materials

Article
Preparation and Characteristics of Ethylene
Bis(Stearamide)-Based Graphene-Modified Asphalt
Xia Zhang 1 , Jun-Xi He 1 , Gang Huang 1, *, Chao Zhou 1 , Man-Man Feng 1 and Yan Li 2
1 National and Local Joint Engineering Laboratory of Traffic Civil Engineering Materials,
Chongqing Jiaotong University, Chongqing 400074, China; [email protected] (X.Z.);
[email protected] (J.-X.H.); [email protected] (C.Z.);
[email protected] (M.-M.F.)
2 Chongqing Tongli Expressway Maintenance Engineering Co., Ltd., Chongqing 400074, China;
[email protected]
* Correspondence: [email protected]; Tel.: +86-23-6265-2574




Received: 7 February 2019; Accepted: 1 March 2019; Published: 5 March 2019


Abstract: In this study, graphene-modified asphalt (GMA) was prepared from SK-70# matrix asphalt
and ethylene bis(stearamide) (EBS). Based on the uniform design method, a model was created using
Data Processing System (DPS) software and First Optimization (1stOpt) software using the graphene
mixing amount, EBS mixing amount, shear rate, shear time, and shear temperature as factors and
using the asphalt penetration, softening point, force ductility, SHRP-PG test, and multistress creep
recovery data as indices. Calculations and analysis showed that the optimal composition and
preparation parameters of GMA are as follows: the graphene proportion is 20‰, the EBS proportion
is 1%, the shear rate is 6000 r.p.m., the shear time is 180 min, and the shear temperature is 140 ◦ C.
The prepared GMA had a significantly improved softening point, low-temperature fracture energy,
antirutting factor, and creep recovery rate, indicating that adding graphene can improve the high- and
low-temperature performance of asphalt. The prepared GMA was characterized by X-ray diffraction
(XRD). The dispersibility of graphene in asphalt was evaluated by fluorescence microscopy and
Image-Pro Plus imaging software. The results show that graphene can exist in asphalt in a stable
form, which increases the loose-layered structure of stacked asphalt or gum. The intense adsorption
effect of graphene strengthens the ordered structure of asphalt. However, due to its dispersibility
characteristics, some graphene exists in asphalt in clustered form. When the graphene-to-dispersant
ratio approaches the optimal value, the dispersant changes the form of graphene in asphalt from
irregular clusters to regular clusters and from large, distinct clusters to small, indistinct clusters.
When dispersant cannot uniformly disperse graphene in asphalt, graphene clusters primarily form
medium-sized grains.

Keywords: graphene-modified asphalt; ethylene bis(stearamide); uniform design; dispersibility;

modification

1. Introduction
Graphene, formed by carbon atoms via sp2 electron orbital hybridization, is a beehive-shaped,
two-dimensional carbon nanometer inorganic material with various superior properties. In recent
years, graphene has become a focus area of scientific research [1–11]. Asphalt pavement is the primary
form of pavement in road engineering. Based on the characteristics of the basic chemical structures
of graphene and asphalt (components), graphene and asphalt share similar structures and the two
should have excellent affinity [12,13]. Graphene has an enormous specific surface area and can have
an intense physical adsorption effect with asphalt. Additionally, graphene is capable of physical

Materials 2019, 12, 757; doi:10.3390/ma12050757 www.mdpi.com/journal/materials

Materials 2019, 12, 757 2 of 19

adsorption and nonpolarized adsorption with light components and polycyclic aromatic hydrocarbons
released by asphalt when heated. Under high temperature, graphene effectively suppresses the
release of poisonous, harmful asphalt fumes and is environmentally friendly [14,15]. Therefore,
graphene-modified asphalt (GMA) has numerous excellent properties and multiple functional groups
which can significantly improve asphalt performance (such as its viscoelasticity), reduce or eliminate
various asphalt pavement hazards, such as ruts, fractures, and surface wear, and reduce the cost of
the entire pavement life cycle. GMA has important scientific and application value for promoting
the development of high-performance and durable long-life asphalt pavement [16]. In recent years,
Wang Z. et al. [17–19] showed that expanded graphite nanoplatelet composite-modified asphalt
materials can effectively enhance the fracture recovery energy, strength, and healing capabilities of
an asphalt mixture. Yao H. et al. [20] found that graphite nanoplatelet-modified asphalt can improve
asphalt’s high- and low-temperature performance, its complex shear modulus, and the antirutting
and waterproof capabilities of the asphalt mixture. Li Y. et al. [21] showed that when graphene oxide
(GO) and asphalt were mixed, CO2 gas was released during GO decomposition; the GO structure was
completely stripped and was scattered in asphalt to form a single layer. Huang Gang et al. [14,22,23]
used expanded graphite to suppress asphalt fumes and proved that expanded graphite was infiltrated
by asphalt and was stripped to form graphene platelets that were partially scattered in asphalt.
Cheng I. F. et al. [24] developed a technique to produce large graphene flakes on an asphalt surface,
which proved that graphene can stably exist in an asphalt medium in a single layer. The existing
studies primarily focus on the modification of pavement asphalt using graphene oxide or graphene
nanoplatelets to improve asphalt performance [25–34]. There is no report of research on pavement
asphalt modification using graphene.
Based on the uniform design method and using the asphalt penetration index, softening point,
force ductility, SHRP-PG test, and multistress creep recovery test data as indices, this paper employed
Data Processing System (DPS) and First Optimization (1stOpt) software to establish a mathematical
model to investigate the material composition and preparation parameters of GMA. In addition, a
microscopic analysis method and Image-Pro Plus software were applied to evaluate the dispersibility
of graphene in asphalt.

2. Experimental Method and Performance Evaluation

2.1. Materials
The matrix asphalt used in this study was SK-70# asphalt (PG64-22). Each index was tested
based on the Standard Test Method of Bitumen and Bituminous Mixture for Highway Engineering
(JTG E20-2011) by the Chinese Ministry of Communications [35]. The graphene was NK-1 graphene
produced by the Sichuan Deyang Graphene Carbon Technology Co., Ltd., Deyang, Sichuan, China.
The dispersant was ethylene bis(stearamide) (EBS) from the Malaysia Kao Company, Petaling Jaya,
Malaysia. The basic solvent was trichloroethylene. The technical parameters of SK-70# asphalt,
graphene, and EBS are listed in Tables 1–3, respectively.

Table 1. Parameters of SK-70# asphalt.

Test Item Test Result Technology Index Test Method

penetration (25 ◦ C, 5 s, 100 g)/0.1 mm 64.70 60.0~80.0 T0604
ductility (15 ◦ C, 5 cm/min)/cm 103.00 ≥100.0 T0605
softening point/◦ C 48.10 ≥45.0 T0606
actual
density (15 ◦ C)g/cm3 1.21 T0603
measurement
wax content/% 2.04 ≤2.2 T0615
dynamic viscosity(60 ◦ C)/Pa·s 197 ≥180 T0620
flash point/◦ C 315 ≥260 T0611
mass change/% −0.18 ≤±0.8 T0610
after RTFOT residual penetration ratio/% 63.50 ≥61.0 T0604
10 ◦ C ductility/cm 8.60 ≥6.0 T0605
Materials 2019, 12, 757 3 of 19

Table 2. Parameters of graphene NK-1.

Parameter Index
graphene layers/thickness 1–3, monolayer rate >80%
ash content/% <3.0
specific surface area/m2 /g 110.0
film electrical conductivity/S/cm 550.0
flake diameter (D50)/um 7.0~12.0
flake diameter (D90)/um 11.0~15.0
appearance Black-grey powder
bulk density/g/mL 0.01~0.02
water content/% <2.0

Table 3. Parameters of dispersant ethylene bis(stearamide).

Parameter Index
appearance White powder
initial melting point/◦ C 141.0~146.0
total amine/mg KOH/g ≤3.0
color value ≤5.0
acid value/mg KOH/g ≤7.0
fineness degree/mesh 600
heating decrement/% ≤0.5
flash point/◦ C ≥28.0

2.2. Equipment and Characterization

The shear processing of the modified asphalt was performed using a BME200L intense shear
and mix emulsion machine (motor power 0.4 kw, rotational speed range 0–10,000 r.p.m.) from the
Shanghai Weikang Machine Manufacturing Co., Ltd., Shanghai, China. The ultrasonic separation of
the graphene mixture solution was performed using JP-040 ultrasonic equipment (ultrasonic wave
power: 240 W, ultrasonic wave frequency: 40 kHz) from the Skymen Cleaning Equipment Shenzhen
Co., Ltd., Shenzhen, China. The asphalt penetration index, softening point, and force ductility were
measured using an SYD-2801D penetration index tester, an SYD-2806E softening point tester, and an
SYD-45DBF ductility/tension tester with temperature and speed regulation from the Shanghai Changji
geological instrument Co., Ltd., Shanghai, China. The asphalt rheological performance was tested with
a Bohlin DSR I dynamic shear rheometer from the Malvern Panalytical Instrument Co., Ltd., Malvern,
UK. The structure characterization of the modified asphalt was performed with a D8-Advance X-ray
diffractometer (copper/palladium, voltage: 40 kV, current: 40 MA, test rate: 0.1 sec/step, wavelength:
1.5418 angstrom) from the Bruker Corporation, Karlsruhe, Germany. The graphene dispersion in GMA
was observed using a DM6 M microscope from the Leica Microsystems Inc. Co., Ltd., Buffalo Grove,
IL, USA.

2.3. GMA Preparation

The GMA preparation process was as follows:
(1) The graphene and EBS were measured using an electric analytical balance (resolution:
0.0001 g, SHIMADZU Co., Tokyo, Japan) and were placed in a 1000 mL beaker. A total of 350 mL
of trichloroethylene was added and mixed with a glass bar to produce a mixed solution. The mixed
solution was heated in a constant temperature (80 ◦ C) hot water bath for 15 min. Then, the opening
was covered with preservative film. The mixed solution was ultrasonically processed for 2.0 h with a
5-min break every 30 min.
(2) First, 350 g of matrix asphalt was prepared. Then, the mixed solution (after ultrasonic
processing) was poured into the container filled with 350 g of matrix asphalt. The container opening
was sealed with 3–4 layers of preservative film and cultured for 12 h so that the asphalt was completely
dissolved in the mixed solution. The trichloroethylene in asphalt was completely removed using a
was covered with preservative film. The mixed solution was ultrasonically processed for 2.0 h with
a 5-minute break every 30 min.

(2) First, 350 g of matrix asphalt was prepared. Then, the mixed solution (after ultrasonic
processing) was poured into the container filled with 350 g of matrix asphalt. The container opening
Materials 2019, 12, 757 4 of 19
was sealed with 3–4 layers of preservative film and cultured for 12 h so that the asphalt was
completely dissolved in the mixed solution. The trichloroethylene in asphalt was completely
rotary
removed evaporator
using a (from
rotarythe Büchi Labortechnik
evaporator AG, Uster,
(from the Büchi Switzerland)
Labortechnik AG,with theSwitzerland)
Uster, following parameters:
with the
oil bath temperature: 110 ◦ C, rotational speed: 85~90 r.p.m., and evaporation time: 60 min. After the
following parameters: oil bath temperature: 110 °C, rotational speed: 85~90 r.p.m., and evaporation
trichloroethylene
time: 60 min. After was
theremoved, the asphalt
trichloroethylene waswas poured into
removed, a container
the asphalt was for the shear
poured into atest to prepare
container for
the
the GMA
shearwith test importing
to prepare nitrogen
the GMAinto the bottom
with of the nitrogen
importing container into
continually. The GMA
the bottom of thepreparation
container
process is shown
continually. in Figure
The GMA 1.
preparation process is shown in Figure 1.

Figure 1. Graphene-modified asphalt preparation process.

Figure 1. Graphene-modified asphalt preparation process.
2.4. Experimental Design
2.4. Experimental Design
Uniform design is an application of the “pseudo-Monte Carlo method” in number theory. Uniform
design can select a subset of typical test points from the entire set of test points, ensure the uniform
distribution of test points in a test range, and reflect major features of the test system. The uniform
design method is widely employed to investigate material composition and demonstrates excellent
applicability and accuracy [36,37]. Therefore, in this paper, the uniform design method was employed
for GMA composition design. In test design, each uniform design table has a code Un (qs ). “U”
represents uniform design; “n” represents n tests; “q” indicates that each factor has q levels; “s” means
the table has s columns [38–40].
Five factors with significant impact (X1 , X2 , X3 , X4 , X5 ) were selected to investigate GMA
composition and preparation parameters [41]. The details of these factors follow: X1 is the shear
rate (r.p.m.); X2 is the shear time (min); X3 is the graphene proportion (‰) (mass fraction of matrix
asphalt); X4 is the EBS proportion (%) (mass fraction of graphene); and X5 is the shear temperature
(◦ C). Each factor has 10 levels, as listed in Table 4.

Table 4. Test design factor levels.

Level
Factor
1 2 3 4 5 6 7 8 9 10
X1 /r.p.m. 2000 2500 3000 3500 4000 4500 5000 5500 6000 7000
X2 /min 30 30 60 60 90 90 120 120 180 180
X3 /‰ 2 4 6 8 10 12 14 16 18 20
X4 /% 1 2 3 4 5 6 7 8 9 10
X5 /°C 110 110 120 120 130 130 140 140 150 150
Materials 2019, 12, 757 5 of 19

Based on the factor levels in Table 4, a corresponding uniform design table and a usage table were
generated to design combinations of test parameters. The obtained test parameter combinations are
listed in Table 5.

Table 5. Test combinations design table.

Factor
Test #
X1 /r.p.m. X2 /min X3 /‰ X4 /% X5 /◦ C
1# 2000 60 8 5 150
2# 2500 90 16 10 140
3# 3000 180 2 4 130
4# 3500 30 10 9 120
5# 4000 60 18 3 110
6# 4500 120 4 8 150
7# 5000 180 12 2 140
8# 5500 30 20 7 130
9# 6000 90 6 1 120
10# 7000 120 14 6 110

Based on the preparation parameters of each test group in Table 5, the GMA was prepared and
subsequent performance tests were performed.

2.5. Performance Evaluation and Microanalysis

The GMA pavement performance was analyzed via its penetration index, softening point, and
force ductility index. An SHRP-PG test and a multistress creep recovery test were performed to
analyze the viscoelasticity of GMA. The GMA structure was characterized via XRD (from the Bruker
Corporation, Karlsruhe, Germany) and a fluorescence microscope (from the Leica Microsystems Inc.
Co., Ltd., Buffalo Grove, IL, USA).

3. Results and Discussion

3.1. Indices Data Analysis

The penetration index represents the asphalt thickness at the test temperature, which reflects
asphalt’s rheological performance to some extent [42,43]. The test conditions were as follows: the
water bath was at a constant temperature of 25 ◦ C, the standard penetration load was 100 g, and the
penetration time was 5 s. The softening point is the critical temperature at which asphalt changes
from a solid state to a liquid, which reflects the temperature response performance of the asphalt
material [44]. The ductility reflects asphalt’s deformation capability at a specified temperature and its
stretch rate before it is stretched to rupture [45,46]. In this study, the force ductility test environment
was as follows: the water bath was at a constant temperature of 5 ◦ C, and the stretch rate was 5 cm/min.
Three indices were obtained during the asphalt specimen tensile process: force, ductility, and fracture
energy (the integral of force and ductility). The test results for the asphalt indices are shown in
Figure 2a,b.
The penetration test result in Figure 2 shows that after graphene was added, except for
test groups 1 and 8, the asphalt penetration indices decreased. Test group 6 had the minimum
penetration at 5.02 mm. Test groups 1 and 8 had the maximum penetration indices, at 6.54 mm.
The penetration test results indicate that the graphene addition hardened the asphalt overall, improving
its high-temperature performance. The softening point test results show that after adding graphene,
the asphalt softening points in all test groups increased. Test group 7 had the maximum softening
point at 51.7 ◦ C. The softening point test results suggest that adding graphene improves asphalt’s
high-temperature performance. The force ductility test results show that after adding graphene,
the maximum ductility force, ductility, and fracture energy improved significantly. Test group 7
 3.1. Indices Data Analysis
The penetration index represents the asphalt thickness at the test temperature, which reflects
asphalt’s rheological performance to some extent [42,43]. The test conditions were as follows: the
water
Materials bath
2019, was at a constant temperature of 25 °C, the standard penetration load was 100 g, and the6 of 19
12, 757
penetration time was 5 s. The softening point is the critical temperature at which asphalt changes
from a solid state to a liquid, which reflects the temperature response performance of the asphalt
had the maximum
material [44]. Theductility force atasphalt’s
ductility reflects 150.0 N; test groupcapability
deformation 6 had theat amaximum ductility at
specified temperature and46.70
its cm;
and test group
stretch 9 had it
rate before the maximum
is stretched fracture[45,46].
to rupture energy Inat 3633.0
this ·mm.
study,Nthe forceThe force test
ductility ductility test results
environment
was as follows:
demonstrate the water
that adding bath was
graphene at a constantimproves
significantly temperature of 5 °C,low-temperature
asphalt’s and the stretch rate was 5
performance.
cm/min. Three indices were obtained during the asphalt specimen tensile
To summarize, graphene addition improves both the high- and low-temperature performance of process: force, ductility,
and The
asphalt. fracture energy
optimal (the integral
material of forceand
composition and preparation
ductility). The test resultsfor
parameters forpreparing
the asphaltGMA
indices
areare
similar
shown in Figure 2a,b.
to the design parameters of test groups 6–9.

Penetration/0.1mm Softening point /℃

Softening point /℃ Penetration/0.1mm

68 68
64 64
60 60
56 56
52 52
48 48
52 52

51 51

50 50

49 49

48 48

SK-70# 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
(a)
Sample Number

Maximum force/N Ductility/cm Fracture energy /N·mm

Maximum force/N

150 150

125 125

100 100
50 50
Ductility/cm

25 25
Fracture energy /N·mm

0 0
3000 3000

1500 1500

0 0
SK-70# 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
(b) Sample Number

Figure 2. (a,b) Conventional asphalt performance index test results.

Figure 2. (a,b) Conventional asphalt performance index test results.
3.2. DSR Test
The rheological parameter of graphene asphalt was tested using the Dynamic Shear Rheological
test (DSR) proposed by the Strategic Highway Research Project (SHRP) in the United States to
characterize viscoelastic energy and evaluate the high- and low-temperature performance and the
antifatigue performance of asphalt [47].

3.2.1. SHRP-PG Test

The SHRP-PG evaluates the high-temperature performance indices of asphalt cement material.
The test reflects two important parameters of asphalt’s viscoelasticity: the complex shear modulus G*
and the phase angle δ. The complex shear modulus G* is the ratio of the maximum shear stress and the
maximum shear strain in the SHRP-PG classification test. The complex shear modulus G* represents
Materials 2019, 12, 757 7 of 19

the overall resistance of a material under repeated shear deformation, which includes the elastic
modulus G0 and the viscous modulus G00 . The elastic modulus is given by G0 = G*cosδ, which reflects
the asphalt energy stored and released during shear deformation. The viscous modulus is given by
G00 = G*sinδ, which represents the dissipated energy in the form of heat due to internal friction during
the asphalt shear process. G*sinδ is defined as the antirutting factor, which represents the capability of
asphalt cement material to resist permanent deformation under high temperature [48,49]. In this study,
the test temperature was 64 ◦ C; the diameter of the smooth metal plate was 25 ± 0.05 mm; the gap
between the test plate and the roof was 1 ± 0.05 mm; and the test frequency was 10 rad/s. The test
results are shown
Materials 2019, 12, in Figure
x FOR PEER 3.
REVIEW 9 of 23

Phase angle/° Change ratio of anti-rutting factor/%

Anti-rutting factor/kPa Complex shear modulus/kPa
Phase angle/°

Complex shear modulus/kPa

87 87
86 86

2000 2000
Anti-rutting factor/kPa

1600 1600

2000 2000

1600 1600
Change ratio/%

140 140
120 120
100 100
SK-70# 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
Sample Number

Figure 3. SHRP-PG
Figure 3. SHRP-PGtesttest
results (64(64◦ C):
results °C):The
Thechanging trendsofofphase
changing trends phase angle,
angle, complex
complex shearshear modulus,
modulus,
antirutting factor,
antirutting andand
factor, change
changeratio
ratioofofantirutting
antirutting factor areshown
factor are shownseparately.
separately.
TheThe change
change ratioratio
of of
antirutting factor
antirutting is that
factor thethe
is that antirutting
antiruttingfactor
factorof
of each testgroup
each test groupisisdivided
dividedby by
thethe antirutting
antirutting factor
factor of of
SK-70#
SK-70# basebase asphalt.
asphalt.

Figure
Figure 3 shows
3 shows thatthat after
after grapheneisisadded,
graphene added, the
the GMA
GMAphase angle
phase angledecreases to some
decreases extent,
to some extent,
while the complex shear modulus and the antirutting factor improve to some extent.
while the complex shear modulus and the antirutting factor improve to some extent. Test groups Test groups 7,
8, and 10 had the most significant improvement in antirutting factor (42.4%, 28.2%, and 25.9%,
7, 8, and 10 had the most significant improvement in antirutting factor (42.4%, 28.2%, and 25.9%,
respectively). It can be inferred that adding graphene improves asphalt’s high-temperature stability.
respectively). It can be inferred that adding graphene improves asphalt’s high-temperature stability.
The optimal proportions of graphene and dispersant for graphene asphalt preparation is similar to
The optimal proportions
the material of graphene
design parameters andgroups
for test dispersant for 10.
7, 8, and graphene asphalt preparation is similar to the
material design parameters for test groups 7, 8, and 10.
3.2.2. Multistress Creep Recovery (MSCR) Test
3.2.2. Multistress Creep Recovery (MSCR) Test
Repeated multistress creep recovery tests were performed to further evaluate GMA’s high-
Repeated
temperaturemultistress
stability. Thecreep recovery was
test temperature tests
basedwere performed
on the to further test
SHRP-PG classification evaluate GMA’s
result and
high-temperature stability.specification
the AASHTO T350-14 The test temperature
[50–52]. First,was
a 100based on the
Pa shear SHRP-PG
stress classification
was applied test result
for 100 s. Then,
while
and the the 100 Pa
AASHTO shear stress
T350-14 was applied,
specification cyclicFirst,
[50–52]. loading (1 sPa
a 100 loading
shearand 9 s unloading)
stress was applied was
forrepeated
100 s. Then,
10 times. Next, a 3200 Pa shear stress was applied to repeat the above process. The
while the 100 Pa shear stress was applied, cyclic loading (1 s loading and 9 s unloading) was entire test included
repeated
30 cycles and took 300 s. The delayed elasticity recovery capability of GMA was evaluated via the
10 times. Next, a 3200 Pa shear stress was applied to repeat the above process. The entire test included
recovery rate R and the unrecoverable creep compliance Jnr. The test results are shown in Figure 4a–
30 cycles and took 300 s. The delayed elasticity recovery capability of GMA was evaluated via the
c.
recovery rate R and the unrecoverable creep compliance Jnr. The test results are shown in Figure 4a–c.
Materials 2019, 12, 757 8 of 19
Materials 2019, 12, x FOR PEER REVIEW 10 of 23

Creep recovery rate R0.1/% Creep recovery rate R3.2/%

16 16

Creep recovery rate R0.1/%

12 12

8 8

4 4

Creep recovery rate R3.2/%

1.0 1.0

0.5 0.5

0.0 0.0
SK-70# 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
(a) Sample Number
-1
Unrecoverable creep compliance/kPa

-1
6.0 Unrecoverable creep compliance Jnr0.1/kPa 6.0

4.5 4.5

-1
Unrecoverable creep compliance/kPa
3.0 3.0

-1
Unrecoverable creep compliance Jnr3.2/kPa
6.0 6.0

4.5 4.5

3.0 3.0

SK-70# 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
(b) Sample Number

Relative difference of strain recovery rate/%

Relative difference of unrecoverable creep compliance/%
Relative difference of strain recovery rate/%

Relative difference of unrecoverable creep compliance /%

100 100

90 90

80 80

70 70
40 40

20 20

0 0
SK-70# 1# 2# 3# 4# 5# 6# 7# 8# 9# 10#
(c) Sample Number

Figure 4. (a–c) Creep recovery test result.

Figure 4 shows that compared with matrix asphalt, GMA’s creep recovery rate under 0.1 kPa shear
stress and its creep recovery rate under 3.2 kPa of shear stress improve to some extent, indicating that
Materials 2019, 12, 757 9 of 19

the addition of graphene improves the asphalt’s viscoelastic recovery capability. Test groups 8, 2, and 7
have superior creep recovery rates at 14.04%, 8.68%, and 5.12%, respectively, which are 6.41 times, 3.96
times, and 2.34 times greater than those for matrix asphalt. In the 3.2 kPa creep recovery test, matrix
asphalt has almost no creep recovery, while groups 2, 8, and 7 have improved creep recovery rates at
0.99%, 0.69%, and 0.53%, respectively. The optimal parameters for GMA are similar to the parameters
for groups 2, 7, and 8.
To summarize, based on a test of three major indices and the DSR test result, the optimal material
composition and parameters for GMA preparation are similar to the design parameters for test groups
7 and 8.

3.3. Determining the Optimum Mixing Ratio

In this paper, Data Processing System (DPS) analysis software (Version DPSv17.10) and
First Optimization (1stOpt) software (Version 7.0) are employed to calculate the optimal material
composition for GMA preparation. DPS is a data processing system that integrates functions such as
numeric calculation, statistical analysis, model simulation, drawing, and table generation [53,54].
1stOpt is general-purpose numerical optimization simulation software with various classical
and modern optimization algorithms that produce accurate solutions for nonlinear optimization
problems [55,56]. Because conventional least square multiple linear regression and progressive
regression analysis methods cannot meet the requirement of multiparameter and nonlinear test design
modeling, three regression models, “partial least square quadratic polynomial”, “partial least square
quadratic term”, and “partial least square interaction term”, are employed in this paper. DPS software
and 1stOpt software are employed to find the optimal GMA material composition.
The interdependency of three force ductility test parameters (force, ductility, and fracture energy)
in modeling results in multiple colinearity and an unstable calculation result, which impacts the
model creation significantly. Therefore, five indices (penetration Y1 , fracture energy Y2 , softening
point Y3 , 64 ◦ C antirutting factor Y4 , and 0.1 kPa creep recovery rate Y5 ) are selected to create the
regression model for calculation and analysis. During modeling, based on the PRESS statistics after data
standardization and a declining trend in the sum of the squared errors, the determinant coefficient R2
is defined as the major criterion to evaluate the regression model’s effectiveness. A larger determinant
coefficient indicates better equation fitting. The relationship between the number of latent variables
and the determinant coefficient in three regression models calculated by DPS software is given in
Table 6.

Table 6. The number of latent variables versus the determinant coefficient.

Partial Least Square Quadratic Partial Least Square Quadratic Partial Least Square
The Number of Polynomial Regression Term Regression Determinant Interaction Term Regression
Latent Variables Determinant Coefficient R2 Coefficient R2 Determinant Coefficient R2
Y1 Y2 Y3 Y4 Y5 Y1 Y2 Y3 Y4 Y5 Y1 Y2 Y3 Y4 Y5
1 0.720 0.274 0.262 0.294 0.001 0.740 0.387 0.278 0.216 0.009 0.694 0.346 0.326 0.363 0.001
2 0.923 0.336 0.401 0.317 0.591 0.777 0.391 0.795 0.714 0.424 0.911 0.374 0.559 0.470 0.646
3 0.944 0.424 0.658 0.764 0.631 0.813 0.760 0.822 0.732 0.882 0.912 0.651 0.663 0.733 0.652
4 0.961 0.688 0.701 0.787 0.699 0.843 0.921 0.921 0.825 0.941 0.973 0.789 0.820 0.849 0.669
5 0.965 0.864 0.796 0.835 0.749 0.976 0.941 0.943 0.876 0.973 0.977 0.922 0.881 0.906 0.879

Table 6 shows that as the number of latent variables increases, the determinant coefficient R2
gradually increases. When the number of latent variables is 5, the determinant coefficient R2 reaches
its maximum level. This means the regression method created using the partial least square method
has a higher degree of fitting, and the model is closer to the actual situation and reliable. The coupling
of five factors in the model leads to significant changes in GMA performance. The equation groups of
three regression models are given in Table 7.
Materials 2019, 12, 757 10 of 19

Table 7. Equation data of regression fitting model.

Regression Partial Least Square Quadratic Partial Least Square Quadratic Partial Least Square Interaction
Model Polynomial Regression Model Term Regression Model Term Regression Model
Y1 = 69.065 + 5.02 × 10−4 × X1 +
0.248 × X2 + 0.236 × X3 − 2.019 × Y1 = 12.794 + 5.05 × 10−3 × X1 +
X4 − 0.291 × X5 − 2.58 × 10−4 × 0.266 × X2 + 1.397 × X3 − 4.966 ×
X2 2 + 1.99 × 10−2 × X3 2 − 8.66 Y1 = 145.630 − 6.78 × 10−3 × X1 + X4 + 0.434 × X5 – 5 × 10−6 × X1 ×
×10−2 × X4 2 + 2.21 × 10−3 × X5 2 – 9.45 × 10−2 × X2 − 1.488 × X3 + X2 + 6.9 × 10−5 × X1 × X3 + 1.91 ×
regression
5 × 10−6 × X1 × X2 + 6.3 × 10−5 × 2.012 × X4 − 1.153 × X5 + 1 × 10−6 10−4 × X1 × X4 − 4.9 × 10−5 × X1
equation of
X1 × X3 + 1.36 × 10−4 X1 × X4 − × X1 2 − 6.22 × 10−4 × X2 2 + 7.31 × × X5 − 1.39 × 10−3 × X2 × X3 +
penetration
3.2 × 10−5 × X1 × X5 − 1.24 × 10−2 × X3 2 − 0.189 × X4 2 + 4.47 × 1.13 × 10−2 × X2 × X4 − 2.39 ×
10−3 × X2 × X3 + 6.94 × 10−3 × X2 10−3 × X5 2 10−3 × X2 × X5 + 9.34 × 10−3 × X3
× X4 − 1.7 × 10−3 × X2 × X5 + 1.5 × X4 − 1.09 × 10−2 × X3 × X5 +
× 10−2 × X3 × X4 − 5.54 × 10−3 × 2.39 × 10−2 × X4 × X5
X3 × X5 + 1.33 × 10−2 × X4 × X5
Y2 = −7.782+1.16 × 10−2 × X1 +
1.081 × X2 − 8.445 × X3 − 15.546 ×
Y2 = 112.752 + 2.48 × 10−2 × X1 +
X4 + 4.022 × X5 + 2 × 10−6 × X1 2 +
0.944 × X2 − 8.115 × X3 − 10.189 ×
5.57 × 10−4 × X2 2 + 4.82 × 10−2 ×
Y2 = −465.825 − 5.36 × 10−2 × X1 + X4 + 1.410 × X5 + 1.3 × 10−5 × X1
X3 2 + 0.233 × X4 2 − 9.80 × 10−3 ×
0.209 × X2 + 0.885 × X3 − 9.127 × × X2 − 2.61 × 10−4 × X1 × X3 −
regression X5 2 − 8 × 10−6 × X1 × X2 − 1.67 ×
X4 + 12.342 × X5 + 7 × 10−6 × X1 2 + 9.33 × 10−4 × X1 × X4 − 1.16 ×
equation of 10−4 × X1 × X3 − 7.05 × 10−4 × X1
5.2 × 10−5 × X2 2 − 1.56 × 10−2 × 10−4 × X1 × X5 + 5.59 × 10−3 × X2
fracture energy × X4 − 1.37 × 10−4 × X1 × X5 +
X3 2 + 0.616 × X4 2 − 4.19 × 10−2 × × X3 − 1.51 × 10−2 × X2 × X4 −
1.92 × 10−3 × X2 × X3 − 5.54 ×
X5 2 5.56 × 10−3 × X2 × X5 + 0.361 × X3
10−3 × X2 × X4 − 6.86 × 10−3 × X2
× X4 + 5.25 × 10−2 × X3 × X5 +
× X5 + 0.349 × X3 × X4 + 4.28 ×
7.08 × 10−2 × X4 × X5
10−2 × X3 × X5 + 7.85 × 10−2 × X4
× X5
Y3 = 41.772 + 1.71 × 10−4 × X1 +
Y3 = 45.499 + 3.88 × 10−4 × X1 +
1.13 × 10−2 × X2 − 0.106 × X3 −
1.39 × 10−3 × X2 − 8.17 × 10−2 ×
0.142 × X4 + 8.69 × 10−2 × X5 + 1.2
X3 − 3.67 × 10−2 × X4 + 2.26 ×
× 10−5 × X2 2 + 1.88 × 10−3 × X3 2 Y3 = 19.483 − 8.74 × 10−4 × X1 −
10−2 × X5 + 1 × 10−6 × X1 × X2 + 1
− 2.17 × 10−3 × X4 2 − 2.02 × 10−4 8.32 × 10−4 × X2 + 0.129 × X3 −
regression × 10−6 × X1 × X3 − 8 × 10−6 × X1
× X5 2 + 1 × 10−6 × X1 × X2 + 4 × 0.348 × X4 + 0.467 × X5 + 2.4 ×
equation of × X4 − 2 × 10−6 × X1 × X5 + 1.98
10−6 × X1 × X3 − 3 × 10−6 × X1 × 10−5 × X2 2 − 2.08 × 10−3 × X3 2 +
softening point × 10−4 × X2 × X3 − 7.9 × 10−4 ×
X5 + 8.6 × 10−5 × X2 × X3 − 4.69 × 2.6 × 10−2 × X4 2 − 1.72 × 10−3 ×
X2 × X4 + 2 × 10−6 × X2 × X5 +
10−4 × X2 × X4 − 8 × 10−5 × X2 × X5 2
5.77 × 10−3 × X3 × X4 + 8.89 ×
X5 + 6.23 × 10−3 × X3 × X4 + 6.17
10−4 × X3 × X5 + 2.43 × 10−4 × X4
× 10−4 × X3 × X5 + 7.55 × 10−4 ×
× X5
X4 × X5
Y4 = 903.586 + 2.12 × 10−4 × X1 −
1.517 × X2 + 1.279 × X3 + 4.146 × Y4 = 1256.714 + 5.72 × 10−3 × X1 −
X4 + 5.787 × X5 + 3 × 10−6 × X1 2 + 3.325 × X2 + 1.769 × X3 + 21.236 ×
2.48 × 10−3 × X2 2 + 5.2 × 10−2 × X4 + 0.849 × X5 + 2.97 × 10−4 × X1
Y4 = −2748.009 − 0.116 × X1 −
X3 2 − 0.291 × X4 2 − 7.68 × 10−3 × × X2 − 1.4 × 10−5 × X1 × X3 −
regression 0.855 × X2 + 55.224 × X3 − 50.766
X5 2 + 2.44 × 10−4 × X1 × X2 + 4.46 6.69 × 10−4 × X1 × X4 + 1.25 ×
equation of × X4 + 63.364 × X5 + 1.8 × 10−5 ×
× 10−4 × X1 × X3 + 1.98 × 10−4 × 10−4 × X1 × X5 + 4.61 × 10−2 × X2
anti-rutting factor X1 2 + 7.32 × 10−3 × X2 2 − 1.742 ×
X1 × X4 − 2.54 × 10−4 × X1 × X5 + × X3 − 0.184 × X2 × X4 + 2.57 ×
X3 2 + 4.757 × X4 2 − 0.228 × X5 2
3.84 × 10−2 × X2 × X3 − 0.114 × 10−2 × X2 × X5 + 0.196 × X3 × X4 +
X2 × X4 + 6.55 × 10−3 × X2 × X5 + 7.24 × 10−2 × X3 × X5 − 9.25 ×
0.361 × X3 × X4 + 3.92 × 10−2 × X3 10−2 × X4 × X5
× X5 − 2.03 × 10−2 × X4 × X5
Y5 = −50.358 − 1.12 × 10−4 × X1 +
0.160 × X2 − 1.083 × X3 − 0.878 × Y5 = −19.031 − 3.4 × 10−5 × X1 +
X4 + 0.748 × X5 + 2.8 × 10−4 × X2 2 0.221 × X2 − 0.521 × X3 − 1.787 ×
+ 2.52 × 10−2 × X3 2 − 3.78 × 10−2 Y5 = −146.464 − 4.88 × 10−3 × X1 X4 + 0.151 × X5 − 1.2 × 10−5 × X1
× X4 2 − 2.43 × 10−3 × X5 2 − 8 × − 1.68 × 10−2 × X2 − 0.597 × X3 + × X2 + 9.8 × 10−5 × X1 × X3 + 1.15
regression
10−6 × X1 × X2 + 6.5 × 10−5 × X1 0.508 × X4 + 2.342 × X5 + 1 × 10−6 × 10−4 × X1 × X4 − 1 × 10−6 × X1
equation of creep
× X3 + 6.1 × 10−5 × X1 × X4 − 7 × × X1 2 + 3.9 × 10−5 × X2 2 + 4.6 × × X5 − 2.75 × 10−3 × X2 × X3 −
recovery rate
10−6 × X1 × X5 − 1.72 × 10−3 × X2 10−2 × X3 2 − 2.84 × 10−2 × X4 2 − 7.99 × 10−4 × X2 × X4 − 1.06 ×
× X3 − 2.55 × 10−4 × X2 × X4 − 8.52 × 10−3 × X5 2 10−3 × X2 × X5 + 5.01 × 10−2 × X3
8.69 × 10−4 × X2 × X5 + 4.20 × × X4 + 3.51 × 10−3 × X3 × X5 +
10−2 × X3 × X4 + 3.57 × 10−3 × X3 7.24 × 10−3 × X4 × X5
× X5 + 5.04 × 10−3 × X4 × X5

Based on Table 6, a comparison of the determinant coefficients in the three regression models
shows that the partial least square quadratic polynomial regression model has small Y3 and Y5
determinant coefficients and a relatively low degree of fitting. Therefore, this model is excluded.
By comparison, partial least square interaction term regression and partial least square quadratic term
regression have large determinant coefficients and regression models with higher degrees of fitting.
Materials 2019, 12, 757 11 of 19

Therefore, these two models are employed to find the optimal solution for GMA material composition
and preparation parameters.
Table 7 shows that all three regression models are nonlinear. Considering that there are
multiple solutions in the actual calculation, 1stOpt software is employed in the regression model
for optimization. The results are listed in Table 8.

Table 8. Optimization solution and corresponding dependent variable in each regression model.

Partial Least Square

Partial Least Square Interaction Term
Quadratic Term
Regression Model and Calculation Method Regression Model
Regression Model
B-1 B-2 B-3
shear rate X1 /r.p.m. 6500 7000 6500
shear time X2 /min 180 200 30
optimization
graphene mixing amount X3 /‰ 20 20 20
solution
stearic amide mixing amount X4 /% 1.00 8.26 10.00
shear temperature X5 /◦ C 140 160 150
penetration index Y1 /0.1 mm 88.15 51.27 66.22
fracture energy Y2 /N·mm 4301.6 3927.4 3541.9
value of dependent
softening point Y3 / 47.51 52.68 51.39
variable
64 ◦ C antirutting factor Y4 /kPa 2099.27 2338.77 1909.48
0.1 kPa creep recovery rate Y5 /% 30.13 9.25 23.43

Based on Table 8, the optimal graphene asphalt material composition and preparation parameters
are obtained to prepare GMA for performance tests and verification. The results are listed in Table 9.

Table 9. Performance test results of optimal formula.

Partial Least Square

SK70# Partial Least Square Interaction Term
Quadratic Term
Matrix Regression Model
Item Regression Model
Asphalt
Change Change Change
B-1 B-2 B-3
Rate/% Rate/% Rate/%
penetration/0.1 mm 64.7 61.5 −4.95 62.3 −3.71 58.6 −9.43
softening point/◦ C 48.1 58.6 21.83 52.3 8.73 54.3 12.89
◦ maximum force/N 96.6 168.0 73.91 136.0 40.79 123.0 27.33
5 C force
ductility/mm 6.11 42.54 596.24 44.21 623.57 48.39 691.98
ductility
fracture energy/N·mm 387.7 4035.7 940.93 3542.4 813.70 3358.3 766.21
64 ◦ C antirutting factor/Pa 1442.22 2099 45.54 1643 13.92 1443 0.05
0.1 kPa creep recovery rate/% 2.19 20.24 824.20 8.75 299.54 7.93 262.10

In Table 9, change rate is that the test value of GMA is divided by that of SK-70# matrix asphalt in
the same test item. Table 9 shows that compared with matrix asphalt, the prepared GMA has a smaller
penetration and a significantly higher softening point, force ductility force, ductility, fracture energy,
64 ◦ C anti-rutting factor, and 0.1 kPa creep recovery rate. In tests B-1, B-2, and B-3, compared with
matrix asphalt, fracture energy values at low temperature improve by 940.93%, 813.70%, and 766.21%,
respectively; 64 ◦ C anti-rutting factors improve by 45.54%, 13.92%, and 0.05%, respectively; and creep
recovery rates improve by 824.20%, 299.54%, and 262.10%, respectively.
To summarize, in three optimal formulae, compared with matrix asphalt, the prepared GMA has
a smaller penetration index, and the asphalt is hardened. Additionally, high- and low-temperature
performance and delayed elasticity recovery improve significantly. This is likely because some of the
graphene has intercalated in the asphalt, which causes a strengthening effect. Test group B-1 had
the most significant performance improvement; hence, test B-1 parameters are selected as optimal
GMA mix parameters: the high-speed shear rate is 6500 r.p.m.; the shear time is 180 min; the graphene
proportion is 20‰; the EBS proportion is 1%; and the shear temperature is 140 ◦ C.
Materials 2019, 12, 757 12 of 19

3.4. Textural Characterization

3.4.1. XRD Test

In the XRD test, the material under analysis undergoes X-ray diffraction to obtain a diffraction
spectrum, which is used to investigate useful material characteristics such as crystal structure and
elemental composition [57]. XRD analysis was performed on the SK-70# matrix asphalt and the BEST-1
Materials 2019, 12, x FOR PEER REVIEW 15 of 23
GMA; the results are shown in Figure 5.

Matrix asphalt Graphene asphalt

400 400

300 0 300
18.8 , 171.5
0
200 9.6 , 94.0 200

100 100
Intensity

0 0
400 0 400
0 19.1 , 271.7
9.6 , 212.8
300 0 300
26.5 , 177.0
200 200

100 100

0 0
5 10 15 20 25 30 35 40
2Theta(degree)

Figure 5. XRD test spectrum of matrix asphalt and GMA.

Figure 5. XRD test spectrum of matrix asphalt and GMA.
Based on Figure 5, the matrix asphalt spectrum shows the most intense peak is at approximately
Based
2θ = 18.8 on Figure
◦ . Based 5, the matrix
on Bragg’s asphalt
law, 2dsinθ = spectrum shows thespacing
nλ, the interplanar most intense
is d1 =peak
0.472isnmat approximately
and there is an
2θ = 18.8°. Based on Bragg’s law, ◦2dsinθ = nλ, the interplanar spacing is d 1 = 0.472 nm and there is an
extremely weak peak at 2θ = 9.6 ; the interplanar spacing is d2 = 0.921 nm, which is a loose-layered
extremelyofweak
structure peak
stacked at 2θ or
asphalt = 9.6°;
gum.the Theinterplanar spacing
GMA spectrum is d2 peaks
shows = 0.921atnm,
2θ =which is a2θ
9.6◦ and loose-layered
= 19.1◦ ; the
structure of stacked asphalt or gum. The GMA spectrum shows peaks
interplanar spacing values are d3 = 0.921 nm and d4 = 0.467 nm, respectively; there is a new at 2θ = 9.6° and 2θ = 19.1°;
peaktheat
interplanar spacing values ◦ are d 3 = 0.921 nm and d4 = 0.467 nm, respectively; there is a new peak at
approximately 2θ = 26.5 , which is the graphene characteristic peak [57] with a strength of 177 cps
approximately
and an interplanar 2θ =spacing
26.5°, which
of d5 =is0.336
the graphene characteristic
nm. The spectrum peak [57]the
demonstrates with a strength
existence of 177 cps
of graphene in
and an interplanar spacing of d 5 = 0.336 nm. The spectrum demonstrates the existence of graphene in
asphalt. After graphene is added, the strength of the asphalt or gum characteristic peak increases to
asphalt.
some Afterwhich
extent, graphene
means is added, the strength
that graphene of theits
increases asphalt or gum characteristic
loose-layered peak increases
structure of stacked asphalt orto
some Peak
gum. extent, whichdecreases
spacing means that graphene
to some increases
extent, its loose-layered
indicating that the intense structure
adsorption of stacked
effect ofasphalt
graphene or
gum. Peak spacing decreases to
enhances the ordered structure of asphalt. some extent, indicating that the intense adsorption effect of graphene
enhances the ordered structure of asphalt.
3.4.2. Microscope Test
3.4.2. Microscope Test
Due to its advantages, including convenient operation and easy sample preparation, the
Due to microscope
fluorescence its advantages, including
has become convenient
a widely used tooloperation
to observeand easy sample preparation,
micromorphology the
of materials, and
fluorescence microscope has become a widely used tool to observe micromorphology
has been used in asphalt characterization [58]. In this paper, SK-70# matrix asphalt, GMA in uniform of materials,
and hastest
design been used1–10,
groups in asphalt
and GMA characterization [58]. In
in the three groups withthis paper,admixtures
optimal SK-70# matrix wereasphalt,
observedGMAusingin a
uniform design
fluorescence test groups
microscope. The 1–10, and GMA
test results in the
are shown in three
Figuregroups
6. with optimal admixtures were
observed using a fluorescence microscope. The test results are shown in Figure 6.
3.4.2. Microscope Test
Due to its advantages, including convenient operation and easy sample preparation, the
fluorescence microscope has become a widely used tool to observe micromorphology of materials,
and has been used in asphalt characterization [58]. In this paper, SK-70# matrix asphalt, GMA in
uniform2019,
Materials design
12, 757test groups 1–10, and GMA in the three groups with optimal admixtures13were
of 19
observed using a fluorescence microscope. The test results are shown in Figure 6.

Materials 2019, 12, x FOR PEER REVIEW 16 of 23

Figure6.6.Microscopy
Figure Microscopytest
testresults
results((a)
(a is
is the
thetest
testresult
resultofofSK-70#
SK-70#matrix
matrixasphalt;
asphalt;(b–k)
b–k are
are the
thetest
testresults
results
ofofGMA
GMAuniform
uniformdesign
designgroups
groups1–10;
1–10;(l–n)
l–n are
are the
the test
test results
results of B-1~B-3
B-1~B-3 GMA).
GMA).

AAcomparison
comparisonof ofmatrix
matrixasphalt
asphaltin
inFigure
Figure6a
6aand
andGMA
GMAin inFigure
Figure6b–k
4b–kshows
showsthat
thatvarious
variousforms
forms
of black substances are observed in all graphene asphalt samples. As graphene
of black substances are observed in all graphene asphalt samples. As graphene is a nanometer is a nanometer
material,
material,observation
observationunder
underaanormal
normalfluorescence
fluorescencemicroscopy
microscopycondition
conditionisisvery
verydifficult.
difficult.IfIfgraphene
graphene
isisdistributed
distributedevenly
evenlyininasphalt
asphaltunder
underthetheeffect
effectofofstearic
stearicamide
amidedispersant,
dispersant,then
thengraphene
grapheneasphalt
asphalt
topography observed in a fluorescence microscopic image with 500× magnification should essentially
be identical to matrix asphalt topography. However, the actual observation shows that graphene
asphalt contains a large amount of a black substance. Graphene has an extremely large specific
surface area and a strong interlayer force, and therefore is very difficult to distribute completely
uniformly [59–61]. Because the XRD test proves the stable existence of graphene in asphalt, this black
Materials 2019, 12, 757 14 of 19

topography observed in a fluorescence microscopic image with 500× magnification should essentially
be identical to matrix asphalt topography. However, the actual observation shows that graphene
asphalt contains a large amount of a black substance. Graphene has an extremely large specific
surface area and a strong interlayer force, and therefore is very difficult to distribute completely
uniformly [59–61]. Because the XRD test proves the stable existence of graphene in asphalt, this black
substance should be graphene clusters. EBS cannot distribute graphene evenly in asphalt.
Figure
Materials 6l–n show
2019, 12, x FORthat
PEERcompared
REVIEW with materials with other compositions, the graphene 17 ofclusters
23
Materials 2019, 12, x FOR PEER REVIEW 17 of 23
in the GMA prepared with the optimal material composition obtained from modeling have more
the spherical
regular, dispersant shapes.
changes the Thisgraphene
means topography
that with the in asphalt;
optimalthe grapheneand
graphene clusters evolve from
dispersant large,ratio,
mixture
the dispersant
distinct, irregularchanges
shapes thetographene topography
small, indistinct, in asphalt;
regular shapes.the graphene clusters evolve from large,
the dispersant changes
distinct, irregular the graphene
shapes topography
to small, indistinct, in asphalt;
regular shapes. the graphene clusters evolve from large,
distinct, irregular
Image-Pro shapes
Plus istowidely
small,used indistinct, regular
microscopy imageshapes.
analysis software with accurate and reliable
imageImage-Pro
Image-Pro analysis
Plus Plus is widely
results.
is widely In used usedmicroscopy
recent microscopy image
years, imageimage analysis
analysis has software
analysis been with
applied
software accurate and and
extensively
with accurate reliable
in civil
reliable
image analysis results. In recent years, image analysis has been applied extensively in civil
imageengineering research
analysis results. In [62–64]. In thisimage
recent years, paper,analysis
Image-Pro hasPlus
been software
appliedisextensively
employed toinanalyze GMA
civil engineering
engineering
images and research
obtain [62–64].
test In this paper,such
groupImage-Pro
parameters, Image-Pro Plus software
as the number is employed
of graphene to analyze
clusters, GMA
the maximum
research [62–64]. In this paper, Plus software is employed to analyze GMA images and
images and obtain test group parameters, such as the number of graphene clusters,
area, minimum area, total area, cluster average area, total area, and ratio to maximum cluster area. the maximum
obtain testminimum
area, group parameters,
area, total suchcluster
area, as the average
numberarea, of graphene
total area,clusters,
and ratiothe maximumcluster
to maximum area, minimum
area.
The results are shown in Figures 7–9.
area,The
total area,are
results cluster
shown average
in Figures area,
7–9.total area, and ratio to maximum cluster area. The results are
shown in Figures 7–9.
1000 1000
1000 Maximum area of graphene clusters 1000
750 Maximum area of graphene clusters 750
750 750
500 500
500 500
250 250
250 250
2
Area/um
2

0 0
Area/um

0 0
Minimum area of graphene clusters
0.12 Minimum area of graphene clusters 0.12
0.12 0.12

0.09 0.09
0.09 0.09

0.06 0.06
0.06 1# 2# 3# 4# 5# 6# 7# 8# 9# 10# B-1 B-2 B-3 0.06
1# 2# 3# 4# 5# Sample
6# 7# number
8# 9# 10# B-1 B-2 B-3
Sample number
Figure
Figure 7. Variationtrend
7. Variation trendof
ofgraphene
graphene cluster
clustermax
maxand
andmin
minareas.
areas.
Figure 7. Variation trend of graphene cluster max and min areas.

Figure 8. Variation
Figure 8. Variationtrend
trendofofgraphene clustertotal
graphene cluster totalarea
area and
and quantity.
quantity.
Figure 8. Variation trend of graphene cluster total area and quantity.
 Materials
Materials 2019,
2019, 12, 12, x FOR PEER REVIEW
757 18 of 23
15 of 19

30 30
Average area of graphene clusters
20 20

2
Area/um
10 10

0 0
Ratio of total area to maximum area of
200 graphene clusters 200
Ratio/%

100 100

0 0
1# 2# 3# 4# 5# 6# 7# 8# 9# 10# B-1 B-2 B-3
Sample number

Figure 9. Variation trend of graphene cluster average area and ratio of total area to maximum area of
Figure
graphene 9. Variation trend of graphene cluster average area and ratio of total area to maximum area of
clusters.
graphene clusters.
Figures 7 and 8 show that the dispersant has significantly different graphene dispersion effects in
Figures 7 and 8 show that the dispersant has significantly different graphene dispersion effects
different test groups (i.e., the graphene distribution in asphalt is affected by differences in parameters
in different test groups (i.e., the graphene distribution in asphalt is affected by differences in
including the dispersant and graphene mix ratio, shear rotating speed, shear time, and shear
parameters including the dispersant and graphene mix ratio, shear rotating speed, shear time, and
temperature). In different
shear temperature). In test groups,
different testthe graphene
groups, clusters clusters
the graphene have similar minimum
have similar areas. areas.
minimum Although
Figure 7 shows the maximum graphene cluster areas in different test groups
Although Figure 7 shows the maximum graphene cluster areas in different test groups differ differ significantly,
such significantly,
differences reflect differencesreflect
such differences between individual
differences graphene
between cluster
individual areas and
graphene cannot
cluster areasrepresent
and
cannot represent
the general variationthe general
pattern ofvariation
graphene pattern of graphene
clusters clusters
in the test in theTherefore,
groups. test groups.the
Therefore,
maximum the and
minimummaximum and minimum
graphene cluster areas graphene
have nocluster areas havesignificance.
comparative no comparative significance.
In the In the optimal
optimal parameter solution,
parameter
the optimal solution,asphalt
graphene the optimal graphene
material asphalt material
composition composition and
and preparation preparation
parameters areparameters
based on test
are based on test group B-1. Figure 8 shows a larger graphene cluster total area and more clusters.
group B-1. Figure 8 shows a larger graphene cluster total area and more clusters. Figure 9 shows a
Figure 9 shows a small graphene cluster average area with a significantly larger total area and
small graphene cluster average area with a significantly larger total area and maximum area ratio than
maximum area ratio than other test groups. This means this test group has properly distributed
othergraphene
test groups. This means this test group has properly distributed graphene in asphalt.
in asphalt.
Based on the above graphene cluster characteristics, clusters in images are divided into three
categoriesBased
basedonon the above graphene
dimension: cluster characteristics,
fine clusters, clusters
medium clusters, andin images
coarse are divided
clusters. Theinto three
fine cluster
categories based on
2 dimension: fine clusters, medium clusters, and
2 coarse clusters.
area is less than 1 µm ; the medium cluster area is between 1 µm and 10 µm ; the coarse cluster area2 The fine cluster
area is less
Materials 12, xthan 1 µm2REVIEW
; the medium cluster area is between 1 µm2 and 10 µm2; the coarse cluster area
is larger2019,
than 10FOR
µm2PEER
. Based on these categories, the graphene cluster distribution patterns in various 19 of 23
is larger than 10 µm . Based on these categories, the graphene cluster distribution patterns in various
2
test groups scattered by EBS are shown in Figures 10 and 11.
test groups scattered by EBS are shown in Figures 10 and 11.

40 40
small-sized graphene clusters

20 20

60 Medium-sized graphene clusters 60

Ratio/%

50 50

40 40
40 Large-sized graphene clusters 40

20 20

1# 2# 3# 4# 5# 6# 7# 8# 9# 10# B-1 B-2 B-3

Sample Number
Figure 10. Variation trend of different categories of graphene clusters.
Figure 10. Variation trend of different categories of graphene clusters.

40 40
 20 20

1# 2# 3# 4# 5# 6# 7# 8# 9# 10# B-1 B-2 B-3

Sample Number

Materials 2019, 12, 757 Figure 10. Variation trend of different categories of graphene clusters. 16 of 19

40 40

30 30

2
Cluster area/um
20 20

10 10

0 0
1# 2# 3# 4# 5# 6# 7# 8# 9# 10# B-1 B-2 B-3
Sample Number

Figure 11. Box plot of graphene cluster area.

Figure 11. Box plot of graphene cluster area.
Figures 10 and 11 show that in different test groups, the coarse- and fine-grain proportions of
grapheneFigures 10 and
clusters 11 show that
in graphene in different
asphalt test groups,In
vary significantly. thecontrast,
coarse- and fine-graingrain
the medium proportions of a
ratio has
graphene clusters in graphene asphalt vary significantly. In contrast, the medium grain ratio has a
small variation and is essentially stable. This means when dispersant cannot distribute graphene
small variation and is essentially stable. This means when dispersant cannot distribute graphene
evenly in asphalt, the majority of graphene clusters in asphalt are medium-sized.
evenly in asphalt, the majority of graphene clusters in asphalt are medium-sized.
The performance comparison shows that test group B-1 had the smallest quartile and median
among all
Thetest groups. Test
performance group B-1
comparison had the
shows thathighest proportion
test group of fine
B-1 had the graphene
smallest clusters,
quartile a small
and median
among all
proportion oftest groups.
coarse Test group
clusters, B-1 had
the largest thecluster
total highestarea,
proportion of with
clusters fine graphene clusters, aand
small dimension, small
the
proportion
maximum of coarse
softening clusters,
point, the largest total
low temperature clusterfracture
ductility area, clusters
energy,with small dimension,
antirutting factor, andand
0.1the
kPa
maximum
creep recoverysoftening
rate at 58.6 ◦ C,low
point, temperature
4035.7 ductility
N·mm, 2099.00 fracture
kPa, energy,respectively.
and 20.24%, antirutting factor,
Again,and 0.1means
this kPa
creep recovery rate at 58.6 °C, 4035.7 N·mm, 2099.00 kPa, and 20.24%, respectively. Again, this
graphene in this test group is distributed properly in asphalt, resulting in a significant improvement in means
graphene in
macroscopic this test
asphalt group is distributed properly in asphalt, resulting in a significant improvement
performance.
inTo
macroscopic
summarize, asphalt performance.
in EBS-based GMA, when the graphene and dispersant proportions and
corresponding preparation parameters are optimal, graphene is distributed properly in asphalt, which
significantly improves the softening point, low-temperature ductility fracture energy, antirutting factor,
and creep recovery rate of the material.

4. Conclusions
(1) A method for calculating the optimal parameters of GMA and a process to prepare GMA were
proposed. For EBS-based GMA, the optimal parameters are as follows: the graphene proportion
is 20‰; the EBS proportion is 1%; the high-speed shear rate is 6000 r.p.m.; the shear time is
180 min; the shear temperature is 140 ◦ C. The prepared GMA had a significantly improved
softening point, low temperature fracture energy, antirutting factor, and creep recovery rate.
(2) The prepared GMA had a softening point of 58.6 ◦ C, a low-temperature ductility force of 168.0 N,
low-temperature ductility of 42.54 mm, low-temperature fracture energy of 2099 N·mm, and a
0.1 kPa creep recovery rate of 20.24%. Compared with SK-70# matrix asphalt, the performance of
GMA was significantly improved.
(3) Graphene can exist in an asphalt medium in a stable form, and some graphene in asphalt is in the
form of clusters. When the graphene and dispersant composition is close to the optimal ratio, the
dispersant changes the form of graphene in asphalt from irregular clusters to regular clusters
and from distinct, large clusters to indistinct, small clusters. When the graphene distribution in
asphalt is closer to the ideal situation, graphene asphalt has improved high- and low-temperature
performance. When the dispersant cannot distribute graphene evenly in asphalt, the majority of
graphene clusters in asphalt are medium-sized.
Materials 2019, 12, 757 17 of 19

(4) Although EBS is used in this study, graphene is still not distributed evenly in asphalt in the form
of flakes but is in the form of small clusters. Methods to ideally disperse or intercalate graphene
in asphalt to substantially improve asphalt performance require further investigation.

Author Contributions: Conceptualization, X.Z., G.H., and J.-X.H.; Methodology, X.Z., G.H., and J.-X.H.; Software,
J.-X.H. and M.-M.F.; Validation, X.Z., J.-X.H., and Y.L.; Formal Analysis, J.-X.H.; Investigation; G.H. and C.Z.;
Resources, G.H. and C.Z.; Data Curation, J.-X.H. and M.-M.F.; Writing—Original Draft Preparation, J.-X.H.;
Writing—Review & Editing, X.Z. and G.H.; Visualization, X.Z. and G.H.; Supervision, G.H.
Funding: This research was funded by National Natural Science Foundation of China (No. 51402030 &
No. 51778096) and Municipal Foundation Project of CQEC (No. yjgl33018) and Natural Science Foundation Project
of CQ CSTC (No. cstc2016jcyjA0119 & No. cstc2017jcyjB0028).
Acknowledgments: The authors would like to gratefully acknowledge the financial supports from National
Natural Science Foundation of China and Municipal Foundation Project of CQEC and Natural Science Foundation
Project of CQ CSTC.
Conflicts of Interest: The authors declare no conflict of interest.

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