polymers
Article
Effect of Thermal Oxygen Aging Mode on Rheological
Properties and Compatibility of Lignin-Modified Asphalt
Binder by Dynamic Shear Rheometer
Meng Cai 1 , Xun Zhao 2 , Xuanzhen Han 3 , Peng Du 2 , Yi Su 1 and Cheng Cheng 1, *
Citation: Cai, M.; Zhao, X.; Han, X.;
Du, P.; Su, Y.; Cheng, C. Effect of
Thermal Oxygen Aging Mode on
Rheological Properties and
Compatibility of Lignin-Modified
Asphalt Binder by Dynamic Shear
Rheometer. Polymers 2022, 14, 3572.
https://doi.org/10.3390/
polym14173572
Academic Editors: Oihana Gordobil,
Stefan Beisl and René Herrera Díaz
Received: 27 June 2022
Accepted: 19 August 2022
Published: 30 August 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
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, 3572. https://doi.org/10.3390/polym14173572
1 School of Civil Engineering, Southwest Forestry University, Kunming 650224, China
2 Shuicheng Highway Administration of Guizhou Province, Shuicheng 553000, China
3 Yanlord Development (Tianjin) Co., Ltd., Tianjin 300090, China
* Correspondence: chengcheng_clx@swfu.edu.cn
Abstract: Lignin is abundant in nature. The use of lignin in the asphalt pavement industry can im-
prove pavement performance while effectively optimizing pavement construction costs. The purpose
of this paper is to study the effect of lignin on the anti-aging properties of asphalt. Commercial lignin
was selected to prepare a lignin-modified asphalt binder. The properties of lignin-modified asphalt
were studied by rheological experiments. The high-temperature rheological properties of two kinds
of base asphalt and modified asphalt samples with different contents of lignin under three conditions
of original, rolling thin film oven (RTFO) aging, and pressure aging vessel (PAV) were tested and
analyzed with temperature sweep, frequency sweep, and multiple stress creep recovery (MSCR) tests.
By comparing the variation laws of evaluation indicators, such as complex shear modulus G*, phase
angle δ, anti-aging index, cumulative strain, and viscous component Gv , we found that lignin could
effectively improve the high-temperature stability of base asphalt, but it had a negative impact on the
compatibility issues of base asphalt. Meanwhile, lignin played a filling role in the base asphalt, and
the increase in viscosity was the fundamental reason for improving the high-temperature stability of
the base asphalt. The research results indicated that lignin could effectively improve the anti-aging
performance of asphalt and play a positive role in prolonging the service life of pavement.
Keywords: lignin; asphalt; short-term aging; long-term aging; rheological properties
1. Introduction
As a viscoelastic material, asphalt comprises a large proportion of high-grade road
surfaces in many countries owing to its superior performance and driving comfort. How-
ever, asphalt has obvious shortcomings, such as high-temperature sensitivity and easy
softening at high temperatures. It easily becomes brittle at low temperatures and may not
meet the requirements of high-grade highways. The insufficient high-temperature stability
caused by aging is also a concern for the road industry. The adhesion between asphalt and
stone and the aging phenomenon of asphalt under the action of heat and oxygen affects
the quality and durability of asphalt on roads [1–5]. In the process of high-temperature
production, storage, transportation, and processing, asphalt comes easily into contact with
oxygen in the air, resulting in short-term aging. The most important type of aging is thermo-
oxidative aging. Thermo-oxidative aging can lead to changes in the chemical composition
and molecular structure of asphalt, and temperature sensitivity may also change; moreover,
different modified asphalts have different aging effects. Prolonged exposure to elevated
temperatures also leads to an increase in viscosity of the asphalt binder and changes in
its viscoelastic characteristics [6]. At present, styrene–butadiene–styrene block copolymer
(SBS)-modified asphalt is widely used in China and other countries. SBS can significantly
improve the high-temperature performance and anti-aging performance of asphalt and
asphalt mixtures [7–9], but SBS-modified asphalt is expensive [10].
https://www.mdpi.com/journal/polymers
Polymers 2022, 14, 3572 2 of 17

Lignin, as the second most abundant renewable natural polymer compound in nature
after cellulose, is an aromatic polymer containing oxyphenylpropanol or its derivative
structural units in its molecular structure [11]. Lignin can not only be used in phenolic resin
materials [12–14], epoxy resin materials [15–17], and polyurethane materials [18–20] instead
of raw petroleum chemical materials, but it can also be blended with polymer materials to
increase the mechanical properties [21], thermal stability [22], anti-aging (oxidation) [23],
and flame retardancy [24] of polymer materials. In recent years, it has been widely used in
plastics [25], adhesives [26], and other fields. Wu et al. [27] analyzed the lignin-modified
asphalt with infrared spectroscopy (FTIR) and differential scanning calorimetry (DSR) and
pointed out that the addition of lignin can significantly delay the aging process of the asphalt
and increase the thermal degradation of the lignin-modified asphalt after aging. Meanwhile,
the stability and low-temperature crack resistance have been improved in the aging process.
Gao et al. [28] studied the high-temperature rheological behavior and fatigue properties of
lignin-modified asphalt binders. The results indicated that the addition of lignin improved
the viscosity and the deformation resistance of asphalt under high temperatures at different
rotating speeds. Batista et al. [29] the high-temperature, low temperature, and aging
properties of a lignin-modified asphalt binder. The results demonstrated that lignin was
conducive to improving the high-temperature rutting resistance and low-temperature
crack resistance of the asphalt binder. Xu et al. [30] studied the rheological properties
and anti-aging properties of a lignin-modified asphalt binder. The results showed that
the addition of lignin helped to inhibit the formation of carbonyl functional groups in the
asphalt binder after the RTFO and PAV aging processes. This indicated that lignin can be
used as antioxidant modifier. However, the addition of lignin has an adverse effect on the
fatigue resistance of the asphalt binder.
In conclusion, lignin can effectively improve the high-temperature stability and anti-
aging performance of asphalt. However, the high-temperature rheological properties of
lignin-modified asphalt under different aging effects should be further studied.
In this paper, the high-temperature rheological properties of two kinds of base asphalt
and modified asphalt samples with different lignin contents under the three states of
original, short-term aging, and long-term aging were analyzed by dynamic shear rheometer
(DSR) temperature sweep, frequency sweep, and repeat creep test. Complex shear modulus
G*, phase angle δ, anti-aging index, cumulative strain, viscous component Gv, and other
indicators were used to study the aging performance of lignin-modified asphalt.
The detailed plan completed in this paper is shown in Figure 1.
 Polymers 2022,14,
Polymers2022, 14,3572
x FOR PEER REVIEW 33ofof17
16

Preparation process
3%，6%，9%，12%
and 15% by mass
Lignin

Mao ming 70 asphalt

Dong hai 90 asphalt

Lignin modified asphalt

RTFOT
Original
PAV

DSR

Temperature Frequency
scanning scanning MSCR

Strain value 12%, After loading for 1s,

loading frequency The strain amplitude is
10rad/s, temperature unloading for 9s, 100
0.5% and the frequency
range 30~100℃ , interval creep recovery cycles
range is 0.1~100rad/s
2℃ were performed

Objective: Objective: Objective:

G * ,δ,G * A I ,δ A I ,G * /sinδto To evaluate the To judge the viscoelasticity
evaluate whether lignin compatibility of lignin of lignin and two kinds of
has anti‐aging properties with two kinds of asphalt by accumulative
and whether lignin has asphalt by Han curve strain and creep viscosity
selective compatibility component Gv
with two kinds of asphalt and vGP diagram

Figure 1. Experiment plan.

Figure 1. Experiment plan.
2. Materials and Methods
2.1. Raw Materials
2. Materials and Methods
2.1.1. Lignin
2.1. Raw Materials
The commercial lignin used herein was produced by Jinan Yanghai Chemical Co., Ltd.
2.1.1. Lignin
(Jinan, China). Lignin that passed a 200-mesh sieve was used for testing, and its main
The commercial lignin used herein was produced by Jinan Yanghai Chemical Co.,
Polymers 2022, 14, x FOR PEER REVIEWtechnical indicators, molecular weight, and pyrolysis parameters are shown in 4Table of 17 1.
Ltd. (Jinan,
Among them,China). Lignin
the lignin that passed
indicator a 200‐mesh
was provided sieve
by the was used for
manufacturer. testing,
The and its
molecular main
weight
of lignin was determined by Agilent pl-gpc50 gel chromatography, and the pyrolysis test1.
technical indicators, molecular weight, and pyrolysis parameters are shown in Table
Among
was them,with
conducted the alignin indicator
Mettler was provided
Toledo tga/sdta851 by the manufacturer.
synchronous The molecular
thermogravimetric analyzer.
Table 1. Main technical indexes, molecular weight, and pyrolysis parameters of lignin.
weight of lignin was determined by Agilent pl‐gpc50 gel chromatography, and the pyrol‐
Figure ysis test
Table wastechnical
1. Main conducted with
indexes,
Main a Mettlerweight,
molecular
Specifications Toledoand
tga/sdta851 synchronous
pyrolysis parameters thermogravimet‐
of lignin.
Scope
ric analyzer. PH 7~8
Figure Main Specifications Scope
Appearance color Brown powder
AshPH(%) 1 7~8
Appearance
Sugar contentcolor
(%) Brown
1~3 powder
Ash (%) 1
Sugar content (%) 1~3
Lignin content (%) 85~90
Lignin content (%) 85~90

Number average relative molecular weight

1.0
960
(Mn)
Lignin
 Appearance color Brown powder
Ash (%) 1
Sugar content (%) 1~3
Lignin content (%) 85~90
Polymers 2022, 14, 3572 4 of 17

Lignin content (%) 85~90

Number average relative molecular weight
Table 1. Cont.
1.0
960
(Mn)
Lignin
0.8
Figure weight-average
Mainmolecular weight (Mw)
Specifications 2964
Scope
Number average relative molecular weight
dW/dlogM

0.6
1.0
Peak molecular weight (Mp) 960
1182
0.4 (Mn)
Lignin
0.8
0.2 weight-average
Number molecular
average relative weight
molecular (Mw(M
weight ) n) 2964960
dW/dlogM

0.6
0.0
2.1 2.4 2.7 3.0 3.3 3.6 3.9 4.2 4.5
Peak molecular
weight-average weight
molecular (Mp)(Mw )
weight 11822964
0.4 logM Dispersion coefficient
Peak molecular (d)p )
weight (M 3.091182
0.2 Dispersion coefficient (d) 3.09
0.0
2.1 2.4 2.7 3.0 3.3 3.6 3.9 4.2 4.5
logM Dispersion coefficient (d) 3.09
Initial decomposition temperature (°C) 189
Maximum decomposition temperature (°C) 339.3

Initial decomposition
Initial decompositiontemperature
temperature ((°C)
◦ C) 189189
Maximum
Maximum decomposition temperature (◦(°C)
decompositiontemperature C) 339.3
339.3
700 ◦ C Residue carbon rate (%) 39.7
700 °C Residue carbon rate (%) 39.7

700 °C Residue carbon rate (%) 39.7

2.1.2. Based Asphalt
2.1.2. Based
In thisAsphalt
paper, Maoming 70# asphalt and Donghai 90# asphalt were used for related
experiments. TheMaoming
In this paper, test results70#
of asphalt
various and
properties
Donghaiare90#
shown in Table
asphalt were2.used for related
experiments. The test results of various properties are shown in Table 2.
2.1.2. Based Asphalt
Table 2. Maoming 70# and Donghai 90# base asphalt performance indexes.
TableIn2. this paper,70#
Maoming Maoming 70# 90#
and Donghai asphalt and Donghai
base asphalt 90# asphalt
performance indexes.were used for related
experiments. The test results of various Testproperties
Result are shown in Table 2. Requirement
Technical
Test Items Unit Test Result Technical Requirement
Test Items Unit Maoming 70# Donghai 90# 70 90
Table 2. Maoming 70# Maoming 70#
and Donghai 90# base Donghai 90#
asphalt performance 70
indexes. 90
◦
Penetration (25 C, 5 s, 100 g) 0.1 mm 65.4 86.2 60~80 80~100
Penetration (25 °C, 5 s, 100 g) 0.1 ◦mm 65.4 86.2 60~80 80~100
Softening point C 46.6
Test Result 45.7 ≥46 Requirement
Technical ≥45
Test Items
Softening
Ductility (15point
◦ C) Unit
°C
cm 46.6>150 45.7>150 ≥46≥100 ≥45≥100
Maoming 70# Donghai 90# 70 90
Ductility (15
TFOT penetration °C)
ratio (25 ◦ C) cm% >150 76.9 >15075.1 ≥100≥61 ≥100
≥57
Penetration
Residual (25 °C, 5 s, 100 g)
(15 ◦ C)
ductilityratio 0.1 cm
mm 65.4132.9 86.2125.6 60~80≥15 80~100
≥20
TFOT penetration (25 °C) % 76.9 75.1 ≥61 ≥57
Softening point °C 46.6 45.7 ≥46 ≥45
Residual ductility (15 °C) cm 132.9 125.6 ≥15 ≥20
Ductility (15 °C) cm >150 >150 ≥100 ≥100
2.2. Preparation of Lignin-Modified Asphalt
TFOT penetration ratio (25 °C) % 76.9 75.1 ≥61 ≥57
2.2. Preparation of Lignin-Modified
The high-speed shear Asphalt
dispersion emulsifying
Residual ductility (15 °C) cm 132.9 125.6 machine (BME ≥15100L) produced≥20 by Shang-
haiThe
Weiyuhigh-speed
Co., Ltd. shear dispersion
(Shanghai, China),emulsifying
was used tomachine (BME 100L) produced
prepare lignin-modified asphalt. byThe
Shanghai Weiyu Co., Ltd. ◦
(Shanghai, China), was used to prepare lignin-modified
base asphalt was heated to 150 C and kept for a period of time, and after passing through asphalt.
2.2. Preparation of Lignin-Modified Asphalt
The base asphalt
a 200-mesh sieve,was
theheated to 150
lignin was °C and and
uniformly keptslowly
for a period
added toofthe
time, and
base after in
asphalt passing
batches
The athe
during
through high-speed
low-speed
200-mesh shear
sieve, dispersion
shearing
the lignin wasemulsifying
process for
uniformly machine
preliminary
and (BME
dispersion.
slowly added 100L)
Then,
to the produced
the speed
base ofby
asphalt the
Shanghai
inhigh-speedWeiyu
batches during Co.,
shearing Ltd. (Shanghai,
machine was
the low-speed China),
gradually
shearing was used
increased
process to prepare lignin-modified
from low speed
for preliminary asphalt.
to 5000Then,
dispersion. r/minthe and
The base
then asphalt
sheared forwas
1 h. heated to 150 °C
After shearing, and
the kept container
sample for a period of time,the
containing andmixture
after passing
of lignin
through a 200-mesh sieve, the lignin was uniformly and slowly
and matrix asphalt was put into a constant temperature oven at 120 C for added to◦ the base
1 h,asphalt
and the
inpreparation
batches during the low-speed shearing
of lignin-modified process
asphalt was for preliminary
completed. dispersion.five
In this experiment, Then, theof
kinds
lignin-modified asphalts with different lignin contents (3, 6, 9, 12, and 15%) were prepared.
The Maoming asphalts were marked as MM-3, MM-6, MM-9, MM-12, MM-15; Donghai
Maoming asphalts were marked as DH-3, DH-6, DH-9, DH-12, DH-15; while the base
asphalt was marked as MM-0 and DH-0. It was developed at 120 ◦ C for 1 h and compared
with the base asphalt to study the influence of its high-temperature rheological properties
and aging properties.

2.3. Preparation of Aged Samples

According to JTGE 20-2011 “Highway Asphalt and Asphalt Mixture Test Regulations”,
the rotating film oven test (T 0610-2011) and the pressure aging container accelerated asphalt
aging test (T 0630-2011) were conducted. Firstly, 35 ± 0.5 g pitches were poured into glass
Polymers 2022, 14, 3572 5 of 17

bottles, the temperature of RTFOT was kept at 163 ◦ C and the time was 85 min. The RTFO
aged samples were prepared for subsequent testing. The sample plate with 50 ± 0.5 g of
lignin-modified asphalt was put in the PAV long-term aging box, the temperature was set
to 100 ◦ C, the holding pressure was 2.1 MPa, and the aging time was 20 h.

2.4. Test Design and Evaluation Index

2.4.1. Temperature Scanning and Frequency Sweep Test
The temperature sweep and frequency sweep tests of asphalt were carried out using
a DHR-1 dynamic shear rheometer. The temperature sweep test was adopted through
the strain control method with 12% of the target strain value and 10 rad/s of the loading
frequency, and the test temperature range was 30~100 ◦ C with 2 ◦ C between the sampling
intervals. The frequency sweep test was used to study the viscoelastic properties of the
modified asphalt. The temperature of the frequency sweep was 30 and 60 ◦ C, the frequency
range was 0.1~100 rad/s, and the strain amplitude was 0.5%. Among them, the original
asphalt and the asphalt after aging in the rotary film oven were scanned with a parallel
plate with a diameter of 25 mm and a spacing of 1 mm, and the asphalt after pressure aging
was scanned with a parallel plate with a diameter of 8 mm and a spacing of 2 mm.

2.4.2. Aging Index Evaluation

The aging performance analysis based on high-temperature rheology was evaluated
with the complex shear modulus aging index (G* AI ), and the specific calculation formula
is shown in Formula (1) [31]. The operating temperature range was 46~82 ◦ C, and the
sampling interval was 6 ◦ C.

Short (long) term aging complex shear modulus

Complex shear modulus aging index( G ∗AI ) = (1)
Unaged complex shear modulus

2.4.3. Repeat Creep Test

At present, the multi-stress repeated creep recovery test (MSCR) of AASHTO MP19-
10 was adopted to evaluate the high-temperature performance of asphalt and modified
asphalt [32]. In this paper, the multi-stress repeated creep recovery test was performed by
loading for 1 s, unloading for 9 s, and 100 cycles of creep recovery process were conducted.
The test temperature was 64 ◦ C, and the test stress was 300 Pa. The viscosity component
was obtained with the Burgers model. The Burgers model equation was divided into two
equations; one was the stress–relaxation mode equation to input constant strain, the other
was the creep loading mode equation with constant input stress. Both equations can be
computed by inverse transformations and Laplace transforms. In this paper, the creep
loading mode equation was adopted, and the Burgers fitting equation was formulated as (2):
tE
 
ε(t) 1 t 1 − 2
= + + 1 − e η2 (2)
σ0 E1 η1 E2

Here, ε(t) is the cumulative creep strain of asphalt specimen; σ0 is the loading stress
of the asphalt test; η 1 and E1 represent the damping coefficient and elastic modulus in
Maxwell’s model, respectively; η 2 and E2 represent the damping coefficient and elastic
modulus in the Kelvin model, respectively; t is the loading time; E1 reflects the elastic
recovery ability of asphalt at high temperature; η 1 is the viscosity coefficient reflecting the
unrecoverable deformation, which is related to the viscosity deformation coefficient of
asphalt; E2 and η 2 reflect the load action under long-term load and at room temperature,
which reflect the ability of asphalt to delay elastic recovery of deformation. In this study,
η 1 is the viscous part Gv of creep stiffness. The test was adopted to evaluate the high-
temperature performance of base asphalt and lignin-modified asphalt.
 asphalt; E2 and η2 reflect the load action under long‐term load and at room temperatu
which reflect the ability of asphalt to delay elastic recovery of deformation. In this stud
η1 is the viscous part Gv of creep stiffness. The test was adopted to evaluate the hig
Polymers 2022, 14, 3572 temperature performance of base asphalt and lignin‐modified asphalt. 6 of 17

3. Results and Discussion Results

3. Results
3.1. Analysis ofand Discussion
Rheological Results of Lignin‐Modified Asphalt
Properties
3.1. Analysis of Rheological Properties of Lignin-Modified Asphalt
The test results of complex modulus G* and phase angle δ for original and differe
The test results of complex modulus G* and phase angle δ for original and different
agingaging
asphalt samples
asphalt samplesare
areshown inFigure
shown in Figure2. 2.

(a) Original 90 (b) Original 90

10,000
Complex modulus（Pa）

88 88

Complex modulus（Pa）
10,000

Phase angle (°)

Phase angle (°)

86 86

84 84
1,000 DH-0
1,000 MM-0
DH-3
MM-3 82 82
DH-6
MM-6
DH-9
MM-9
80 DH-12 80
MM-12
DH-15
MM-15
100 78 100 78
46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82
Temperature(℃) Temperature(℃)
100,000 90 90

(c) RTFOT (d) RTFOT

88
88

86
Complex modulus（Pa）
Complex modulus（Pa）

86 10,000
10,000

Phase angle (°)

Phase angle (°)

84
84
82
82
MM-0 DH-0 80
1,000
1,000 MM-3 80 DH-3
MM-6 DH-6 78
MM-9 DH-9
78 DH-12
MM-12
76
MM-15 DH-15
76
100 100 74
46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82

Temperature(℃) Temperature(℃)
84 82
(e) PAV (f) PAV 80
82
100,000 78
100,000 80
76
Complex modulus（Pa）
Complex modulus（Pa）

78 74
Phase angle (°)

76 72
Phase angle (°)

10,000 10,000 70
74
72 68
DH-0
66
MM-0 70 DH-3
MM-3 DH-6 64
1,000 68 1,000
MM-6 DH-9 62
MM-9 66 DH-12 60
MM-12 DH-15
64 58
MM-15
100 62 100 56
46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82

Temperature(℃) Temperature(℃)

Figure 2. Results of complex shear modulus and phase angle of original and different aged asphalt
Figurewith
2. Results of complex
temperature. shearthe
(a,b) represent modulus
G* and δ and phaseasphalts
of different angle of original
before aging,and
(c,d)different aged asph
represent the
with temperature. (a,b)asphalts
G* and δ of different represent
afterthe G*andaging,
short-term δ of different asphalts
(e,f) represent before
the G* and aging, (c,d)
δ of different represent t
asphalts
G* andafter
δ oflong-term
different asphalts
aging. after short‐term aging, (e,f) represent the G* and δ of different aspha
after long‐term aging.
As seen in Figure 2a,b, compared with the original asphalt, the complex modulus of
the modified asphalt increased owing to the addition of lignin. The lignin-modified asphalt
As seen in Figures 2a,b, compared with the original asphalt, the complex modulus
the modified asphalt increased owing to the addition of lignin. The lignin‐modified a
phalt showed the trend of reducing the complex shear modulus and increasing the pha
Polymers 2022, 14, 3572 7 of 17

showed the trend of reducing the complex shear modulus and increasing the phase angle
with the increase in temperature, but the change trend gradually flattened. The increase in
lignin improved the high-temperature performance, but did not change the temperature
sensitivity, so temperature had an effect on it. As asphalt is a temperature-sensitive material,
it exhibited elasticity when the temperature was low, and gradually transformed into a
viscous flow state with the increase in temperature.
After comparing the effects of different lignin contents on the rheological parameters
of the base asphalt, we found that for Maoming 70# base asphalt, the addition of too much
lignin led predominantly to an increase in viscous resistance (internal friction). The increase
in viscosity resulted from the decreased complex shear modulus and the increased phase
angle. It was shown that the inflection point of the rheological parameters appeared when
the lignin content was 9%, indicating that there was an optimal lignin content.
However, for Donghai 90# asphalt, the same trend did not appear, and the complex
shear modulus and phase angle of the asphalt binder linearly increased and decreased with
the increase in lignin content, respectively.
With the increase in lignin content, although the colloidal structure type of asphalt
did not change, the increase in asphalt colloidal structure composition ration may have
led to the change of its phase structure [33]. Compared with Donghai 90#, Maoming 70#
had a higher proportion of asphaltenes [34]. Therefore, the asphaltene content was the
fundamental reason that the different rheological parameters of the two base asphalts
changed with the lignin content.
It can be seen in Figure 2c,d that the complex modulus and phase angle of each asphalt
sample showed different degrees of decrease and increase after RTFO aging.
With the increase in lignin content, the complex modulus of Maoming asphalt first
increased and then decreased, which was the same as that before aging. The phase angle
was larger than that of original asphalt except for the content of 15%. Meanwhile, the
complex modulus and phase angle of Donghai asphalt increased and decreased with the
increase in lignin content, respectively.
In Figure 2e,f, the complex modulus of Maoming asphalt after PAV aging was opposite
to that of the base and RTFO aging binder sample and decreased with the increase in lignin
content, and the phase angle of Maoming lignin-modified asphalt was larger than that of
the base asphalt. The complex modulus of Donghai lignin-modified asphalt was larger
than that of the base asphalt except for the asphalt with lignin contents of 3 and 15%, which
was consistent with the RTFO aging condition.

3.2. Analysis of PG Classification of Lignin-Modified Asphalt

The rutting factor G*/sinδ was used to evaluate the rutting resistance of the asphalt
binder at high temperatures. The larger the rutting factor G*/sinδ, the better the high-
temperature resistance and the stronger the permanent deformation resistance of the asphalt
binder. Figure 3 shows the results for the rutting factor G*/sinδ of each asphalt sample
before and after aging at 58~82 ◦ C.
As seen in Figure 3, with the increase in lignin content, the rutting factor G*/sinδ
value of the two kinds of asphalts before and after aging increased greatly, and the lignin-
modified asphalt sample with 15% lignin content for Maoming asphalt showed the best
anti-rutting performance after aging, but the PG high-temperature grade did not change.
Donghai asphalt showed the strongest high-temperature rutting resistance when the lignin
content was 15% before and after aging, and the high-temperature grade of PG increased
by one level at this content.
 The rutting factor G*/sinδ was used to evaluate the rutting resistance of the asphalt
binder at high temperatures. The larger the rutting factor G*/sinδ, the better the high‐tem‐
perature resistance and the stronger the permanent deformation resistance of the asphalt
Polymersbinder. Figure 3 shows the results for the rutting factor G*/sinδ of each asphalt sample 8 of 17
2022, 14, 3572

before and after aging at 58~82 °C.

85
52 (a) Original (b) RTFOT
80
48 Asphalt style Condition Fault temperatur PG grade
MM-0 75
MM-0 Original 72.4℃ 70
44 MM-3 70
RTFOT 76.4℃
MM-6 65
40 MM-3 Original 72.6℃ 70
MM-9 60 RTFOT 74.6℃
36 MM-12 55 MM-6 Original 73.3℃ 70
32 MM-15 50
G*/sinδ(KPa)

RTFOT 76.4℃
28 45 MM-9 Original 75.1℃ 70
40 RTFOT 77.4℃
24
35 MM-12 Original 75.5℃ 70
20 30 RTFOT 77.4℃

25 MM-15 Original 75.4℃ 70

16
RTFOT 79.0℃
12 20
15
8
10
FOR PEER REVIEW 4 2.2KPa 8 of 16
1KPa 5
0 0
46℃ 52℃ 58℃ 64℃ 70℃ 76℃ 82℃ 46℃ 52℃ 58℃ 64℃ 70℃ 76℃ 82℃

34 70 (d) RTFOT
(c) Original
32 65 Asphalt style Condition Fault temperature PG grade
30 60 DH-0 Original 68.0℃ 64℃
28 DH-0 55 RTFOT 72.7℃
26 DH-3 DH-3 Original 68.5℃ 64℃
24 50
DH-6 RTFOT 72.9℃
22 DH-9 45 DH-6 Original 69.8℃ 70℃
G*/sinδ(KPa)

20 DH-12 40 RTFOT 73.7℃

18 DH-15 DH-9 Original 69.8℃ 70℃
35
16 RTFOT 74.9℃
30 DH-12 Original 70.5℃ 70℃
14
25 RTFOT 73.9℃
12 DH-15 Original 71.2℃ 70℃
10 20
RTFOT 76.3℃
8 15
6 10
4 2.2KPa
1KPa 5
2
0
0
46℃ 52℃ 58℃ 64℃ 70℃ 76℃ 82℃ 46℃ 52℃ 58℃ 64℃ 70℃ 76℃ 82℃

Figure 3. Rutting factor and3.PG

Figure grading
Rutting ofand
factor 70#PGandgrading
90# asphalt
of 70# with different
and 90# asphalt lignin contents.
with different (a–d)
lignin contents.
rutting factors representing different
(a–d) rutting factorsasphalts before
representing andasphalts
different after short‐term aging
before and after short-term aging.

3.3. Complex Shear Modulus Aging Index of Lignin-Modified Asphalt

As seen in Figure 3, with the increase in lignin content, the rutting factor G*/sinδ value
In order to further clarify the aging degree, the complex shear modulus aging index
of the two kinds ofG*asphalts before and after aging increased greatly, and the lignin‐mod‐
AI in different test temperature ranges was calculated. The G*AI values of different
ified asphalt sample withunder
binders 15% the
lignin
RTFO content
and PAV for Maoming
aging asphalt
conditions showed
are shown the4.best anti‐
in Figure
It can be seen in Figure 4a,b that
rutting performance after aging, but the PG high‐temperature the G* AI of Maoming asphalt under RTFO
grade did not change. Don‐aging
decreased first and then increased with the increase in lignin content to values slightly less
ghai asphalt showed the strongest high‐temperature rutting resistance when the lignin
than that of base asphalt. The G*AI of the lignin-modified asphalt binder with 9% lignin
content was 15% before
contentand
wasafter aging,
the lowest. Theand
RTFOtheaging
high‐temperature
index G*AI of the grade
Donghaiofasphalt
PG increased
binder had no
by one level at thisobvious
content.regularity with the increase in lignin content, which may be the change in asphalt
composition owing to aging. It can be seen in Figure 4c,d that the index G*AI under PAV
aging changed
3.3. Complex Shear Modulus Aging inIndex
a parabolic Asphaltin temperature. The index G*AI of
form with the increase
of Lignin‐Modified
Maoming asphalt with the 9% lignin content under PAV aging condition was the lowest,
In order to further
which clarify the aging
was consistent with degree,
the RTFOtheagingcomplex shear
condition, modulus
indicating that theaging index
addition of lignin
G*AI in different testcould
temperature ranges the
effectively improve was calculated.
resistance The G*ofAIMaoming
performance values of different
asphalt underbind‐
PAV aging
conditions. However, the G* index of
ers under the RTFO and PAV aging conditions are shown in Figure 4.
AI Donghai asphalt with 12% lignin content was the
lowest, which was the same as the index under the RTFO aging condition. However, it
did not mean that it had no aging resistance. The reason may be that this method could
2.2
(a) RTFOT not be well characterized, and it further indicated that its applicability to asphalt with a
(b) RTFOT
1.8
2.1

1.7
2.0
aging index

aging index

1.6 1.9
MM-0 MM-3
 ghai asphalt showed the strongest high‐temperature rutting resistance when the
content was 15% before and after aging, and the high‐temperature grade of PG incr
by one level at this content.

Polymers 2022, 14, 3572 9 of 17

3.3. Complex Shear Modulus Aging Index of Lignin‐Modified Asphalt
In order to further clarify the aging degree, the complex shear modulus aging
G*AI in different
high grade wastest
nottemperature ranges
significant. To sum was calculated.
up, Maoming Thea lignin
asphalt with G*AI values of9%
content of different
had the
ers under bestRTFO
the anti-aging
andeffect,
PAVand Donghai
aging asphalt with
conditions arelignin
showncontent of 12% had
in Figure 4. the best
anti-aging effect.
2.2
(a) RTFOT (b) RTFOT
1.8
2.1

1.7
2.0
Short-term aging index

Short-term aging index

1.6 1.9
MM-0 MM-3
MM-6 MM-9 1.8
1.5
MM-12 MM-15
DH-0 DH-3
1.7 DH-6 DH-9
1.4
DH-12 DH-15
1.6
ers 2022, 14, x FOR1.3PEER REVIEW
1.5
1.2
46 52 58 64 70 76 82 46 52 58 64 70 76 82
Temperature(℃) Temperature(℃)

12 22
(c) PAV (d) PAV
20
10
18
Long aging index

Long aging index

8
16

6 14

12
4
10
MM-0 MM-3 MM-6 DH-0 DH-3 DH-6
2 MM-9 MM-12 MM-15 8 DH-9 DH-12 DH-15

46 52 58 64 70 76 82 46 52 58 64 70 76 82
Temperature(℃) Temperature(℃)

Figure 4. The results of G* AI under different aging conditions. (a,b) represent the aging index of
Figuredifferent
4. The asphalt
resultswith
of Gshort-term
*AI underaging, (c,d) represent
different the aging index
aging conditions. (a,b)ofrepresent
different asphalt
index with
the aging
long-term aging.
different asphalt with short‐term aging, (c,d) represent the aging index of different asphalt w
long‐term aging.
3.4. Creep and Recovery Behavior of Lignin-Modified Asphalt
3.4.1. Creep Test Viscous Component
It can be on
Based seen
the in Figure
repeated 4a,b
creep test,that the G*AI
the viscosity of Maoming
component GV value asphalt
of creep under
stiffness RTFO
was fitted
decreased firstbyand
Formula
then(2)increased
as the evaluation
with theindex of high-temperature
increase stability perfor-
in lignin content to values sl
mance [35]. The Burgers model was used to fit the curve at the creep loading stage to
less than that
obtain the of base asphalt.
viscosity parameter,The
which AI of the lignin‐modified asphalt binder with 9%
G*was the viscosity part GV of creep stiffness (as seen
content was6the
Figures and lowest. The of
7). The value RTFO agingthe
Gv reflected index G*AI of
resistance the Donghai
of asphalt asphalt
to permanent binder h
defor-
mation. The larger the Gv, the better the rutting ability of the asphalt
obvious regularity with the increase in lignin content, which may be the change in as [36]. The unloading
stage mainly reflected the measured viscous deformation and delayed elastic deformation.
composition owing to aging. It can be seen in Figure 4c,d that the index G*AI under
Figure 5 shows the creep recovery of asphalt with and without lignin for the first 10 cycles
agingofchanged
the MM-0, in a parabolic
MM-9, DH-0, and form
DH-12 with
samples the
at aincrease inPa.
stress of 300 temperature. The index G
Maoming asphalt with the 9% lignin content under PAV aging condition was the lo
which was consistent with the RTFO aging condition, indicating that the addition of
could effectively improve the resistance performance of Maoming asphalt under PA
ing conditions. However, the G*AI index of Donghai asphalt with 12% lignin conten
the lowest, which was the same as the index under the RTFO aging condition. How
it did not mean that it had no aging resistance. The reason may be that this method
not be well characterized, and it further indicated that its applicability to asphalt w
high grade was not significant. To sum up, Maoming asphalt with a lignin content
 3400 0.40
3200 MM-0
0.35 Loading stage Recovery
3000 Loading stage MM-9
Polymers 2022, 14, x FOR PEER REVIEW2800 0.30 strain

Change shape
0.25 fitting line DH-0
2600 Unloading stage
0.20 DH-12
Polymers 2022, 14, 3572 2400 Total Measured elastic 10 of 17
2200 0.15 deformation deformation
2000 0.10

Strain(%)
1800 0.05
1600 0.00
3400 0 2 4 6 8 10
1400 0.40 Time(s)
3200
1200 MM-0
0.35 Loading stage Recovery
3000
1000 Loading stage MM-9
0.30 strain
2800

Change shape
800 0.25 fitting line DH-0
2600 Unloading stage
600 0.20 DH-12
2400 Total
400
2200 0.15 Measured elastic
deformation deformation
200
2000 0.10
Strain(%)
18000 0.05
1600 0 10 20 30 40 50 60
70 80 90 100
0.00
0 2 4 6 8 10
1400 Time(s) Time(s）
1200
1000
800
Figure
600 5. Burgers Model–Creep Test Diagram and Creep Recovery Diagram
400
200
0
Under the same stress and temperature, the creep cycle data f
0 10 20 30 40 50 60 70 80 90 100

times were fitted Time(s for ） two asphalts with different aging degrees, w
times.
Figure As seen
5. Burgers in Figures
Model–Creep 6 and
Test Diagram and 7, theRecovery
Creep Gv values
Diagram. of the Donghai and M
Figure 5. Burgers Model–Creep Test Diagram and Creep Recovery Diagram.
different
Under thechanges
same stress inanddifferent
temperature,aging
the creepdegrees
cycle data after
from theadding lignin,
1st to 100th times whic
were
ingfitted for two asphalts
> short‐term with different
aging > before aging degrees,This
aging. with an interval of 10 times.
demonstrated As the ad
that
seen in Under
Figures 6the same
and 7, the Gvstress
values and
of the temperature,
Donghai and Maoming the creepbinderscycle data from t
had different
significantly
changes
times inwere
different improve
agingfor
fitted degrees theasphalts
twoafter
high‐temperature
adding lignin,
with which was
different
resistance
long-term
aging aging
of asphalt.
> short-
degrees,
The
with an
uesaging
term
times. were consistent
> before
As seen
aging. Thisin
in Figures 6evaluating
and 7, the Gthe
demonstrated high‐temperature
that the addition performanc
of lignin can significantly
v values of the Donghai and Maomi
improve the high-temperature resistance of asphalt. The G*/sinδ and Gv values were
asphalt,
different
consistent
but there
changes
in evaluating inwere
the differentdifferences in theafter
agingperformance
high-temperature degrees evaluation
adding conclusions
of lignin-modified lignin,
asphalt,which
but
betw
was
fied
there asphalts.
were differences However,
in the the
evaluation value of
conclusions G suddenly
between different
ing > short‐term aging > before aging. This demonstrated that the additio
v increased
modified during
asphalts. th
However, the value of Gv suddenly increased during the PAV aging process of Donghai
of Donghai 90#
significantly improveasphalt the after adding lignin,
high‐temperature which may
resistance have been
of asphalt. cau
The G*/s
90# asphalt after adding lignin, which may have been caused by the difference between the
between
ues
two the two
wereasphalt
matrix consistent matrix
components. asphalt the
in evaluating components.
high‐temperature performance of li
asphalt, but there were differences in the evaluation conclusions between d
22 20
fied asphalts.
(c) PAV However, the value of G v suddenly increased during the PAV
Mean value
of20Donghai 90# asphalt after adding lignin, which may have been caused by
Original
between the two matrix asphalt components. RTFOT
PAV
15
12
22 20
10.0 (c) PAV
(b) RTFOT Mean value
20 Original
Gv(×103)

6 RTFOT
10 PAV
15
12
5
10.0
(b) RTFOT
4.2
Gv(×103)

(a) Original MM-0 MM-9

6
4.1 5
10
4.0
5

4.2
2.4 (a) Original MM-0 MM-9
4.1
2.1 5 0
1 10 20 30 40 50 60 70 80 90 100 MM-0 MM-9
4.0 Times

Figure
Figure 6. The
6. viscous component
The viscous Gv of the Maoming
component Gv of70# thebinder and the lignin-modified
Maoming 70# binder and
lign binder.
the
2.4
(a–c)
2.1 creep test viscosity component representing as
0 is, short-term aging and long-term aging.
(a–c)1 creep
10 20 test viscosity
30 40 50 60 70 component
80 90 100 representing
MM-0 as is, short‐term aging and
MM-9
Times

Figure 6. The viscous component Gv of the Maoming 70# binder and the lignin‐mo
(a–c) creep test viscosity component representing as is, short‐term aging and long‐
Polymers 2022, 14, x FOR PEER REVIEW

olymers 2022, 14, x FOR PEER REVIEW

55
Polymers 2022, 14, 3572 (c) PAV 11 of 17
50
50
Mean value
Original
40 RTFOT
55
15 (c) PAV PAV
7.0 50
50 (b) RTFOT

Gv(×103)
30 Mean value
3 Original
40 RTFOT
15 PAV
7.0
2 20
(b) RTFOT
Gv(×103)

1.8 (a) Original DH-0 DH-12 30

3
10
1.5

2 20
1.2 0
1.8 1 (a)10 20 30
Original 40 50 60 70 80 90 100 DH-0 DH-12
Times DH-0 DH-12

10
Figure
1.5
7. The viscous component Gv of the Donghai 90# binder and the lignin‐modi
c) creep test viscosity component representing as is, short‐term aging and long‐term
1.2 0
1 10 20 30 40 50 60 70 80 90 100 DH-0 DH-12
3.4.2. Accumulated Strain
Times

7. The
Figure As viscous component
a typical Gv of the
viscoelastic Donghai 90#
material, binder and
hasthea90#
lignin-modified binder.elastici
Figure 7. The viscous component Gv of asphalt
the Donghai certain delayed
binder and the
(a–c) creep test viscosity component representing as is, short-term aging and long-term aging.
lignin
ent kindstest
c) creep of viscosity
asphalts component
and asphalts with different
representing as is,lignin contents
short‐term aging had
anddiffe
lon
3.4.2. Accumulated
degrees. Strain
The delayed elasticity could be separated from permanent defor
As a typical viscoelastic material, asphalt has a certain delayed elasticity, and different
creep
3.4.2. recovery
Accumulated test. The initial strain in the recovery stage, i.e., the instanta
kinds of asphalts and asphaltsStrain
with different lignin contents had different recovery degrees.
ingdelayed
The strain,elasticity
was denoted by εL. The
could be separated residual deformation
from permanent strain at by thetheend
creepof the recov
recov-
As a typical viscoelastic material, asphalt has a certain delayed e
denoted
ery test. Theby εp,strain
initial and inεLthe
/εprecovery
was used stage,toi.e.,denote the permanent
the instantaneous unloading deformation
strain, was ac
ent kinds
denoted
total deformation, of asphalts
by εL . The residual and
i.e.,strain
the asphalts
atproportion
the end of theof withthe different
recovery stage waspart
viscous lignin
denoted
of by contents
the , and ha
εp deformatio
L /εp was used
εdegrees. to denote
The delayedthe permanent
elasticity deformation
could accounts for the total
be separated deformation,
single
i.e., temperature
the proportion of the level
viscous(64 part°C), the
of the εL/εp values
deformation. of 10,
Selecting 20,from
a single30, 40,permanent
50, 60, 70, 8
temperature
creep
loading
level recovery
◦
(64 C), times test.
the εLaccording The
/εp values ofto initial
10,the strain
abovementioned
20, 30, in the recovery
40, 50, 60, 70, 80, 90,optimal stage, i.e.,
contenttimes
and 100 loading the ins
of asphal
ing strain,
according
(MM‐0, to the was
MM‐9, denoted
abovementioned
DH‐0, DH‐12) bywere
optimal εLcontent
. The residual
of asphalt The
calculated. strain
before agingat
results theshown
(MM-0,
are end ofinthe
MM-9, Fig
DH-0, DH-12) were calculated. The results are shown in Figure 8.
denoted by εp, and εL/εp was used to denote the permanent deformat
total
1.01 deformation, i.e., the proportion of the viscous part of the defo

single temperature level (64 °C), the εL/εp values of 10, 20, 30, 40, 50, 6
loading times according to the abovementioned optimal content of a
(MM‐0,
1.00 MM‐9, DH‐0, DH‐12) were calculated. The results are shown
εp/εL

1.01
0.99 MM-0
MM-9
DH-0
DH-12
1.00
0.98
εp/εL

0 10 20 30 40 50 60 70 80 90 100
0.99 MM-0
Loading number(times)
MM-9
Figure 8. Results of ε /ε as a function DH-0
of
Figure 8. ResultsL ofp εL/εp as a function the number of loads
of the before of
number aging.
loads before aging.
DH-12
0.98
It
can be seen in Figure 8 that with the increase in the loading times, t
of different lignin‐modified asphalts also increased, which reflected the con
mulation0 of
10 the
20 permanent
30 40 50 deformation
60 70 80 of90the100
asphalt with the increase
 Polymers 2022, 14, 3572 12 of 17

It can be seen in Figure 8 that with the increase in the loading times, the εL /εp values
of different lignin-modified asphalts also increased, which reflected the continuous accumu-
lation of the permanent deformation of the asphalt with the increase in the loading times.
Polymers 2022, 14, x FOR PEER REVIEWεL /εp values were very close, which was not similar to SBS-modified asphalt [37,38]
The
and rubber-modified asphalt [39], indicating that the addition of lignin did not improve
the elasticity of the asphalt and was only for filling. The reason may be that the molecular
structure of lignin itself is complex. It has a three-dimensional network molecular structure,
containing many aromatic
tallic derivatives groups and high carbon
of hydrocarbons. Throughcontent
the[40], while analysis
further the base binder is aworking
of the
mixture of extremely complex high-molecular hydrocarbon and non-metallic derivatives
ofnism in FigureThrough
hydrocarbons. 9, the the
addition
further of a lignin
analysis modifier
of the working led to the absorption
mechanism in Figure 9, of th
liquid
the phase
addition of ainto
ligninthe asphalt–lignin
modifier interaction
led to the absorption of area during
the asphalt the phase
liquid mixingintoprocess,
anasphalt–lignin
the asphalt–lignin working
interaction areasystem
during theand changing
mixing process,the viscoelastic
forming behavior of th
an asphalt–lignin
working
bindersystem
[41]. and changing the viscoelastic behavior of the asphalt binder [41].

Figure
Figure 9. Schematic
9. Schematic diagram
diagram of the mechanism
of the mechanism of the asphalt–lignin
of the asphalt–lignin working systemworking
[41]. system [41]

The cumulative strain was reflected in the total residual strain of the asphalt sample
The cumulative strain was reflected in the total residual strain of the aspha
after cyclic loading. The smaller the cumulative strain, the better the high-temperature
after cyclic
resistance of the loading.
asphalt. In The
ordersmaller
to furtherthe cumulative
illustrate that ligninstrain,
had goodthe better the high‐tem
high-temperature
resistance
stability, of the asphalt.
the relationship betweenInthe
order to further
cumulative strainillustrate that lignin
and the number of cyclehad good high‐
loadings
isture
shown in Figure 10.
stability, the relationship between the cumulative strain and the number
It can be seen in Figure 10 that the cumulative strain of asphalt increased with the
loadings is shown in Figure 10.
increase in loading times, which was consistent with the actual load of the road. Under
the same loading times, the cumulative strain of Donghai asphalt and Maoming asphalt
25,000 before aging or RTFO aging decreased after 14,000
adding lignin, indicating that the addition
(a) Original of lignin could reduce the temperature sensitivity of
(b)asphalt
RTFOT and give it better resistance
12,000
20,000 MM-0 to high-temperature deformation. It can be seen fromMM-0 the slope of the curve that the
MM-9 performance of each asphalt sample under RTFO aging MM-9 tended to be consistent with that
10,000
Accumlated strain(%)

Accumlated strain(%)

DH-0 DH-0
15,000 DH-12 before aging, while in Figure 10c, it was found that theDH-12 slope of the curve of MM-9 was
8,000
significantly higher than that of MM-0, and the curve slope of DH-12 also had an increasing
trend, indicating that the addition of lignin could6,000
effectively prevent the base asphalt from
10,000
hardening after PAV aging, so as to prevent the aging of the base asphalt. Meanwhile, the
slope of the MM-0 curve during PAV aging was 4,000 greater than that of DH-0, indicating that
5,000 the hardening degree of 70# asphalt was less significant than that of 90# asphalt after PAV
2,000
aging. The main reason was that the content of heavy components in 90# asphalt increased
0 during the aging process. 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Loading number(times) Loading number(times)

2500

(c) PAV
2000 MM-0
MM-9
)
 The cumulative strain was reflected in the total residual strain of the asphalt s
after cyclic loading. The smaller the cumulative strain, the better the high‐tempe
resistance of the asphalt. In order to further illustrate that lignin had good high‐tem
Polymers 2022, 14, 3572 ture stability, the relationship between the cumulative strain and the13number
of 17 o
loadings is shown in Figure 10.

25,000 14,000

(a) Original (b) RTFOT

12,000
20,000 MM-0 MM-0
MM-9 MM-9
10,000
Accumlated strain(%)

Accumlated strain(%)
DH-0 DH-0
15,000 DH-12 DH-12
8,000

10,000 6,000

4,000
5,000
2,000

0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Loading number(times) Loading number(times)

2500

(c) PAV
2000 MM-0
MM-9
Accumlated strain(%)

DH-0
1500 DH-12

1000

500

0
0 10 20 30 40 50 60 70 80 90 100
Loading number(times)

Figure 10. Relationship

Figure 10. Relationshipbetween cumulative
between cumulative strain
strain and cycle
and cycle loadingloading times.
times. (a–c) (a–c) represents
represents the
cumulative strain of as is, short-term aging and long-term aging.
cumulative strain of as is, short‐term aging and long‐term aging.
3.5. Compatibility Analysis of Lignin and Asphalt
Chang et al. [42,43] studied the rheological properties of compatible and incompatible
polymer blends based on viscoelasticity theory and proposed a method to judge the
compatibility of blends by taking the double logarithm curve of storage modulus (G0 )
and loss modulus (G00 ), also known as the Han curve. Using the Han curve to judge
the compatibility of polymers, two basic conditions must be satisfied: (1) The G0 -G00
logarithm curves at different temperatures are superimposed; (2) The slope of the curve
at the low frequency end is equal to or close to 2. Through these two requirements, the
compatibility between modifier and asphalt can be judged [44]. In order to further analyze
the compatibility of the blends, the original binder and lignin-modified asphalt were
analyzed with a van Gurp–Palmen (VGP) diagram [45]. The VGP diagram is a plot of the
phase angle (δ) of asphalt against the corresponding complex shear modulus (G*). The
compatibility of the two asphalts and different contents of lignin was analyzed by frequency
sweep of Han curve and VGP map at 30 and 60 ◦ C, as shown in Figure 11.
 ibility of the blends, the original binder and lignin‐modified asphalt were analyzed w
a van Gurp–Palmen (VGP) diagram [45]. The VGP diagram is a plot of the phase angle
of asphalt against the corresponding complex shear modulus (G*). The compatibility
Polymers 2022, 14, 3572 the two asphalts and different contents of lignin was analyzed by frequency sweep
14 of 17 of H
curve and VGP map at 30 and 60 °C, as shown in Figure 11.

7 (a) MM-0 7
30℃ Original (b)MM-9
30℃ Original
6 30℃ RTFOT 6 30℃ RTFOT
30℃ PAV 30℃ PAV
5 60℃ Original 5 60℃ Original
60℃ RTFOT
lgG＇/Pa

60℃ RTFOT

lgG＇/Pa
4 60℃ PAV 90 4
80 60℃ PAV 90
70 80
3 δ/（°） 60 3 70

δ/（°）
50 60
40 50
2 30 2 40
2 20 2 30
ymers 2022, 14, x FOR PEER
1 REVIEW 10 2 3 4 5 6 7 20 14 o
1 10 10 10 10 10 10 1 1 10 2 3 4 5 6 7
G*/Pa 10 10 10 10 10 10
0 G*/Pa
0
2 3 4 5 6 7 2 3 4 5 6 7
lgG＂/Pa lgG＂/Pa

7 (c) DH-0 7 (d) DH-12

30℃ Original
30℃ Original
6 6 30℃ RTFOT
30℃ RTFOT
30℃ PAV
30℃ PAV 5
5 60℃ Original
60℃ Original
60℃ RTFOT
lgG＇/Pa
lgG＇/Pa

60℃ RTFOT 4 90
4 90 60℃ PAV
60℃ PAV 80
80

δ/ （° ）
3 3 70
δ/（°）

70
60 60
2 50 2 50
2 40 2 40
1 30 2 1
1 10 103 104 105 106 1 102 103 104 105 106
G*/Pa G*/Pa
0 0
2 3 4 5 6 7 2 3 4 5 6 7
lgG＂/Pa
lgG＂/Pa

Figure 11. Han diagram and VGP diagram of two asphalts and lignin-modified asphalt under
Figure 11. Han diagram and VGP diagram of two asphalts and lignin‐modified asphalt under
different aging conditions. (a–d) represent two types of asphalt with different temperatures and
ferent aging conditions. (a–d) represent two types of asphalt with different temperatures and
different aging.
ferent aging.
It can be seen in Figure 11 that the Han curves of the two asphalts and the lignin-
It can be
modified seen with
asphalt in Figure 11lignin
different thatcontents
the Han curves
were of the two
approximately asphalts
straight lines atandhighthe lign
temperatures before aging, and the slope of the Han curve was close
modified asphalt with different lignin contents were approximately straight lines at h to 2, which indicated
that the asphalt binder belonged to a homogeneous mixed system at this temperature.
temperatures before aging, and the slope of the Han curve was close to 2, which indica
The lignin had good compatibility with the matrix asphalt. However, the bifurcation
that phenomenon
the asphalt binder
occurredbelonged
in the unagedto astate
homogeneous mixed indicating
at low temperatures, system atthat thisthere
temperature.
was T
lignin had goodphase
microscopic compatibility
separation atwith
low the matrix asphalt.
temperatures. However,
After RTFOT aging, the bifurcation
the two original pheno
enonasphalts
occurred and in
thethe
lignin-modified
unaged state asphalt withtemperatures,
at low different lignin contents
indicating appeared
that to showwas mic
there
bifurcation at a low temperature, but did not separate at a high temperature, indicating
scopic phase separation at low temperatures. After RTFOT aging, the two original
that the compatibility of original asphalt and lignin-modified asphalt was better in high-
phalts and the conditions.
temperature lignin‐modified asphalt
After PAV aging,with different
the base asphaltlignin contents
and modified appeared
asphalt both to sh
bifurcation
displayedatthe a separation
low temperature,
phenomenon but did temperatures,
at high not separatebut atthere
a high
was temperature,
no separation at indicat
that the compatibility of original asphalt and lignin‐modified asphalt
low temperatures, which indicated that thermal oxygen and pressure aging was better
promoted the in hi
decomposition
temperature of matrix After
conditions. asphaltPAV
and modified
aging, theasphalt,
baseresulting
asphaltin and
largemodified
differences asphalt
in inter- both d
nal molecular weight distribution. In the VGP curve, it was found that the aged Maoming
played the separation phenomenon at high temperatures, but there was no separation
70# base asphalt and lignin-modified asphalt were superimposed at different temperatures,
low while
temperatures,
the Donghai which indicated
90# base binder and that thermal oxygen
lignin-modified and
asphalt werepressure agingonly
superimposed promoted
decomposition
before aging. Theof matrix asphalt
dispersion andaging
of different modified asphalt,
states could not beresulting
superimposed,in large differences
indicating
that the 70# binder was more compatible than the 90# binder.
internal molecular weight distribution. In the VGP curve, it was found that the ag
Maoming 70# base asphalt and lignin‐modified asphalt were superimposed at differ
temperatures, while the Donghai 90# base binder and lignin‐modified asphalt were
perimposed only before aging. The dispersion of different aging states could not be
perimposed, indicating that the 70# binder was more compatible than the 90# binder.
Polymers 2022, 14, 3572 15 of 17

4. Conclusions
In this paper, the aging properties of asphalt materials improved by a lignin modifier
were evaluated in detail based on a rheological test. A series of tests were conducted on
untreated and lignin-modified asphalt materials. Based on the test results, the following
conclusions can be drawn:
(1) The addition of lignin had a significant effect on the high-temperature resistance
of asphalt, but the degree of improvement in the high-temperature performance of
the two matrix asphalts was not the same. The results indicated that there was a
compatibility problem with lignin in improving the performance of matrix asphalt.
(2) The results of the repeated creep and recovery test indicated that lignin-modified
asphalt and base asphalt showed the same behavior, and lignin did not increase the
elastic recovery rate of modified polymer binders such as SBS. However, the addition
of lignin increased the viscosity resistance of the asphalt binder, which significantly
reduced the cumulative strain of the lignin-modified asphalt, and this was also the
fundamental reason for improving the high-temperature stability of matrix asphalt.
(3) After long-term aging, the cumulative strain of lignin-modified asphalt was higher
than that of base asphalt, and the long-term aging performance was significantly
improved. This was owing to the probable depolymerization and molecular weight
reduction of lignin during long-term aging.
This study provided a new understanding of the aging properties of lignin-modified
asphalt. Future research should focus on the thermal characteristics, field verification, and
life cycle assessment of asphalt pavement with different lignin modifiers.

Author Contributions: The authors contributed to this research article as follows: M.C. and C.C;
writing—original draft preparation, M.C.; writing—review and editing, literature review and method-
ology, Y.S.; experimental work and testing, X.H.; investigation and writing—original draft preparation,
X.Z. and P.D.; supervision and funding acquisition, C.C. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by the Science and Technology Planning Project of Yunnan
Science and Technology Department (Joint Agricultural Project), grant number 202101BD070001-060;
Science and Technology Project of Gui Zhou Highway Bureau, grant number 2021QLM06; Scientific
Research Fund of Yunnan Provincial Department of Education, grant number 2020J0420.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Chen, X.P.; Ma, Y.F. Research on performance of crumb rubber modified asphalt. New Chem. Mater. 2010, 38, 118–120.
2. Ouyang, C.; Wang, S.; Zhang, Y.; Zhang, Y. Improving the aging resistance of asphalt by addition of Zinc dialkyldithiophosphate.
Fuel 2006, 85, 1060–1066. [CrossRef]
3. Tian, W.M. On aging performance analysis of SBS modified asphalt. Shanxi Archit. 2012, 38, 139–141.
4. Zhang, Q.C.; Wang, Y.; Xiong, L. Study on anti ultraviolet aging ability of nano TiO2 modified asphalt. Roads Mot. 2011, 27, 88–91.
5. Qian, X.O. Study on improving adhesion between Asphalt and acid stone in Qinghai area by anti-spalling agent. Highway 2011,
56, 141–146.
6. Yadykova, A.Y.; Ilyin, S.O. Rheological and adhesive properties of nanocomposite bitumen binders based on hydrophilic or
hydrophobic silica and modified with bio-oil. Constr. Build. Mater. 2022, 342, 127946. [CrossRef]
7. Ilyin, S.O.; Arinina, M.P.; Mamulat, Y.S.; Malkin, A.Y.; Kulichikhin, V.G. Rheological properties of road bitumens modified with
polymer and solid nanosized additives. Colloid J. 2014, 76, 425–434. [CrossRef]
8. Zhang, W.; Zou, L.; Wang, Y.; Liu, J.; Yang, C.; Di, J.; Hu, H.; Yang, Z. Influence of High Viscosity Petroleum Resin (HV-PR) on the
Intermediate and High Temperature Performances of Styrene–Butadiene–Styrene Block Copolymer (SBS) Modified Bitumen.
Arab. J. Sci. Eng. 2022, 12, 1–13. [CrossRef]
Polymers 2022, 14, 3572 16 of 17

9. Pi, Y.H. Test Research on the Road Performance of Asphalt Mixtures with Bonifibers and SBS Modified. J. Transp. Eng. Inf. 2008, 6,
56–60. [CrossRef]
10. Cheng, Z.S. Demand for Oil Will Exceed Supply After 2007; China Petroleum & Chemical Corporation: Beijing, China, 2005; p. 53.
11. Wen, J.L.; Chen, T.Y.; Sun, R.C. Research progress on separation and structural analysis of lignin in lignocellulosic biomass. J. For.
Eng. 2017, 2, 76–84. [CrossRef]
12. Ren, L.F.; He, Q.Q.; Qing, T.T.; Wang, X.C. Activation of enzymatic hydrolysis lignin and used for preparation of phenol-
formaldehyde Resin. New Chem. Mater. 2016, 44, 47–49.
13. Ma, Z.M.; Li, S.J.; Yang, D.M. Activation of enzymatic hydrolysis lignin and used for preparation of phenol-formaldehyde resin.
For. Eng. 2017, 33, 64–67.
14. Pinheiro, F.G.C.; Soares, A.K.L.; Santaella, S.T. Optimization of the acetosolv extraction of lignin from sugarcane bagasse for
phenolic resin production. Ind. Crops Prod. 2017, 96, 80–90. [CrossRef]
15. Li, Y.; Han, Y.M.; Qin, T.F.; Chu, F.X. Research progress of lignin is synthesis of polyurethane materials. Chem. Ind. Eng. Prog.
2011, 30, 1990–1997.
16. Ferdosian, F.; Yuan, Z.; Anderson, M.; Xu, C.C. Synthesis and characterization of hydrolysis lignin-based epoxy resins. Ind. Crops
Prod. 2016, 91, 295–301. [CrossRef]
17. Kumari, S.; Chauhan, G.S.; Monga, S.; Kaushik, A.; Ahn, J.H. New lignin-based polyurethane foam for wastewater treatment.
RSC Adv. 2016, 6, 77768–77776. [CrossRef]
18. Feng, P.; Chen, F.G. Application progress of lignin in epoxy resin synthesis. J. Mater. Sci. Technol. 2010, 2, 54–60. [CrossRef]
19. Arshanitsa, A.; Krumina, L.; Telysheva, G.; Dizhbite, T. Exploring the application potential of incompletely soluble organosolv
lignin as a macromonomer for polyurethane synthesis. Ind. Crops Prod. 2016, 92, 1–12. [CrossRef]
20. Zhao, Z.; Chen, M.Q.; Wang, Y.S.; Ding, S.S.; Yang, J. Synthesis and property of epoxy resin based on degrading lignin. J. Mater.
Sci. Technol. 2017, 3, 46–52. [CrossRef]
21. Li, J.H.; Liu, C.Z.; Li, Q.L. Study on properties of lignin-filled polysulfide sealant. Adhesion 2017, 38, 39–42. [CrossRef]
22. Luiz, F.N.; Scremin, F.R.; Werncke, E.; Basso, R.L.D.O.; Possan, E.; Bittencourt, P.R.S. Thermal evaluation by DSC and tensile
strength of extrudated blends from polyethylene terephthalate and kraft lignin. Waste Biomass Valorization 2018, 6, 367–373.
[CrossRef]
23. Dizhbite, T.; Telysheva, G.; Jurkjane, V.; Viesturs, U. Characterization of the Radical Scavenging Activity of Lignins-Natural
Antioxidants. Bioresour. Technol. 2004, 95, 309–317. [CrossRef] [PubMed]
24. Thakur, V.K.; Thakur, M.K. Recent advances in green hydrogels from lignin: A review. Int. J. Biol. Macromol. 2015, 72, 834–847.
[CrossRef]
25. Yu, H.; Zhu, Z.; Zhang, Z.; Yu, J.; Oeser, M.; Wang, D. Recycling waste packaging tape into bituminous mixtures towards enhanced
mechanical properties and environmental benefits. J. Clean. Prod. 2019, 229, 22–31. [CrossRef]
26. Sun, Q.N.; Qin, T.F.; Li, G.Y. Progress on activation and application to wood adhesives of lignin. Polym. Bull. 2008, 9, 55–60.
27. Wu, W.J.; Wang, T.; Wu, J.T. Impact of Lignin on Aging Property of Modified Asphalt. Pap. Sci. Technol. 2018, 37, 19–24.
28. Gao, J.; Wang, H.; Liu, C.; Ge, D.; You, Z.; Yu, M. High-temperature rheological behavior and fatigue performance of lignin
modified asphalt binder. Constr. Build. Mater. 2020, 230, 117063. [CrossRef]
29. Batista, K.B.; Padilha, R.P.L.; Castro, T.O.; Silva, C.F.S.C.; Araújo, M.F.A.S.; Leite, L.F.M.; Pasa, V.M.D.; Lins, V.F.C. High-
temperature, low-temperature and weathering aging performance of lignin modified asphalt binders. Ind. Crops Prod. 2018, 111,
107–116. [CrossRef]
30. Xu, G.; Wang, H.; Zhu, H. Rheological properties and anti-aging performance of asphalt binder modified with wood lignin.
Constr. Build. Mater. 2017, 151, 801–808. [CrossRef]
31. Zhang, H.L.; Duan, H.H.; Tang, J.C. Effects of Different Anti-stripping Agents on Physical, Rheological and Aging Properties of
Asphalt. J. Highw. Transp. Res. Dev. 2021, 38, 1–9. [CrossRef]
32. Lin, J.T.; Pan, L. High Temperature Performance Evaluation of Asphalt Based on MSCR Test and Burgers Model Analysis. J.
Highw. Transp. Res. Dev. 2018, 35, 22–29. [CrossRef]
33. Cheng, C.; Tao, G.X.; Wang, Q. Experimental study on performance of lignin modified asphalt at high temperatures. China For.
Sci. Technol. 2019, 4, 148–154.
34. Chen, P.Q.; Zhang, Y.Y.; Luo, Y.C. Discussion on Formation Mechanism of Epoxy Asphalt by Four-component Analysis. China
Build. Waterproofing 2012, 10, 16–19. [CrossRef]
35. Henoy, A. Refinement of the superpave specification parsmeter for performance grading of asphalt. J. Transp. Eng. 2001, 127,
357–362.
36. Chen, Z.J.; Hao, P.W. High temperature performance of chemical modified asphalt based on repeated creep and recovery test. J.
Jiangsu Univ. Nat. Sci. Ed. 2017, 38, 479–483.
37. Peng, X.L.; Gao, D.H. Research on Elastic Recovery Performance of SBS Modified Asphalt. Guangdong Highw. Commun. 2018, 44,
1–6. [CrossRef]
38. Yin, H.; Li, K. Grey Correlation Analysis of Zero Shear Viscosity and High Temperature Rheological Parameters of Asphalt. J.
Build. Mater. 2020, 23, 108–113. [CrossRef]
39. Cui, Y.X.; Hao, P.W. High Temperature Performance of Rubber Modified Asphalt Based on MSCR Test. Road Mach. Constr. Mech.
2019, 36, 47–51. [CrossRef]
Polymers 2022, 14, 3572 17 of 17

40. Zeng, M.Z.; Hu, Y.B. Progress in preparation and application of lignin porous carbon. Chem. Ind. Eng. Prog. 2021, 40, 4573–4586.
[CrossRef]
41. Xu, C.; Wang, D.; Zhang, S.; Guo, E.; Luo, H.; Zhang, Z.; Yu, H. Effect of lignin modifier on engineering performance of bituminous
binder and mixture. Polymers 2021, 13, 1083. [CrossRef]
42. Han, C.D.; Baek, D.M.; Kim, J.K.; Ogawa, T.; Sakamoto, N.; Hashimoto, T. Effect of volume fraction on the order-disorder
transition in low molecular weight polystyrene-block-polyisoprene copolymers. 1. Order-disorder transition temperature
determined by rheological measurements. Macromolecules 1995, 28, 5043–5062. [CrossRef]
43. Han, C.D.; Kim, J.; Kim, J.K. Determination of the order-disorder transition temperature of block copolymers. Macromolecules
1989, 22, 383–394. [CrossRef]
44. Zan, X.Y.; Zhang, X.N.; Wang, D.Y. Microstructure of asphalt mastic using dynamic mechanical analysis. J. Jilin Univ. Eng. Technol.
Ed. 2009, 39, 916–920.
45. Wang, W.M.; Xie, X.B.; Lan, X. Phase structure analysis of nano-carbon powder–rubber powder–SBS–modified asphalt based on
dynamic mechanics. Silic. Bull. 2021, 40, 2444–2453. [CrossRef]