molecules

Article
High-Temperature Performance Evaluation of
Asphaltenes-Modified Asphalt Binders
Amirhossein Ghasemirad, Nura Bala and Leila Hashemian *
Department of Civil and Environmental Engineering, University of Alberta, Edmonton, AB T6G 1H9, Canada;
ghasemir@ualberta.ca (A.G.); bala1@ualberta.ca (N.B.)
* Correspondence: hashemia@ualberta.ca; Tel.: +1-780-492-8934

Academic Editors: Zhanping You and Shihui Shen




Received: 30 June 2020; Accepted: 18 July 2020; Published: 22 July 2020

Abstract: Asphalt binder comprises four main fractions—asphaltenes (A), saturates (S), aromatics
(A), and resins (R)—referred to as “SARA”. Asphaltenes plays an important role in determining the
linear viscoelastic behavior of asphalt binders. In this research, asphaltenes are added as a distinct
modifier to improve the performance properties of asphalt binder. The modified binders are aged
using a rolling thin film oven. A dynamic shear rheometer is then used to measure the rheological
properties of the binders at high temperatures. Changes in the chemical composition of the modified
binders are also studied through the determination of SARA fractions, using precipitation and
gravity-driven chromatography methods. The rheological results show that asphaltenes improve the
stiffness and elasticity of asphalt binder. It is also shown that the addition of asphaltenes raises the
high Performance grade (PG) temperature of the asphalt binder, with every 6% of asphaltenes added
resulting in a one-interval increase in high PG temperature grade. SARA analysis shows that the
increase in polar fraction content due to the addition of asphaltenes causes the stiffness, elasticity,
and viscosity of asphalt binders to increase. The results indicate that asphaltenes are an effective yet
inexpensive additive to improve asphalt binder properties at high temperatures.

Keywords: modified asphalt binder; asphaltenes; SARA; high-temperature performance; rheology;

chemical composition

1. Introduction
Asphalt pavements are the most common type of pavement in North America, making them
an important infrastructure asset. Asphalt mixture is composed of asphalt binder, aggregates,
and fillers. In some cases, additives or modifiers are also added to improve the mixture properties [1,2].
Asphalt binder is a hydrocarbon product produced in crude oil refineries, mainly through fractional
distillation [3]. After separation of lighter fractions (liquid petroleum gas, gasoline, aviation fuel,
kerosene, etc.), the heaviest fraction taken from crude oil distillation, which is a complex mixture of
high molecular weight hydrocarbons, is processed further to obtain asphalt binder [3]. Although in the
pavement industry, asphalt binder is used as a binding agent for the aggregates, it also adds several
characteristics to the asphalt mixture and plays an important role in determining distresses during
the pavement’s service life [4]. Therefore, it is important to ensure that the asphalt binder used in the
production of asphalt mixture performs well under different environmental conditions.
Increasing traffic demand, harsh weather conditions, and the tendency for infrastructure operators
to reduce the cost (and, therefore, the frequency) of maintenance are among the major reasons for
asphalt performance improvement strategies [3]. This has motivated researchers to seek ways to
modify conventional asphalt binders to improve their performance and extend their service life [1,5].
In this regard, polymers, which are one of the most common materials used in asphalt modification,
have significantly enhanced asphalt mixtures in terms of performance [6]. Despite the improvements

Molecules 2020, 25, 3326; doi:10.3390/molecules25153326 www.mdpi.com/journal/molecules

Molecules 2020, 25, 3326 2 of 14

recorded with these modifiers, some drawbacks are also associated with the use of polymers for asphalt
binder modification. Perhaps the most notable disadvantage is polymer-modified asphalt being much
more expensive than conventional asphalt binder [7,8]. Furthermore, phase separation may occur
during the storage and application of polymer-modified asphalt binders [9–11].
Recently, due to increasing public concerns about sustainability, and given the high cost of some
modifiers, the application of waste materials to improve asphalt binder properties has gained more
attention by researchers [12,13]. Asphaltenes are one of the waste materials obtained through the
deasphaltation process in oil sand asphalt binder production. Despite their high rate of production,
asphaltenes have generally been considered a waste, with minimal value and few useful applications in
industry [14,15]. However, there have been some efforts recently to make use of asphaltenes, including
the development of a gasification technique to convert asphaltenes to gas fuel [16]; however, gasification
is an expensive process that generates a considerable amount of environmental pollution [15].
According to its polarity, asphalt binders can be classified by chemical composition into saturates,
aromatics, resins, and asphaltenes—collectively referred to as “SARA” [17,18]. The polarity of asphalt
binder compounds and their interactions, in turn, play important roles in influencing the rheological
properties of the asphalt binder [19].
The polar fractions of asphalt binder—asphaltenes and resins—account for its elastic behavior,
while the non-polar fractions—saturates and aromatics—are responsible for its viscous behavior [20,21].
Due to differences in polarity, asphaltenes particles may agglomerate and become unstable in the
surrounding matrix of the remaining fractions [22,23].
Two general methods of altering asphaltenes content in asphalt binders have been identified in
the literature. The first is to use a mechanical stirrer to mix the asphalt binder with materials rich
in asphaltenes [24,25], while the second is to add the asphaltenes separated from the asphalt binder,
by n-heptane extraction, back into the binder [20,26]. The second method has the advantage of the
asphaltenes content being adjustable, which has made this procedure more popular and has led to the
emergence of the concept of artificial bitumen [27].
Previous investigations have shown that the temperature susceptibility of an asphalt binder
decreases with an increase in asphaltenes content [8,25]. On the other hand, the addition of asphaltenes
could improve the resistance of asphalt binders against aging [8]. Furthermore, it has been shown that it
is the asphaltenes content that is primarily responsible for the elastic component of an asphalt binder’s
viscoelastic response [20,26,28]. Higher asphaltenes content causes the asphalt stiffness to increase,
which in return decreases the penetration and creep compliance [20,24], and increases the binder’s
viscosity [18]. The abrupt change in asphalt binder properties resulting from the addition of asphaltenes
is indicative of a fortifying of the network formed by the polar fractions (mainly asphaltenes) within
the asphalt binder; a phenomenon which gives elastic characteristics to the binder [26,28].
Based on a review of the existing literature, to the authors’ knowledge there has been no
investigation of the effects of using asphaltenes produced as a waste material in crude oil refineries
as a distinct modifier in performance improvement of asphalt binders. The present study thus aims
to investigate the high-temperature performance of asphalt binders modified with different levels of
asphaltenes content in specific reference to binders produced at oil refineries.
The main objective of this study is to investigate the rheological performance of asphalt binders
modified with asphaltenes derived from Alberta oil refineries at high temperatures, as well as their
chemical compositions.

2. Materials and Test Methods

2.1. Materials

2.1.1. Asphalt Binder

The asphalt binder used for this study was a straight-run asphalt binder with a performance
grade (PG) of 70–22, and Table 1 shows the specifications of this binder
2.1. Materials

2.1.1. Asphalt Binder

The asphalt binder used for this study was a straight-run asphalt binder with a performance
grade (PG)
Molecules 2020,of
25,70–22,
and Table 1 shows the specifications of this binder
3326 3 of 14

Table 1. Specifications of the PG 70–22 binder [29].

Table 1. Specifications of the PG 70–22 binder [29].
Specification
Property ASTM Specification Typical Value
Property ASTM Minimum Maximum Typical Value
Minimum Maximum
Density @ 15 °C, kg/L D 70 [30] --- --- 1.0341
Density ◦
Penetration @@ 2515°CC, kg/L
(100 g, 5 s), dmm D 70D [30]
5 [31] —80 —
100 1.0341
90
Penetration @ 25 ◦ C (100 g, 5 s), dmm D 5 [31] 80230 100 90
Flash Point (COC), °C D 92 [32] --- 276
Flash Point (COC), ◦ C D 92 [32] 230 — 276
Ductility @ 25 °C (5cm/min),
Ductility @ 25 ◦ C (5cm/min), cm
cm D 113 [33]
D 113 [33] 100
100 —
--- 150+
150+
Solubilityinin
Solubility trichloroethylene,
trichloroethylene, % % D 2042 D 2042
[34] [34] 99.5
99.5 —--- 99.9
99.9
Absolute
Absolute viscosity
viscosity @ 60@ ◦60
C, °C,
Pa.sPa.s D 2171
D 2171 [35] [35] 150150 —--- 183
183
Viscosity @ 135 ◦ C, Pa.s D 4402 [36] [36] —--- 3.00 0.42
Viscosity @ 135 °C, Pa.s D 4402 3.00 0.42
Mass loss, % D 1754 [37] — 1.0 0.37
Mass loss, % D 1754 [37] --- 1.0 0.37

2.1.2. Asphaltenes
Asphaltenes are a macro-polar
macro-polar structure
structure that
that isis found
found in solution within the oil matrix, and there
are aafew methods to extract asphaltenes from their
few methods to extract asphaltenes from their sources, sources, among whichwhich
among solventsolvent
dissolution, or solvent
dissolution, or
deasphalting, is the oneisthat
solvent deasphalting, thecommonly
one that used [22,38].used
commonly The solvent
[22,38].deasphalting
The solventprocess consistsprocess
deasphalting mainly
of precipitation
consists mainly of ofasphaltenes
precipitation by ofusing n-alkanesby
asphaltenes as using
an anti-solvent
n-alkanes[39].
as anThe asphaltenes[39].
anti-solvent usedThe
in
this research were produced in northern Alberta facilities from SAGD produced
asphaltenes used in this research were produced in northern Alberta facilities from SAGD produced Athabasca bitumen,
by adding abitumen,
Athabasca non-polarby solvent
adding (e.g., typically NC3
a non-polar to NC7)
solvent (e.g., in enough NC3
typically quantity to theinoilenough
to NC7) matrix,quantity
in order
to disrupt the solubility
the oil matrix, in order oftothe asphaltenes
disrupt and force
the solubility of them to precipitate.
the asphaltenes and force them to precipitate.
Asphaltenes
Asphalteneshave havebeen
been considered
considered to betoa waste, with minimal
be a waste, value andvalue
with minimal few potential
and few applications
potential
in industry. The
applications asphaltenes
in industry. The used in this study
asphaltenes used in werethisobtained
study were in chunk form,
obtained as shown
in chunk in Figure
form, as shown1a.
In order to make the mixing process more effective and provide adequate
in Figure 1a. In order to make the mixing process more effective and provide adequate surface area surface area for mixing,
the
for solid asphaltenes
mixing, the solidwere ground into
asphaltenes werepowder
groundform intobefore
powder adding
formthem to asphalt
before adding binder,
them to asasphalt
shown
in Figureas1b.
binder, Asphaltenes
shown in Figureparticles passing through
1b. Asphaltenes particlesa #100
passingsieve with ana opening
through #100 sieve size
withof 150 microns
an opening
were
size ofused
150 to modifywere
microns the asphalt
used to binder.
modify the asphalt binder.

(a) (b)
Figure 1. Asphaltenes:
Figure (a)(a)
1. Asphaltenes: solid
solidform;
form;(b)
(b)powder formafter
powder form afterpassing
passing through
through a #100
a #100 sieve.
sieve.

2.2. Test Methods

2.2. Test Methods
2.2.1. Preparation of Asphaltenes-Modified Asphalt Binders
All modified binders were prepared using a high shear mixer (L5M-A model, Silverson Co.,
East Longmeadow, MA, USA). In order to prevent aging at elevated temperatures during mixing,
a hot plate was used to maintain the temperature of the asphalt binder at 140 ± 5 ◦ C while mixing.
The desirable amount of asphaltenes was then added to the heated asphalt binder and mixed at a
rotation speed of 2000 rpm for 60 min in order to achieve a uniform blend.
Molecules 2020, 25, 3326 4 of 14

In order to investigate the effects of asphaltenes across a wide range of asphaltenes content levels,
asphaltenes-modified binders were prepared by adding 0% to 20% asphaltenes content (as a proportion
of the weight of the asphalt binder) at increments of 3%, with the exception of the last mix, for which
the asphaltenes content was increased from 18% to 20%.

2.2.2. Aging Process and Aging Indices

In order to simulate the short-term aging that occurs in the asphalt binder during mixing in asphalt
plants, a rolling thin film oven (RTFO) was used to age the asphalt binders in accordance with the
AASHTO T240 standard [40]. The impact of asphaltenes on the aging characteristics of asphalt binders
was studied by estimating the aging indices. These indices, are defined as the ratio of a performance
parameter of the aged binder to that of the unaged binder [41,42]. Two aging indices, complex modulus
aging index (CAI) and phase angle aging index (PAI), were estimated in this study using Equations (1)
and (2), respectively [41]:

CAI = (aged complex modulus)/(unaged complex modulus), (1)

PAI = (aged phase angle)/(unaged phase angle), (2)

where a higher value aging index indicates a more severe impact of aging on the properties of the
asphalt binder [41,43].

2.2.3. Dynamic Shear Rheometry (DSR)

To characterize the viscoelastic behavior of asphalt binders at high temperatures, samples were
tested according to the AASHTO T315 standard [44] using a dynamic shear rheometer (DSR) (Smartpave
102 model by Anton Paar, Co., Ltd., Graz, Austria). DSR applies sinusoidal shear loadings to samples
and measures the stress and resulting strain response. Using these data, this device is able to calculate
the complex shear modulus (G* ), and phase angle (δ) of viscoelastic materials, where G* is the ratio
of maximum applied shear stress to the maximum value of strain, and δ is the time lag between
shear stress and shear strain response. The complex shear modulus, in turn, is representative of the
material’s stiffness, while the phase angle is an indicator of how elastic or viscous the material behaves.
According to AASHTO M320 standard [45], at a loading frequency of 1.59 Hz, the temperatures at
which the parameter G* /sinδ drops below 1.0 kPa and 2.2 kPa, would be recorded as the binder’s
failure temperatures in regard to rutting resistance for unaged and RTFO-aged binders, respectively.
The lower of these two temperatures is thus identified as the high PG grade of the binder.

2.2.4. Rotational Viscosity

In this study, a Brookfield rotational viscometer was used to measure the viscosity of the asphalt
binders at elevated temperatures in accordance with AASHTO T316 standard [46]. In order to
ensure adequate workability of the asphalt mixture, AASHTO M320 standard [45], which restricts
the maximum viscosity of binders at 135 ◦ C to 3 Pa·s, was applied. The viscosities of the binders
were investigated across a wide range of high temperatures (135 ◦ C to 185 ◦ C) in order to calculate
the mixing and compaction temperature ranges of the asphalt binders. According to Superpave,
compaction specimens require mixing and compaction under equiviscous temperature conditions
corresponding to 170 ± 20 mPa·s and 280 ± 30 mPa·s, respectively.

2.2.5. SARA Analysis

SARA analysis was conducted to separate different fractions of asphalt binders. The SARA test
is composed of two main techniques: solvent dissolution to separate asphaltenes from maltenes,
and gravity-driven chromatography to separate different fractions of maltenes. In this process,
asphaltenes are first separated from the sample according to ASTM D6560 standard [47] using
Molecules 2020, 25, 3326 5 of 14

n-heptane as the solvent. Saturates, aromatics, and resins fractions are then determined using the
clay-gel adsorption chromatography method in accordance with ASTM D2007 standard [32].
In order to quantify the stability of the asphaltenes in the maltenes phase, the colloidal index (CI)
was calculated for the asphalt binders using Equation (3) [48,49].

CI = (Asphaltenes in wt% + Saturates in wt%)/(Resins in wt% + Aromatics in wt%), (3)

where a lower value of CI represents a higher stability of asphaltenes micelles in the asphalt binder.
In this regard, according to Lesueur [18], for CI values greater than 1.2, the asphaltenes fraction tends
to be unstable within the maltenes matrix. When the CI value is between 0.7 and 1.2, the asphaltenes
stability is uncertain, while, for CI indices less than 0.7, the asphaltenes fraction is stable.

3. Results and Discussion

The results and analysis from different tests are available in this section. All the results presented
in different tables and figures are the average of at least three repetitions, with the maximum allowable
standard deviation of 10%.

3.1. PG Grading Results

In order to determine the high PG grade of the binders, DSR testing was conducted on all unaged
and RTFOT-aged control and asphaltenes-modified binders. The results for high PG grading of asphalt
binders are presented in Table 2. It can be seen that a noticeable increase in the high PG grade of
asphaltenes-modified binders was observed, as compared to the base binder; this increase indicates a
considerable improvement in resistance against permanent deformation. It can be concluded from
Table 2 that, on average, a one-interval increase in high PG of the asphalt binder can be expected as a
result of addition of every 6% asphaltenes. This enhancement in high PG grade is comparable with the
improvement associated with some other well-known additives such as crumb rubber [11].

Table 2. High PG grading results for PG 70–22 modified with asphaltenes.

Binder + High PG Grade

High PG Grade Continuous High Standard High PG
Asphaltenes, (RTFO-Aged
(Unaged Binder) ◦ C PG Grade ◦ C Grade ◦ C
(% Binder wt) Binder) ◦ C
0% Asph 70.5 71.1 70.5 70
3% Asph 73.9 75.1 73.9 70
6% Asph 76.5 78.2 76.5 76
9% Asph 81.3 81.1 81.1 76
12% Asph 82.9 84.6 82.9 82
15% Asph 85.9 87.6 85.9 82
18% Asph 88.0 90.3 88.0 88
20% Asph 89.9 92.6 89.9 88

The PG grade improvement of the binder at high temperatures corresponding to the addition of
asphaltenes for both unaged and rolling thin film oven (RTFO)-aged binders is represented graphically
in Figure 2. As can be seen in the figure, at both states of aging, the rate of improvement of the asphalt
binder’s performance at high temperatures is roughly proportional to the increase in asphaltenes
content. On the other hand, the slope of the RTFO-aged plot is more inclined than that of the unaged
one, suggesting that the contribution of asphaltenes to rutting resistance increases as the binder ages.
Molecules 2020, 25, 3326 6 of 14
Molecules 2020, 25, x FOR PEER REVIEW 6 of 14
Molecules 2020, 25, x FOR PEER REVIEW 6 of 14

100
100
94 Unaged
(°C)
94 Unaged
(°C)

RTFO-Aged R² = 0.9948
88 R² = 0.9948
Grade

88 RTFO-Aged
Grade

82 R² = 0.9948
82 R² = 0.9948
PG
PG

76
High

76
High

70
70
64
64
0 3 6 9 12 15 18 21
0 3 6 9 12 15 18 21
Asphaltene Content (% Binder Weight)
Asphaltene Content (% Binder Weight)
Figure 2. PG grading results for unaged and RTFO-aged binders.
Figure 2. PG
Figure grading
2. PG gradingresults
results for
for unaged andRTFO-aged
unaged and RTFO-aged binders.
binders.
3.2. Rheological Properties
3.2. Rheological Properties
The modified binders were divided into two groups: the first group included the binders
The modified binders were divided divided into
into two
two groups:
groups: the first group included the binders binders
containing 0%, 3%, 6% and 9% asphaltenes content, and the second category consisted of asphalt
containing 0%, 3%, 6% and 9% asphaltenes asphaltenes content, and the second category consisted of asphalt
binders modified with 12%, 15%, 18%, and 20% asphaltenes content (relative to the binder weight).
binders modified with 12%, 15%, 18%, and 20% asphaltenes content content (relative
(relative to
to the binder weight).
weight).
Figures 3 and 4 compared the rheological specifications of the asphalt binders in the first and second
Figures 3 and 4 compared the rheological specifications of the asphalt binders in the first and second
groups, respectively.
groups, respectively.
respectively.
From Figures 3 and 4, it can be seen that increasing asphaltenes content was found to noticeably
From Figures 3 and 4, it can be seen that increasing asphaltenes content was found to noticeably
increase the complex shear modulus and decrease the phase angle, indicating an improvement in
increase the complex shear modulus and decrease the phase phase angle,
angle, indicating an improvement in
stiffness and elasticity of the asphalt binder at high temperatures. According to Figures 3a and 4a, the
stiffness elasticity of
and elasticity ofthe
theasphalt
asphaltbinder
binderatathigh
high temperatures.
temperatures. According
According to Figures
to Figures 3a and
3a and 4a,
4a, the
‫ ∗כ ܩ‬plots are steeper in the RTFO-aged state than in the unaged state. Furthermore, this higher rate of
G* plots
𝐺 plots
the are are steeper
steeper in the
in the RTFO-aged
RTFO-aged state
state thanthan in the
in the unaged
unaged state.
state. Furthermore,
Furthermore, thisthis higher
higher rate
rate of
improvement was found to be more significant at higher temperatures. In the case of phase angle (Έ),
of improvement was found to be more significant at higher temperatures. In the
improvement was found to be more significant at higher temperatures. In the case of phase angle (δ), case of phase angle
in reference to Figures 3b and 4b, the rate of increase in elasticity in the aged state was found to be
(δ), in reference
in reference to Figures
to Figures 3b 3b
andand
4b,4b,
thethe rate
rate ofof increaseininelasticity
increase elasticityininthe
theaged
agedstate
state was
was found
found to be
noticeably more than that in the unaged state. These observations reveal that the impact of
noticeably
noticeably moremorethan thatthat
than in the
in unaged state. These
the unaged state. observations reveal that
These observations the impact
reveal that theof asphaltenes
impact of
asphaltenes on improving high-temperature performance parameters is more pronounced as the
on improvingonhigh-temperature
asphaltenes performance parameters
improving high-temperature performance is more pronounced
parameters is moreas the binder ages.
pronounced as the
binder ages.
binder ages.
10.0
10.0
(kPa)
(kPa)

Unaged-70 C Unaged-76 C R² = 0.9537

8.0 Unaged-70 C Unaged-76 C R² = 0.9537
Modulus

8.0 RTFO-70 C RTFO-76 C

Modulus

RTFO-70 C RTFO-76 C
6.0
6.0
R² = 0.9587
Shear

R² = 0.9587
Shear

4.0
4.0
Complex
Complex

2.0 R² = 0.9353
2.0 R² = 0.9353
R² = 0.9408
0.0 R² = 0.9408
0.0
0 3 6 9
0 3
Asphaltenes Content (% Binder 6Weight) 9
Asphaltenes Content (% Binder Weight)
(a)
(a)
Figure 3. Cont.


Molecules 2020, 25, x FOR PEER REVIEW 7 of 14
Molecules 2020, 25, 3326 7 of 14

Molecules 2020, 25, x FOR PEER REVIEW 7 of 14

90.0

90.0
88.0
Phase Angle (degree) R² = 0.9899
88.0
86.0
Phase Angle (degree)
R² = 0.9899
86.0
84.0
R² = 0.9818
84.0
82.0 R² = 0.9818
Unaged-70 C Unaged-76 C
82.0 R² = 0.9905
80.0 Unaged-70
RTFO-70 C C Unaged-76
RTFO-76 C C R² = 0.9905
R² = 0.9909
80.0
78.0 RTFO-70 C RTFO-76 C
R² = 0.9909
78.00 3 6 9
0 3
Asphaltenes Content (% Binder 6Weight) 9
Asphaltenes Content (% Binder Weight)
(b)
(b)
10.0
10.0
R² = 0.952
8.0 Unaged-70 C Unaged-76 C R² = 0.952
8.0 Unaged-70 C Unaged-76 C
G*/sin(Έ) (kPa)

RTFO-70 C RTFO-76 C
G*/sin(δ) (kPa)

RTFO-70 C RTFO-76 C
6.0
6.0
R² = 0.9576
4.0 R² = 0.9576
4.0

2.02.0 R² = 0.9347
R² = 0.9347

R²==0.9406
R² 0.9406
0.00.0
0 0 33 66 99
Asphaltenes
AsphaltenesContent
Content (%
(% Binder Weight)
Weight)

(c)
(c)
Figure
Figure
Figure 3. 3. Comparison
3. Comparison
Comparison ofofofrheological
rheological
rheological properties
properties offirst
of the
properties of the group
the first group of
ofmodified
of modified
group binders:
binders:
modified (a)(a)
(a) complex
binders:
complex
shear
complex shear
modulus;
shear (b)modulus; (b)phase
phase angle;
modulus; (b) phase
(c) angle;
rutting (c)rutting
factor.
angle; (c) rutting factor.

12.0
12.0
Complex Shear Modulus (kPa)
Complex Shear Modulus (kPa)

Unaged-70
Unaged-70 CC Unaged-76CC
Unaged-76
10.0
10.0
RTFO-70 C RTFO-76 C R² = 0.8185
RTFO-70 C RTFO-76 C R² = 0.8185
8.0
8.0
6.0 R² = 0.8144
6.0 R² = 0.8144
4.0 R² = 0.8472
4.0 R² = 0.8472
2.0
2.0
0.0 R² = 0.8491
0.0 R² = 0.8491
12 15 18 21
12 15
Asphaltenes Content (% Binder 18
Weight) 21
Asphaltenes Content (% Binder Weight)
(a)
(a)
Figure 4. Cont.


Molecules 2020, 25, 3326 8 of 14

Molecules 2020, 25, x FOR PEER REVIEW 8 of 14

90.0
88.0
R² = 0.9559
Phase Angle (degree)

86.0
84.0
82.0 R² = 0.9596
80.0 R² = 0.9008
78.0 Unaged-70 C Unaged-76 C

76.0 RTFO-70 C RTFO-76 C R² = 0.9086

74.0
12 15 18 21
Asphaltenes Content (% Binder Weight)

(b)

12.0

10.0 Unaged-70 C Unaged-76 C

R² = 0.8154
G*/sin(δ) (kPa)

8.0 RTFO-70 C RTFO-76 C

6.0 R² = 0.8121

4.0
R² = 0.8465
2.0

0.0 R² = 0.8487
12 15 18 21
Asphaltenes Content (% Binder Weight)

(c)
Figure4.4.Comparison
Figure Comparison of rheological
of rheological properties
properties of the group
of the second secondof group of binders:
modified modified(a) binders:
complex
(a) complex
shear shear
modulus; modulus;
(b) phase angle;(b) phase angle;
(c) rutting factor. (c) rutting factor.

According
AccordingtotoFigureFigure 3a,b andand
3a,b Figure 4a,b,4a,b,
Figure at relatively lower temperatures,
at relatively the differences
lower temperatures, between
the differences
RTFO-aged rheological
between RTFO-aged parameters
rheological and corresponding
parameters unaged parameters
and corresponding were found
unaged parameters to be
were higher.
found to
From this observation it can be inferred that, as the temperature decreases,
be higher. From this observation it can be inferred that, as the temperature decreases, asphaltenes asphaltenes show a
more significant impact in terms of increasing the asphalt binder’s stiffness and
show a more significant impact in terms of increasing the asphalt binder’s stiffness and elasticity due elasticity due to
aging.
to aging.Given
Giventhat higher
that higher values
valuesof of
stiffness and
stiffness andelasticity adversely
elasticity adversely affect thethe
affect cracking
crackingresistance at
resistance
relatively lower temperatures, it can be expected that the possibility of cracking
at relatively lower temperatures, it can be expected that the possibility of cracking would increase atwould increase at
lower
lower temperatures
temperatures with with increased
increased asphaltenes
asphaltenes content.
content.
As
As shown in Figures 3 and 4, under the same aging
shown in Figures 3 and 4, under the same aging condition,
condition, the
the rate
rate of
of modulus
modulus change
change waswas
found
found to increase as the temperature decreases, which implies that asphaltenes have more impact
to increase as the temperature decreases, which implies that asphaltenes have more impact on
on
the
the shear
shearmodulus
modulus at at
lower
lower temperatures.
temperatures.The relatively consistent
The relatively slope inslope
consistent phaseinangle
phase plots, however,
angle plots,
reflects
however, the reflects
similar impact of asphaltenes
the similar impact of on asphaltenes
this parameter onat this
lowerparameter
and higherattemperatures.
lower and higher
The same trends as those observed in the complex modulus plots can be seen in the rutting
temperatures.
factorThe /sin δ)trends
(G*same chartsasshown in Figuresin3cthe
those observed and 4c. These
complex trendsplots
modulus servecan
to be
confirm
seen inthat,
the as the binder
rutting factor
∗ the impact of asphaltenes on improving rutting resistance becomes more effective. Furthermore,
ages,
(𝐺 /sin δ) charts shown in Figures 3c and 4c. These trends serve to confirm that, as the binder ages,
the impact of asphaltenes on improving rutting resistance becomes more effective. Furthermore, the
rutting resistance resulting from the addition of asphaltenes increases at a higher rate as the
temperature decreases.
Molecules 2020, 25, 3326 9 of 14

the rutting resistance resulting from the addition of asphaltenes increases at a higher rate as the
temperature decreases.
Molecules 2020, 25, x FOR PEER REVIEW 9 of 14

3.3. Aging Indices

3.3. Aging Indices
The aging indices for the two groups of modified binders (at 70 ◦ C and 82 ◦ C) are presented in
The aging indices for the two groups of modified binders (at 70 °C and 82 °C) are presented in
Figure 5a,b, respectively. According to these figures the phase angle aging index values for all modified
Figure 5a,b, respectively. According to these figures the phase angle aging index values for all
binders remained consistently around 1.0 during aging, indicating that regardless of asphaltenes
modified binders remained consistently around 1.0 during aging, indicating that regardless of
content aging has almost no effect on the phase angle and elasticity of the binder. However, in the case
asphaltenes content aging has almost no effect on the phase angle and elasticity of the binder.
of the complex modulus aging index, generally, the addition of asphaltenes was found to increase the
However, in the case of the complex modulus aging index, generally, the addition of asphaltenes was
CAI for both groups of binders.
found to increase the CAI for both groups of binders.

4.0

CAI PAI R² = 0.8369

Aging Index

2.0

R² = 0.9911
0.0
0 3 6 9
Asphaltenes Content (% Binder Weight)

(a)

4.0
R² = 0.7988
CAI PAI
Aging Index

2.0

R² = 0.8145
0.0
12 15 18 21
Asphaltenes Content (% Binder Weight)

(b)
Figure Aging indices
Figure5.5. Aging indices for
for asphaltenes-modified
asphaltenes-modified binders: (a)(a)
binders: aging indices
aging of of
indices thethe
first group
first of
group
modified binders ◦
at 70 atC;70
(b)°C;
aging ◦
of modified binders (b)indices
aging of the second
indices group
of the of modified
second group ofbinders at 82 binders
modified C. at
82 °C.
3.4. High-Temperature Viscosity
High-temperatureViscosity
3.4. High-Temperature viscosities of modified binders over a wide range of temperatures for different
asphaltenes content are plotted and presented in Figures 6 and 7 in relation to binder content and
High-temperature viscosities of modified binders over a wide range of temperatures for
temperature, respectively. From Figure 6, it can be seen that, at all asphaltenes contents, the workability
different asphaltenes content are plotted and presented in Figures 6 and 7 in relation to binder content
and temperature, respectively. From Figure 6, it can be seen that, at all asphaltenes contents, the
workability criterion of viscosity being less than 3 Pa·s at 135 °C, as specified in AASHTO M320
standard [45], was satisfied.
As shown in Figures 6 and 7, it was observed that, generally, the addition of asphaltenes
increases the viscosity of the asphalt binder. Furthermore, it can be seen that the effect of asphaltenes
on viscosity was found to be more evident at higher asphaltenes contents and at lower temperatures.
Molecules 2020, 25, x FOR PEER REVIEW 10 of 14
Molecules 2020, 25, 3326
x FOR PEER REVIEW 10 of 14

Moreover, the viscosities of different binders were found to exhibit a converging trend as the
Moreover, the viscosities of different binders were found to exhibit a converging trend as the
temperature
criterion increased,
of viscosity as seen
being in
less in Figure
than 7. This
3 Pa·s at 135 ◦ C, asthat,
shows as the temperature
specified increased, the effect
temperature increased, as seen Figure 7. This shows that, as the in AASHTO M320
temperature standard
increased, [45],
the effect
of asphaltenes
was satisfied. content on the viscosity of the binder was found to decrease.
of asphaltenes content on the viscosity of the binder was found to decrease.

1600
1600
135 C 145 C
1400 135 C 145 C
1400 155 C 165 C
1200 155 C 165 C
(mPa·s)

1200
Viscosity(mPa·s)

1000
1000
800
800
Viscosity

600
600
400
400
200
200
0
0
6 0 3
9 12 15 18 21
6 0
Asphaltenes 3
9
Content (%12 15
Binder Weight) 18 21
Asphaltenes Content (% Binder Weight)
Figure 6. High-temperature viscosity of asphaltenes-modified binders versus asphaltenes
Figure
Figure 6.
6. High-temperature viscosity
High-temperature viscosity of asphaltenes-modified
of asphaltenes-modified bindersbinders versus asphaltenes
versus asphaltenes content.
content.
content.
1600
1600 PG 70-22 PG 70-22+3% Asph
1400 PG 70-22 PG 70-22+3% Asph
1400 PG 70-22+6% Asph PG 70-22+9% Asph
PG 70-22+6% Asph PG 70-22+9% Asph
1200 PG 70-22+12% Asph PG 70-22+15% Asph
(mPa·s)

1200 PG 70-22+12% Asph PG 70-22+15% Asph

Viscosity(mPa·s)

PG 70-22+18% Asph PG 70-22+20% Asph

1000 PG 70-22+18% Asph PG 70-22+20% Asph
1000
800 Mixing Range
800 Mixing Range
Viscosity

600
600 Compaction Range
Compaction Range
400
400
200
200
0
0
125 135
155 145
165 175 185 195
125 135
155 145
165 175 185 195
Temperature (℃)
Temperature (℃)
Figure 7. High-temperature
Figure viscosity
7. High-temperature of
viscosityof asphaltenes-modified
ofasphaltenes-modified binders
asphaltenes-modified binders versus
versus temperature.
temperature.
Figure 7. High-temperature viscosity binders versus temperature.
The data shown
As in Figure
6 and777,were
were also used to estimate the mixing and compaction temperatures
Theshown in Figures
data shown in Figure it was observed
also used tothat, generally,
estimate the addition
the mixing of asphaltenes
and compaction increases
temperatures
of the
the asphaltofbinders containing different asphaltenes contents, and the results are presented in Table
of the asphalt binders containing different asphaltenes contents, and the results are presentedviscosity
viscosity the asphalt binder. Furthermore, it can be seen that the effect of asphaltenes on in Table
3.
wasAs shown in the table, it was found that an increase in the viscosity of the asphalt binders due to
3. Asfound
shown toinbethe
more evident
table, it wasatfound
higherthat
asphaltenes
an increase contents and at lower
in the viscosity temperatures.
of the Moreover,
asphalt binders due to
the viscosities
the addition ofof asphaltenes leads to an increase
different binders in the mixing and compaction temperature for the
the addition of asphaltenes leads towere found in
an increase to exhibit
the mixinga converging
and compaction trend temperature
as the temperature
for the
modified
increased, asphalt binders.
as seen binders. Accordingly,
in FigureAccordingly, the
7. This showsthe addition
that, of every
as the temperature percent of
increased, asphaltenes content
the effect of to the
asphaltenes
modified asphalt addition of every percent of asphaltenes content to the
base binder
content on thePG 70–22 on average was found to increase the mixing and compaction temperatures by
base binder PGviscosity
70–22 onofaverage
the binder
waswasfoundfound to decrease.
to increase the mixing and compaction temperatures by
1.4 °C and
The 1.3 °C, respectively.
data
1.4 °C and 1.3shown in Figure 7 were also used to estimate the mixing and compaction temperatures of
°C, respectively.
the asphalt binders containing different asphaltenes contents, and the results are presented in Table 3.
Table 3. Mixing
As shown and compaction temperature range of base and asphaltenes-modified
Tablein3.the table,and
Mixing it was found thattemperature
compaction an increase range
in the ofviscosity
base and of the asphalt binders due to
asphaltenes-modified
binders.of asphaltenes leads to an increase in the mixing and compaction temperature for the
the addition
binders.
modified asphalt binders.
Binder + Accordingly, the addition of every percent of asphaltenes content to the base
Binder + Mixing Temperature Range Compaction Temperature Range ◦
binder PG 70–22 on average was
Asphaltenes, found
Mixing to increaseRange
Temperature the mixing and compaction
Compaction temperatures
Temperature Range by 1.4 C
Asphaltenes, (°C) (°C)
and 1.3 ◦ C, respectively.
(% Binder wt) (°C) (°C)
(% Binder wt)
0% Asph 152–158 141–145
0% Asph 152–158 141–145
3% Asph 158–164 147–152
3% Asph 158–164 147–152
6% Asph 161–167 149–154
6% Asph 161–167 149–154
Molecules 2020, 25, 3326 11 of 14

Table 3. Mixing and compaction temperature range of base and asphaltenes-modified binders.

Binder + Asphaltenes,
Mixing Temperature Range (◦ C) Compaction Temperature Range (◦ C)
(% Binder wt)
0% Asph 152–158 141–145
3% Asph 158–164 147–152
6% Asph 161–167 149–154
9% Asph 164–170 152–157
12% Asph 167–173 154–160
15% Asph 169–175 158–163
18% Asph 173–179 161–166
20% Asph 177–184 165–170

3.5. SARA Analysis

In addition to the base binder PG 70–22, a few modified asphalt binders with higher asphaltenes
contents were selected for SARA analysis, because of their superior performances at high temperatures.
Those selected were the asphalt binders with 12%, 18%, and 20% asphaltenes content. The asphaltenes
were also tested for SARA content in order to determine its purity. The results of these analyses are
summarized Table 4.

Table 4. SARA analysis results for select asphalt binders.

Polar Non-Polar Colloidal

Binder/Material Saturate Aromatic Resin Asphaltenes
Fraction Fraction Index
Asphaltenes 6.85 9.68 3.84 79.62 83.46 16.53 6.40
0% Asph 25.41 20.36 31.58 22.59 54.17 45.77 0.92
12% Asph 21.63 20.94 24.75 32.17 56.92 42.57 1.18
18% Asph 18.83 20.25 25.23 35.16 60.39 39.08 1.19
20% Asph 17.93 19.74 21.57 39.76 61.33 37.67 1.40

As can be seen in Table 4, the addition of asphaltenes content was found to noticeably increase the
polar fraction of the asphalt binder. Comparing the rheological and SARA analysis results, it can be
concluded that the increase in polar fraction content causes the stiffness, elasticity, and viscosity of
asphalt binder to increase.
The colloidal index (CI) values for the different asphalt binders were also calculated as presented
in Table 4. It was observed that the addition of asphaltenes increases the instability of the asphaltenes
particles in the maltenes matrix. Among the asphaltenes-modified binders, the one with 20% asphaltenes
content tended to be the most unstable, with a CI value greater than 1.2 [18].

4. Conclusions
The effects of asphaltenes at different levels of content on the performance of asphalt binder PG
70–22 at high temperatures have been studied. Based on the analysis conducted in this study, the main
conclusions drawn are presented as follows:
• The addition of asphaltenes increases the stiffness and elasticity of the asphalt binder, which in
turn results in a considerable improvement in resistance against permanent deformation. On
average, a 6% increase in asphaltenes content corresponds to a one-interval increase in high PG
temperature grade of the asphalt binder.
• The effect of asphaltenes on high-temperature performance parameters, shear modulus, phase
angle, and rutting factor is more pronounced as the binder ages.
• As the temperature decreases, the asphaltenes exhibit a stronger impact in terms of increasing the
asphalt binder’s stiffness and elasticity due to aging. Since higher values of stiffness and elasticity
adversely affect the cracking resistance at lower temperatures, this indicates that the possibility of
cracking would increase at lower temperatures with increased asphaltenes content.
Molecules 2020, 25, 3326 12 of 14

• The use of asphaltenes to modify asphalt binder serves to increase the binder’s high-temperature
viscosity. The effect of asphaltenes on the binder viscosity is more evident at higher levels of
asphaltenes content and lower temperatures.
• Comparing the rheological and SARA analysis results, it can be concluded that the increase in polar
fraction content due to the addition of asphaltenes, causes the stiffness, elasticity, and viscosity of
the asphalt binder to increase.
• From the CI values, it can be concluded that the addition of asphaltenes increases the instability
of the asphaltenes particles in the maltenes matrix; a phenomenon which is largely the result of
polarity level differences between the asphaltenes and other fractions of the asphalt binder.

Author Contributions: Conceptualization, L.H.; methodology, L.H. and A.G.; software, A.G.; validation, A.G.,
N.B. and L.H.; formal analysis, A.G.; investigation, A.G.; resources, L.H.; data curation, A.G.; writing—original
draft preparation, A.G.; writing—review and editing, N.B. and L.H.; visualization, A.G.; supervision, L.H.; project
administration, L.H.; funding acquisition, L.H. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by Alberta Innovates.
Acknowledgments: The authors of this paper would like to thank Alberta Innovates for funding this study. Also,
Husky Energy Inc., and Nestor Zerpa are much appreciated for providing materials for this research.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.

References
1. Kocak, S.; Kutay, M. Fatigue performance assessment of recycled tire rubber modified asphalt mixtures using
viscoelastic continuum damage analysis and AASHTOWare pavement ME design. Constr. Build. Mater. 2020,
248, 118658.
2. Liu, H.; Chen, Z.; Wang, Y.; Zhang, Z.; Hao, P. Effect of poly phosphoric acid (PPA) on creep response of base
and polymer modified asphalt binders/mixtures at intermediate-low temperature. Constr. Build. Mater. 2018,
159, 329–337. [CrossRef]
3. Hunter, R.N.; Self, A.; Read, J. The Shell Bitumen Handbook; ICE Publishing: Westminster, UK, 2015.
4. Junaid, M.; Irfan, M.; Ahmed, S.; Ali, Y. Effect of binder grade on performance parameters of asphaltic
concrete paving mixtures. Int. J. Pavement Res. Technol. 2018, 11, 435–444. [CrossRef]
5. Vamegh, M.; Ameri, M.; Naeni, S.F.C. Performance evaluation of fatigue resistance of asphalt mixtures
modified by SBR/PP polymer blends and SBS. Constr. Build. Mater. 2019, 209, 202–214. [CrossRef]
6. Siddig, E.A.; Feng, C.P.; Ming, L.Y. Effects of ethylene vinyl acetate and nanoclay additions on
high-temperature performance of asphalt binders. Constr. Build. Mater. 2018, 169, 276–282. [CrossRef]
7. Polacco, G.; Filippi, S.; Merusi, F.; Stastna, G. A review of the fundamentals of polymer-modified asphalts:
Asphalt/polymer interactions and principles of compatibility. Adv. Colloid Interface Sci. 2015, 224, 72–112.
[CrossRef]
8. Firoozifar, S.H.; Foroutan, S.; Foroutan, S. The effect of asphaltene on thermal properties of bitumen. Chem.
Eng. Res. Des. 2011, 89, 2044–2048. [CrossRef]
9. Behnood, A.; Gharehveran, M.M. Morphology, rheology, and physical properties of polymer-modified
asphalt binders. Eur. Polym. J. 2019, 112, 766–791. [CrossRef]
10. Padhan, R.K.; Sreeram, A. Enhancement of storage stability and rheological properties of polyethylene (PE)
modified asphalt using cross linking and reactive polymer based additives. Constr. Build. Mater. 2018, 188,
772–780. [CrossRef]
11. Ghasemirad, A.; Asgharzadeh, S.M.; Tabatabaee, N. A comparative evaluation of crumb rubber and
devulcanized rubber modified binders. Pet. Sci. Technol. 2017, 35, 1091–1096. [CrossRef]
12. Choudhary, J.; Kumar, B.; Gupta, A. Utilization of solid waste materials as alternative fillers in asphalt mixes:
A review. Constr. Build. Mater. 2020, 234, 117271. [CrossRef]
13. Kalantar, Z.N.; Karim, M.R.; Mahrez, A. A review of using waste and virgin polymer in pavement. Constr.
Build. Mater. 2012, 33, 55–62. [CrossRef]
Molecules 2020, 25, 3326 13 of 14

14. Meisen, A. Bitumen Beyond Combustion (BBC) Project Phase 1 Report; BBC Project-Phase 1 Report 0416x.docx;
Alberta Innovates Corp.: Edmonton, AB, Canada, 2017; Available online: https://albertainnovates.ca/wp-
content/uploads/2018/04/BBC-Report-1.pdf (accessed on 10 June 2020).
15. Ashtari, M. New pathways for asphaltenes upgrading via oxy-cracking in liquid phase. In Chemical
Engineering; University of Calgary: Calcary, AB, Canada, 2016.
16. Alipour, M.; Kurian, V.; Dhir, S.; Gupta, R. Analysis of syngas cooler fouling from asphaltene gasification.
Fuel Process. Technol. 2016, 152, 7–14. [CrossRef]
17. Yang, C.; Xie, J.; Wu, S.; Amirkhanian, S.; Zhou, X.; Ye, Q.; Yang, D.; Hu, R. Investigation of physicochemical
and rheological properties of SARA components separated from bitumen. Constr. Build. Mater. 2020, 235,
117437. [CrossRef]
18. Lesueur, D. The colloidal structure of bitumen: Consequences on the rheology and on the mechanisms of
bitumen modification. Adv. Colloid Interface Sci. 2009, 145, 42–82. [CrossRef] [PubMed]
19. Michalica, P.; Kazatchkov, I.B.; Stastna, J.; Zanzotto, L. Relationship between chemical and rheological
properties of two asphalts of different origins. Fuel 2008, 87, 3247–3253. [CrossRef]
20. Xu, Y.; Zhang, E.; Shan, L. Effect of SARA on Rheological Properties of Asphalt Binders. J. Mater. Civ. Eng.
2019, 31, 04019086. [CrossRef]
21. Sultana, S.; Bhasin, A. Effect of chemical composition on rheology and mechanical properties of asphalt
binder. Constr. Build. Mater. 2014, 72, 293–300. [CrossRef]
22. Ramírez-Corredores, M.M. The Science and Technology of Unconventional Oils: Finding Refining Opportunities;
Academic Press: Cambridge, MA, USA, 2017. [CrossRef]
23. Airey, G. Styrene butadiene styrene polymer modification of road bitumens. J. Mater. Sci. 2004, 39, 951–959.
[CrossRef]
24. Mangiafico, S.; Di Benedetto, H.; Sauzéat, C.; Olard, F.; Pouget, S.; Planque, L. Effect of colloidal structure
of bituminous binder blends on linear viscoelastic behaviour of mixtures containing reclaimed asphalt
pavement. Mater. Des. 2016, 111, 126–139. [CrossRef]
25. Varanda, C.; Portugal, I.; Ribeiro, J.; Silva, A.; Silva, C.M. Influence of polyphosphoric acid on the consistency
and composition of formulated bitumen: Standard characterization and NMR insights. J. Anal. Methods
Chem. 2016, 2016. [CrossRef]
26. Hofko, B.; Eberhardsteiner, L.; Füssl, J.; Grothe, H.; Handle, F.; Hospodka, M.; Grossegger, D.; Nahar, S.N.;
Schmets, A.J.M.; Scarpas, A. Impact of maltene and asphaltene fraction on mechanical behavior and
microstructure of bitumen. Mater. Struct. 2016, 49, 829–841. [CrossRef]
27. Eberhardsteiner, L.; Füssl, J.; Hofko, B.; Handle, F.; Hospodka, M.; Blab, R.; Grothe, H. Influence of asphaltene
content on mechanical bitumen behavior: Experimental investigation and micromechanical modeling.
Mater. Struct. 2015, 48, 3099–3112. [CrossRef]
28. Robertson, R.E.; Branthaver, J.F.; Plancher, H.; Duvall, J.J.; Ensley, E.K.; Harnsberger, P.M. Chemical Properties of
Asphalts and Their Relationship to Pavement Performance; National Research Council Washington: Washington,
DC, USA, 1991.
29. Specifications and Typical Anlyses of an Asphalt Cement 80/100 A PEN used in the Construction of Pavements;
DS No. 0303; Husky Asphalt: Saskatoon, SK, Canada, 2019.
30. ASTM D70-18. Standard Test Method for Density of Semi-Solid Asphalt Binder (Pycnometer Method);
ASTM International: West Conshohocken, PA, USA, 2018.
31. ASTM D5-05. Standard Test Method for Penetration of Bituminous Materials; ASTM International: West
Conshohocken, PA, USA, 2005.
32. ASTM D92-18. Standard Test Method for Flash and Fire Points by Cleveland Open Cup Tester; ASTM International:
West Conshohocken, PA, USA, 2018.
33. ASTM D113-17. Standard Test Method for Ductility of Asphalt Materials; ASTM International:
West Conshohocken, PA, USA, 2017.
34. ASTM D2042-15. Standard Test Method for Solubility of Asphalt Materials in Trichloroethylene; ASTM International:
West Conshohocken, PA, USA, 2015.
35. ASTM D2171-18. Standard Test Method for Viscosity of Asphalts by Vacuum Capillary Viscometer; ASTM
International: West Conshohocken, PA, USA, 2018.
36. ASTM D4402-15. Standard Test Method for Viscosity Determination of Asphalt at Elevated Temperatures Using a
Rotational Viscometer; ASTM International: West Conshohocken, PA, USA, 2015.
Molecules 2020, 25, 3326 14 of 14

37. ASTM D1754-14. Standard Test Method for Effects of Heat and Air on Asphaltic Materials (Thin-Film Oven Test);
ASTM International: West Conshohocken, PA, USA, 2014.
38. Zuo, P.; Qu, S.; Shen, W. Asphaltenes: Separations, structural analysis and applications. J. Energy Chem. 2019,
34, 186–207. [CrossRef]
39. Speight, J.G. Petroleum Asphaltenes-Part 1: Asphaltenes, resins and the structure of petroleum. Oil Gas
Sci. Technol. 2004, 59, 467–477. [CrossRef]
40. AASHTO T240-13. Effect of Heat and Air on a Moving Film of Asphalt Binder (Rolling Thin-Film Oven Test).
In AASHTO Provisional Standards; American Association of State Highway and Transportation Officials:
Washington, DC, USA, 2017.
41. Zhang, H.; Chen, Z.; Xu, G.; Shi, C. Physical, rheological and chemical characterization of aging behaviors of
thermochromic asphalt binder. Fuel 2018, 211, 850–858. [CrossRef]
42. Zhao, X.; Wang, S.; Wang, Q.; Yao, H. Rheological and structural evolution of SBS modified asphalts under
natural weathering. Fuel 2016, 184, 242–247. [CrossRef]
43. Yu, J.Y.; Feng, P.C.; Zhang, H.L.; Wu, S.P. Effect of organo-montmorillonite on aging properties of asphalt.
Constr. Build. Mater. 2009, 23, 2636–2640. [CrossRef]
44. AASHTO T315-12. Determining the Rheological Properties of Asphalt Binder Using a Dynamic Shear
Rheometer (DSR). In AASHTO Provisional Standards; American Association of State Highway and
Transportation Officials: Washington, DC, USA, 2016.
45. AASHTO M320-17. Performance-Graded Asphalt Binder. In AASHTO Provisional Standards; American
Association of State Highway and Transportation Officials: Washington, DC, USA, 2017.
46. AASHTO T316-13. Viscosity Determination of Asphalt Binder Using Rotational Viscometer. In AASHTO
Provisional Standards; American Association of State Highway and Transportation Officials: Washington, DC,
USA, 2017.
47. ASTM D6560-17. Standard Test Method for Determination of Asphaltenes (Heptane Insolubles) in Crude Petroleum
and Petroleum Products; ASTM International: West Conshohocken, PA, USA, 2017.
48. Wang, J.; Wang, T.; Hou, X.; Xiao, F. Modelling of rheological and chemical properties of asphalt binder
considering SARA fraction. Fuel 2019, 238, 320–330. [CrossRef]
49. Siddiqui, M.N.; Ali, M.F. Studies on the aging behavior of the Arabian asphalts. Fuel 1999, 78, 1005–1015.
[CrossRef]

Sample Availability: Samples of the compounds are not available from the authors.

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(CC BY) license (http://creativecommons.org/licenses/by/4.0/).