
to the content of rejuvenator in P10-RE being much higher than is much less.
8 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748
Table 5
Quantitative analysis of micelles in the AFM phase images.
Asphalt Micelle number Average micelle Micelle
area (lm2) proportion (%)
P90 858 0.13 27.67
P50 799 0.16 31.54
P30 680 0.22 37.04
P10 69 4.58 78.92
RA 1068 0.16 43.95
P50-RE 1045 0.10 25.30
P30-RE 1243 0.08 24.79
P10-RE 765 0.11 20.31
RA-RE 1377 0.05 22.06
Since the AFM phase images can reflect the micelle changes of
the aged and rejuvenated asphalts, which relate to the distribution
of the SARA fractions in the asphalt, the SARA fraction distribution
can be indirectly analyzed by the proportion of micelles in the AFM
phase images. This method avoids the long testing time and the
errors that can easily occur in the traditional SARA analysis pro-
cess. Comparing RA and RA-RE shows that the micelle proportion
decreased from 43.95% to 22.06% due to the content of asphaltene
and resin significantly decreasing after rejuvenation (Table 5). Fur-
thermore, the decrease of average micelle area and increase in
micelle number indicates that the originally aggregated micelles
dispersed into small micelles, which improved the stability of the
colloidal structure of the asphalt. The variation of the microstruc-
ture for RA is consistent with that of the aged asphalt in the labo-
ratory simulation.
3.5. Physical properties
After aging, the SARA fractions, chemical composition, and
microstructure of the asphalt have changed significantly, which
will inevitably influence the macro-properties of the asphalt. In
addition, the addition of a rejuvenator softened the hardened
asphalt and restored its colloidal stability, factors that can be char-
acterized by the basic physical properties of penetration, softening
point, and ductility, as shown in Fig. 7.
Obviously, aging makes asphalts harder, which was mainly
reflected in the decreases in penetration and ductility, and the
increase in softening point. After rejuvenating, the physical proper-
ties were restored to the original levels of the control asphalt P90
and meet the specifications of JTG F40-2004, except the ductility of
RA-RE, which was less than 100 cm. The physical properties of the
aged asphalts and rejuvenated asphalts are consistent with the
SARA fraction distributions and micelle morphologies in the AFM
phase images; that is, aging caused the asphaltene and resin con-
tent to increase, corresponding to micelles with a high viscosity
in the AFM phase images, such asphalt belongs to the colloidal
structure of gel-like that has low penetration and ductility, and a
high softening point. Through decreasing the asphaltene and resin
content and diluting the micelles, the rejuvenator affects aged
asphalts via a thermodynamically reversible process; the stability
of the asphalt colloidal structure is restored, thus restoring the
physical properties and pavement performance of the asphalt.
In the ductility test, each specimen underwent tensile deforma-
tion under an external force. The tensile stress is balanced by slip-
page between molecules; deformation is affected by factors such as
intermolecular forces, molecular size, and distance. The content of
the carbonyl and sulfoxide groups in the aged asphalt from RAP
was much higher than that in the samples from the laboratory sim-
ulation. These two functional groups have extremely strong polar-
ities, which significantly increases the intermolecular forces and
limits the ability to deform. Therefore, the ductility of the aged
asphalts from laboratory simulation (P50, P30, and P10) can be
restored to that of the neat asphalt, whereas that of RA cannot be
recovered.
3.6. Rheological properties
Fig. 8 gives the complex modulus (G*) and the phase angle (d) of
the control, aged, and rejuvenated asphalts at temperatures rang-
ing from 10 °C to 70 °C. In general, aging has a significant effect
on both G* and d. This trend becomes more obvious with aging
times longer than 170 min, as illustrated by the evidently increas-
ing G* and decreasing d for P10 over the whole temperature range.
Since G* is an overall intensity index and d reflects the viscous
response of asphalt, a higher G* and lower d generally indicate
greater stiffness and a more elastic component in the asphalt, that
is, aging hardening. As shown in Fig. 8(a), the G* value increased
with an increase in aging level and decreased with an increase in
testing temperature, while d showed the opposite trend. The tem-
perature dependence of asphalt’s rheological properties is closely
related to its aging level. As for RA, the effect on G* and d of actual
aging during a long-term service life was between that of P30 and
P10.
After rejuvenation, though the penetration of all the aged
asphalts was restored to the original level, minor differences still
existed in G* and d between the restored asphalts and the control
asphalts. The control asphalt had higher G* and lower d. This differ-
ence is even more pronounced at high temperatures for G* and at
middle temperatures for d, indicating that the addition of rejuvena-
tor alone cannot restore the viscous components in aged asphalt.
The viscosities of the control, aged, and rejuvenated asphalts
measured at various shear rates by a dynamic shear rheometer
flow sweep procedure are given in Fig. 9. These viscosities were
used to analyze the evolution of the asphalt aging and rejuvena-
tion. As shown in Fig. 9(a), asphalt aging is expressed by the viscos-
ity increasing, which could be attributed to the increase in
asphaltene content (as it has the highest viscosity among the four
SARA fractions [30]) during aging (Fig. 4). Considering the rate of
change of viscosity with the rate of shear defines the shear suscep-
tibly (SS) of the asphalt, that is, the slope of the plot of the log shear
rate versus log viscosity [33]. Comparing P50, P30, P10, and RA
shows that aging can increase the SS of asphalt from 0.017 to
0.319, as shown in Fig. 9(b). Consequently, the viscosity of the
asphalt begins to decrease significantly at lower shear rates as
the aging level increases. This decrease occurs because the reduc-
tion of the oil phase during aging can damage the stability of the
colloidal structure of the asphalt, making the asphalt more suscep-
tible to shear [34]. The viscosities at shear rates of 0.01, 0.1, 1, and
10 1/s shown in Fig. 9(b) show that the addition of RE decreased
the viscosity of the aged asphalts significantly, but that their vis-
cosities were still much higher than that of the control asphalt
P90. RE helped reduce the viscosity of RA to a value between those
of P30-RE and P10-RE. However, the viscosity of P10-RE is even
greater than that of P50. The RE content, which was determined
by penetration, was not enough to restore the viscosities of the
aged asphalts to their original level.
Fig. 10 shows the fatigue factor (G*sind) of the control, aged, and
rejuvenated asphalts at 10 °C, 25 °C, and 40 °C. The smaller the
G*sind, the better the fatigue resistance of asphalt. Aging clearly
enhanced the G*sind of the asphalts at all testing temperatures
and therefore decreased their fatigue resistance performance. This
trend was more obvious at aging times greater than 170 min (com-
pare P30 to P10); that is, the G*sind of aged asphalt increased shar-
ply. For rejuvenated asphalts, adding RE could effectively replenish
the light oil phase lost in the aging process and provide the viscous
component. Therefore, the asphalts’ G* decreased and d increased,
but the former decreased far more than the latter increased
(Fig. 8); hence, the G*sind of the rejuvenated aged asphalts were
 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748 9

Fig. 7. Physical properties of the control, aged, and rejuvenated asphalts: (a) penetration; (b) softening point; and (c) ductility.

Fig. 8. Complex modulus and phase angle versus temperature: (a) control and aged Fig. 9. Flow sweep testing results at 60 °C: (a) viscosity versus shear rate; and (b)
asphalts; and (b) control and rejuvenated asphalts. viscosity and SS at various shear rates.
10 T. Zhou et al. / Construction and Building Materials 249 (2020) 118748
Fig. 10. Fatigue factors of the control, aged, and rejuvenated asphalts at different
temperatures.
significantly reduced. Furthermore, although the G*sind of all the
asphalts decreased with increasing temperature, the effects of tem-
perature on the anti-fatigue performance of different rejuvenated
asphalts were inconsistent; for example, the G*sind of all the reju-
venated asphalts were slightly higher than that of the control
asphalt at 40 °C, but at 25 °C and 10 °C, they were lower than that
of the control asphalt (except for P30-RE at 25 °C). The results of
the asphalt properties show that a gap existed between the phys-
ical and rheological properties of the asphalts after rejuvenation;
the restoration of physical properties cannot guarantee the recov-
ery of rheological properties. Hence, a design method that balances
these properties should be used to ensure the comprehensive per-
formance of rejuvenated asphalt in construction.
4. Conclusions
The primary objective of this study was to investigate (1) the
aging behaviors of asphalt, using both laboratory simulation (the
RTFO test) and asphalt recovered from RAP, and (2) the rejuvena-
tion capabilities, restoring the aged asphalts to their unaged states
as closely as possible. To achieve this objective, the distributions of
SARA fractions were analyzed; specific functional groups were
investigated by FTIR; microstructures were investigated by AFM;
and performance-related properties were analyzed. Based on the
results and analysis, the following conclusions can be drawn:
(1) The evolution of the penetration and the variation in the dis-
tributions of SARA fractions agree in terms of the effect of
RTFO time on the aging level of the asphalt. Regarding reju-
venation, despite penetration being recovered, the asphal-
tene content as well as the characteristic functional group
indexes (carbonyl and sulfoxide) in the rejuvenated asphalts
cannot be restored to the unaged levels.
(2) The AFM phase image is a powerful tool to characterize the
changes that occur during asphalt aging and rejuvenation.
The number and size of micelles in the AFM phase images
obviously related to the distribution of the SARA fractions;
aging increased both micelle size and proportion, and
decreased the number of micelles due to micelle aggrega-
tion, while rejuvenation showed the opposite trend.
(3) The results of tests of the physical and rheological properties
helped show the hardening and brittleness caused by aging
and the recovery of softening caused by rejuvenation. Even
so, the optimum content of rejuvenator, determined by the
physical properties, cannot guarantee the recovery of the
rheological properties; thus, it is necessary to design a com-
prehensive properties-based method to select the proper
rejuvenator amount.
(4) Generally, the aged asphalt RA from field RAP had similar
aging and rejuvenation behaviors with the samples from
RTFO aging with condition times of 300 min to 600 min,
but (when rejuvenated) its asphaltene content was still
higher compared with the control and the other rejuvenated
asphalts. Although the SARA fractions of the rejuvenated RA
are basically the same as those of the control asphalt, there
is still a gap between them due to the complex service envi-
ronment of asphalt in the field.
In summary, laboratory simulations of aging like the use of an
RTFO can reproduce asphalt aging to some extent, and use of a
rejuvenator with a high content of aromatics can restore the prop-
erties of the asphalt to some extent. But these tests cannot consider
all of the factors that influence asphalt in the complex service envi-
ronment in which it is used, and cannot ensure the pavement per-
formance of rejuvenated asphalt, due to the complex rejuvenation
process. Hence, future work should consider the coupling of multi-
ple aging factors like oxygen, heat, UV light, pressure, and so on. In
addition, the chemical aspects of the interaction between aged
asphalt and rejuvenator should be studied to investigate the funda-
mental mechanism of the rejuvenation process, rather than view-
ing it only as a physical mixing of two components.
CRediT authorship contribution statement
Tao Zhou: Formal analysis, Investigation, Writing - original
draft, Writing - review & editing, Visualization. Liping Cao: Con-
ceptualization, Methodology, Resources, Writing - review & edit-
ing, Supervision, Project administration. Elham H. Fini:
Conceptualization, Formal analysis. Lingwen Li: Investigation,
Data curation. Zhiyang Liu: Data curation. Zejiao Dong: Resources,
Funding acquisition.
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.
Acknowledgments
This research work was sponsored by the National R&D Pro-
gram of China (Grant No. 2016YFE0202400), National Natural
Science Foundation of China (Grant Nos. 51978219 and
51878228), and Science & Technology Project of DOT of Jilin Pro-
vince (Grant No. 2018-1-2). The authors gratefully acknowledge
the financial support from the China Scholarship Council. Also, spe-
cial appreciation is given to the Analysis & Test Center of Harbin
Institute of Technology for their generous assistance during the
laboratory tests.
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