Materials and Structures (2020) 53:64

https://doi.org/10.1617/s11527-020-01506-8 (0123456789().,-volV)
( 01234567
89().,-volV)

ORIGINAL ARTICLE

Compatibility of sunflower oil with asphalt binders: a way

toward materials derived from renewable resources
Muhammad Akhtar Tarar . Ammad Hassan Khan . Zia ur Rehman .
Sabih Qamar . Majid Niaz Akhtar

Received: 17 December 2019 / Accepted: 26 May 2020 / Published online: 9 June 2020
Ó RILEM 2020

Abstract The interest in utilization of renewable
resources like vegetable oils in the modification of
asphalt binders has been increasing for last few years.
This study aims to evaluate the sunflower oil (SO)
compatibility with three types of asphalt binders for its
future application in pavement and building construc-
tion. The chemical changes, aging behavior and
mixing uniformity of binders due to addition of SO
were studied through storage stability and fourier
transform infrared (FTIR) analysis. The potential of
SO modification in binders was assessed by using
rotational viscometer, dynamic shear rheometer and
bending beam rheometer tests. The Superpave,
Glover-Rowe diagram and master curve were used
for different tests analysis. FTIR results revealed the
induction of new peaks of esterification at 1163 cm-1
and 1745 cm-1 in binders mixed with SO. The SO
M. A. Tarar (&)  A. H. Khan  Z. ur Rehman
Department of Transportation Engineering &
Management, University of Engineering and Technology
(UET), Lahore, Pakistan
e-mail: akhtartarar2000@yahoo.com
S. Qamar
Department of Chemical Engineering, Muhammad Nawaz
Sharif University of Engineering and Technology,
MNSUET, Multan 60000, Pakistan
M. N. Akhtar
Department of Physics, Muhammad Nawaz Sharif
University of Engineering and Technology, MNSUET,
Multan 60000, Pakistan
modified binders showed antiaging behavior which
may be due to the presence of a-tocopherol in SO. It
was observed that use of SO in binders improved
fatigue parameter up to 58%. The linear amplitude
sweep test results showed that the addition of SO
increased the fatigue life of asphalt binders. The
sunflower oil as an additive in asphalt binders will be a
sustainable and durable material in pavement and
building constructions.
Keywords Asphalt  Sunflower oil  FTIR analysis 
Antiaging phenomenon  Fatigue
1 Introduction
Asphalt binder is the costly and more usable material
of the pavement. A huge quantity of asphalt binder is
required for the construction and maintenance of
highways around the globe [1]. About 95% of the
worldwide production of the asphalt binder is utilized
in the pavement industry [2] and the remaining is
consumed as a water proofing material in the buildings
construction. The qualities of the asphalt binders are
being improved by using different types of additives
and modifiers from non-renewable and renewable
resources. It is stated that the different artificial
petroleum and non-petroleum modifiers are the main
cause of environmental pollution [3–5].
64 Page 2 of 15
The factors like environmental issues, short supply
and rising cost of the asphalt binder urged the
researchers to investigate the renewable resources
derived materials for the replacement and modifica-
tion of the asphalt binders [6–10]. The derived
materials from renewable resources like vegetables,
plants and biomaterials can be used for the modifica-
tion of asphalt binders [11–16].
The sunflower is produced abundantly in most of
the countries like Ukraine, Russia, European Union,
Argentina, China, Turkey, United States and South
Africa. The extraction of oil from the sunflower is easy
and available at an affordable cost. It was found that
the aged binders can be softened by the addition of SO
during the recycling process of asphalt binders [17].
Further, it was investigated that the asphalt binder
mixed with SO was harder than the asphalt binder
modified with rapeseed oil. The study revealed that the
addition of sunflower and rapeseed oil reformed hard
asphalt binder 15/35 grade to 35/50 grade. The thermal
gravimetric results showed that the sunflower and
rapeseed oils were found to be nonvolatile [18]. The
sunflower and rapeseed oil improved the low temper-
ature resistance of the binders [19]. Shirzad et al. [20]
evaluated the effects of SO in aged asphalt binder and
determined that the SO had potential to restore aging
of binders. In addition, Garcia et al. [21] investigated
the self-healing potential of the SO as rejuvenator in
asphalt mixes. They found that SO reduced the tensile
strength of asphalt mixes produced using SO modified
binder.
Al-Mansoori et al. [22] examined the mechanical
and thermal properties of encapsulated SO with
asphalt mixes. It was observed that the capsules
hindered the mixing, compaction and broke due to the
external pressure. The study also revealed that the
healing level increased with the increase of
temperature.
The renewable resources derived oils have been
used in different studies for the modification of asphalt
binders. Tarar et al. [23] evaluated the rheological
properties of asphalt binders using soybean oil and
concluded that the addition of soybean oil in asphalt
binders increased the fatigue parameter by 67%. In
this study it was found that the use of soybean oil
decreased the high temperature performance of
asphalt binders by 14.8%. The study also reported
that the use of soybean oil in asphalt binders decreased
the complex shear modulus up to 75% and increased
Materials and Structures (2020) 53:64
the fatigue life up to 44%. Cavalli et al. [24]
investigated the effect of bio rejuvenators (natural
seed oil, cashew nut shell oil and tall oil) on the
mechanical and chemical properties of 50/70 and
reclaimed asphalt pavement (RAP) binders. The study
found that the bio rejuvenators have the potential to
restore the mechanical properties of RAP binders.
Elkashef el al [25–28]. examined the potential of
soybean oil as a rejuvenator in asphalt binders and
showed the significant improvement in fatigue and
low temperature resistance of asphalt binders. Chen
et al. [29] compared the properties of asphalt binder
modified with laboratory produce and commercial
oils. The study revealed that the use of soybean oil
decreased the viscosity, mixing and compaction
temperatures of asphalt binders. This study also
reported that the use of soybean oil improved resis-
tance against the fatigue damage of asphalt binders.
Lei et al. [30] reported that the use of oils in the
modification of asphalt binders could increase the low
temperature resistance of binders. Wang et al. [31]
used bio oil derived from waste cooking oil for the
modification of asphalt binders and concluded the
increase in fatigue life of asphalt binders. Cao et al.
[32] investigated the likelihood of waste vegetable oil
as rejuvenator and showed the increase in fatigue life
of the binders.
In the past studies, the SO was only used with
asphalt binders as rejuvenator or self-healing agent
and limited literature is available about its effect on the
rheology part. Further, the literature also lacks the
information on the chemical compatibility of SO with
binders along with aging considerations.
This study aimed to investigate the effect of SO on
the performance characteristics of the asphalt binder.
The objectives of this research are to determine the
effects of SO modification on chemical composition of
binders and to evaluate the performance related
rheological characteristics of binders modified with
SO. Different techniques were adopted to check the
performance of the binders. FTIR analysis was used to
evaluate the vibrational modes of these binders. The
compatibility of SO with asphalt binders was checked
by storage stability tests (SSTs). The rolling thin film
oven (RTFO) and pressure aging vessel (PAV) were
used for aging of binders. The effects of SO modifi-
cation with binders were assessed by using RV, DSR
and BBR testing.
Materials and Structures (2020) 53:64
2 Materials and methods
Three asphalt binders used in this study were obtained
from national refinery limited Karachi, Pakistan. The
penetration grades of asphalt binders were 40/50,
60/70 and 80/100. The binders were investigated in
laboratory according to the guideline provided in
AASHTO M320. The performance grades of unmod-
ified binders 40/50, 60/70 and 80/100 were determined
as PG64-16, PG64-22 and PG58-22 respectively, and
were designated as A, B and C, respectively. The
binders A, B and C were modified with SO and labeled
as Ao, Bo and Co, respectively. The SO was extracted
in laboratory from commercially available sunflower
seeds using squeezer with 100 rpm at temperature of
20 °C. The sunflower seeds and oil are depicted in
Fig. 1. The SO was mixed with asphalt binders at 5%
by weight of binders using shear mixer with 3000 rpm
for two hours at temperature of 180 °C. The mixing
procedure adopted in this study was also reported by
Tarar et al. [23, 33].
The rolling thin film oven (RTFO) was used for
short term aging of asphalt binders according to
AASHTO T-240 at 163 °C for 85 min. The RTFO
specimens of asphalt binders were used for long term
aging in pressure aging vessel (PAV) according to
AASHTO R-28 at 100 °C for 20 h and 2.1 MPa
pressure.
The rotational viscometer (RV) was used to deter-
mine the viscosity of asphalt binders according to the
AASHTO T 316 using spindle of SC4-21 with speed
of 20 rpm. The temperatures range was adopted as
135–165 °C. The viscosity temperature susceptibility
(VTS) was calculated by using the Eq. (1) [25] below.
a b
Fig. 1 a Sunflower seeds, b Sunflower oil
Page 3 of 15 64
log½logðg1 Þ  log½logðg2 Þ
VTS ¼ ð1Þ
logðT2 Þ  logðT1 Þ
where g1 and g2 are the viscosities in cP at corre-
sponding points of T1 and T2. The T1 and T2 are the
temperatures in Rankine.
The storate stability test (SST) was performned
according to the guidelines provided in the ASTM D
7173. The specimens of SO modified asphalt binders
were prepared in the test tubes at 163 °C for 48 h. The
specimens after removing from oven were placed in
the freezer at temperature of - 10 °C for 4 h. The
specimens within the test tubes were cut into three
equal parts by placing the tubes at plane surface
utilizing hacksaw. The specimens in the top and
bottom parts of tubes were used for testing and
discarded the specimens from the middle parts. The
SST technique for specimens preparation of modified
asphalt binders was also reported by the other study
[29]. The phase angle, complex shear modulus and
seperation ratio measurements of top and bottom parts
asphalt binders specimens were found according to the
procedure adopted by the Bahia and Zhai [34] and
Youtcheff et al. [35]. The temperature difference of
top and bottom parts specimens was determined by the
ASTM D36.
The Cary 630 FTIR-ATR was used for the assess-
ment of the functional groups in the asphalt binders.
The FTIR-ATR spectra of asphalt binders were
observed in the range of 650–4000 cm-1 at resolution
of 16 cm-1 with 90 scans. The circular silicone rubber
molds with 8 mm in diameter and 2.5 mm depth were
used for the preparation of FTIR test specimens. The
specimens for FTIR testing were put directly at the
ATR interface. The trichloroethylene was used for
cleaning of ATR interface. The carbonyl and sulfoxide
64 Page 4 of 15
indices of asphalt binders were calculated in according
to the procedure adopted by Mouillet et al. [36]. The
carbonyl and sulfoxide indices of binders were
calculated using Eqs. (2) and (3) below:
Carbonyl peak value around 1700 cm1
ICO ¼
Ethyl peak value around 1460 cm1 þ Methyl peak value around 1375 cm1
Sulfoxide peak value around 1030 cm1
ISO ¼
Ethyl peak value around 1460 cm1 þ Methyl peak value around 1375 cm1
The D-value of carbonyl indices of unaged and
aged asphalt binders were calculated according to
Eq. (4) as stated by Cong et al. [37].
D ¼ Iagedðc¼oÞ  Iunagedðc¼oÞ ð4Þ
Here, D-value represents the influence of thermal
aging, Iaged(C=O) (carbonyl index of aged binders),
Iaged(C=O) (carbonyl index of unaged binders).
The DSR test was conducted according to
AASHTO T 315 for the determination of high
temperature performance grades. The performance
grades of unmodified and SO modified asphalt binders
were measured according to the guidelines provided in
the AASHTO M320. standard. The fatigue parameter
(G*sind) was determined by employing DSR test at
PAV aged unmodified and SO modified asphalt
binders. The DSR test was performed at temperatures
rang of 6–36 °C with frequency of 10 rad/s. The
Superpave specifies the fatigue parameter at the point
where the G*sind value is equal to 5000 kPa. The
rutting parameter (G*/sind) was measured on unaged
and RTFO aged unmodified and SO modified asphalt
binders. For high temperature, Superpave specifies
G*/sind C 1 kPa for unaged asphalt binders and G*/
sind C 2.2 kPa for RTFO aged asphalt binders.
The BBR test was performaned according to
AASHTO T 313 for the measurement of low temper-
ature performance grades. For the the BBR tests,
asphalt binder specimens ware prepared in the silicone
molds. The length, width and thickness of specimens
were 125 mm, 12.5 mm and 6.25 mm, respectivley.
For low temperature, Superpave specifies s B 300
MPa and m C 0.300 using PAV aged asphalt binders.
Materials and Structures (2020) 53:64
The frequecy sweep test was conducted using DSR
at uaged, RTFO and PAV aged asphalt binders by
employing AASHTO T 315 guidelines. The unmod-
ified and SO modified asphalt binders were tested at
ð2Þ
ð3Þ
temperatures range of 6 °C to 36 °C using frequency
range of 0.1 rad/s to 100 rad/s and 1% strain rate.
The linear amplitude sweep (LAS) test was per-
formed according to AASHTO TP 101 on PAV aged
asphalt binders using DSR with 8 mm plate and 2 mm
gap geometry at the temperature of 18 °C. The
damage accumulation in the asphalt binder’s speci-
mens was calculated using Eq. (5) below.
X
N  a 1
Dð t Þ ffi pID c20 ðjG j sini1 jG j sini Þ 1þa ðti  ti1 Þ1þa
i¼1
ð5Þ
where DðtÞ is damage intensity, ID is initial value of
jG j in MPa, c0 is applied strain in percent, jG j is
complex modulus in MPa,a is the undamaged property
of binder, and t is testing time in seconds.
The fatigue life of asphalt binders was calculated by
Eq. (6) below:
Nf ¼ Aðcmax ÞB ð6Þ
where Nf is number of cycles to fatigue failure, cmax is
maximum expected asphalt binder strain for given
pavement structure, A and B are coefficients of model.
Minimum three specimens were tested for each test
to maintain the necessary precesion and accuracy.
3 Results and discussion
3.1 Temperature performance
In Table 1, true grades of high temperatures of binders
A, B and C are 68.9 °C, 65.3 °C and 60.9 °C,
respectively. The addition of SO in binders A, B and
Materials and Structures (2020) 53:64 Page 5 of 15 64

Table 1 Performance properties of binders

Description Unmodified binders SO modified binders Methods
A B C Ao Bo Co

Unaged (High Temperature), °C 68.9 65.3 60.9 56.7 55.2 49.1 AASHTO T315
RTFO (High Temperature), °C 69.8 65.5 63.3 57.8 56.1 52.5 AASHTO T315
PAV (Intermediate temperature), °C 25.3 22.6 21.2 23.7 20.6 16.7 AASHTO T315
PAV (Low Temperature), °C - 17 - 24 - 25 - 24 - 30 - 35 AASHTO T313
Performance grade (PG) 64–16 64–22 58–22 52–22 52–28 46–34 AASHTO M320
Continuous grade range, °C 85.9 89.3 85.9 80.7 85.2 84.1 –
D Tc, °C - 1.74 - 1.34 - 1.29 - 0.84 - 0.87 - 0.75 [38]
Viscosity (Pa*s) at 135 °C 0.462 0.445 0.375 0.255 0.241 0.231 AASHTO T316
Viscosity (Pa*s) at 145 °C 0.337 0.323 0.273 0.195 0.185 0.192 AASHTO T316
Viscosity (Pa*s) at 155 °C 0.237 0.213 0.193 0.156 0.165 0.160 AASHTO T316
Viscosity (Pa*s) at 165 °C 0.116 0.110 0.097 0.128 0.113 0.105 AASHTO T316
Viscosity temperature susceptibility (VTS) - 3.557 - 3.381 - 3.642 - 1.869 - 2.035 - 2.100 –
Mass loss at 163 °C, % 0.078 0.056 0.075 0.081 0.065 0.081 AASHTO T240
Average value of three replicates is reported

C decreased the high temperature true grades by
12.2 °C, 10.1 °C and 11.8 °C, respectively. The use of
SO leads to the higher decrease in the true grade of
binder A compared to binders B and C. The other
studies also proved the decrease in high temperature
grades due to addition of oils [23, 25–29]. The low
temperatures true grades of A, B and C, are - 17 °C,
- 24 °C, and - 25 °C, respectively. The SO
decreased the low temperature true grades of binders
A, B and C by 7 °C, 6 °C, and 10 °C, respectively.
The similar behavior of asphalt binders due to addition
of oils was also reported by other study [30]. The SO
exhibited more decrease in low temperature true grade
of binder C. Figure 2 depicts the continuous grade

80
High temperature true grades
Low temperature true grades

60
Continuous grade temperature (oC)

40
68.9 65.3
60.9
56.7 55.2
49.1
20

-17
-24 -25 -24
-30
-35
-20

-40
A B C Ao Bo Co
Binder types

Fig. 2 Grade range of binders

64 Page 6 of 15 Materials and Structures (2020) 53:64

range of unmodified and SO modified binders. It was stress relaxation ability of asphalt binders [7]. The
noticed that the use of SO leads to change of higher negative value of DTc represents the weak
continuous grades of binders A, B and C from performance of stress relaxation [27]. The addition of
85.9 °C, 89.3 °C and 85.9 °C to 80.7 °C, 85.2 °C SO decreased the viscosity of binders A, B, and C in
and 84.1 °C, respectively. Therefore, the SO reduced the temperature range of 135–165 °C as presented in
minimum continuous grade range of binder C. Table 1. The other researchers also reported the
similar behavior of decrease in viscosity of asphalt
3.2 DTc parameter binder using oil [25, 40]. The SO modified binders
showed less temperature susceptibility than unmodi-
The parameter DTc (difference in temperature between fied binders at higher temperature as represented by
m = 0.300 and S = 300 MPa at 60 s loading time) the viscosity temperature susceptibility (VTS) results
[38] was calculated according to the guidelines in Table 1. Addition of SO increased the mass loss of
provided in transportation research board (TRB) binders A, B and C, but this loss in mass was within the
circular [39] by using the BBR data (flexural creep Superpave criterion (viscosity \ 3 Pa.s at 135 °C).
stiffness, m-value i.e. slope of master stiffness curve Table 2 summarizes the properties of the SO inves-
and temperature) to estimate age related cracking tigated in the laboratory.
potential of binders. The DTc values are summarized
in Table 1. The DTc values of SO modified binders 3.3 Storage stability tests (SSTs)
showed higher ability to relax stresses in comparison
with original binders. This may be due to the higher Table 3 shows the summary of the SSTs results at
binder’s stress relieve rate during plastic flow. It was 25 °C and 58 °C intermeditate and high temperatures,
reported that the mixing of oil in binders improved the respectively. The results showed that the SO modified
binders satisfy the separation ratio range (0.8–1.2) as
Table 2 Summary of the SO properties elaborated by the other studies [34, 35]. The results in
Table 3 also fulfilled the criterion reported by other
Tests Results Methods
researchers for softening point test i.e. when the
Flash point, °C 315 ASTM D93 difference between the test results of top and bottom
Fire point, °C 340 ASTM D93 parts of test tube is less than 2.5 °C then the sample is
Carbon residue, % 0.35 ASTM D189 considered a thermally stable [41-43].
Dynamic viscosity @ 25 °C, Ps*s 0.061 AASHTO
T-316 3.4 FTIR analysis
Cloud point, °C -9 ASTM D5551
Melting point, °C 0.5 ASTM D5440 Figure 3 illustrates the carbonyl indices and D-values
a-tocopherol, Mg/100 g 70 [43] of unmodified and SO modified binders at different
aging conditions. Figure 3 indicates that the addition
Average value of three replicates is reported
of SO in binders A, B and C decreases the carbonyl

Table 3 Storage stability test results

Binders Softening point (°C) Difference between top High temperature Intermediate temperature
and bottom parts (°C) (Separation ratio) (Separation ratio)
After stability test
Top Bottom (G*) (d) (G*) (d)

Ao 47.6 46.5 0.7 0.98 0.95 0.97 0.97

Bo 44.7 44.4 0.3 1.03 1.00 1.01 1.00
Co 38.9 38.6 0.3 0.96 0.98 0.97 0.98
Average value of three replicates is reported
Materials and Structures (2020) 53:64 Page 7 of 15 64

indices and D-values up to 1.2 times and 2.5 times binders confirmed the presence of carboxylic acid
respectively. Figure 4 shows the decrease in sulfoxide (C=O at 1722 cm-1, O–H at 3300 cm-1 and C–O at
indices of asphalt binders A, B and C due to addition of 1312 cm-1) and anhydride (C=O at 1737 cm-1). The
SO. This revealed that, the aging press was hindered SO contains a-tocopherol (antiaging agent-
by the addition of SO. C29H50O2) from 64.80 mg to 73.02 mg per 100 g
[44, 45]. In Figs. 5, 6 and 7, the FTIR spectrum of SO
3.5 Antiaging phenomenon shows the presence of a-tocopherol (Oxane at
1088 cm-1, aromatic ring at 1460 cm-1). The induc-
FTIR spectra of asphalt binders A, B and C are tion of new peaks in Figs. 5, 6 and 7 at 1163 cm-1 and
depicted in Figs. 5, 6 and 7. The spectra asphalt 1745 cm-1 in SO modified asphalt binders indicate

-3 -3
5.0x10 3.0x10
D = Iaged(C=O) - I unaged(C=O) RTFO aged
A Ao B Bo C Co PAV aged
SO modified binders show less 2.5x10
-3
-3
4.0x10 SO modified binders show less D-value than unmodified binders
increase in carbonyl index
than unmodified binders 2.0x10
-3
Carbonyl index

-3
3.0x10
D
-3
1.5x10

-3
2.0x10
-3
1.0x10

-3
1.0x10 -4
5.0x10

0.0 0.0
Unaged RTFO PAV A Ao B Bo C Co

Fig. 3 Carbonyl indices and D-values of binders

4.0x10 -3
A Ao B Bo C Co

3.0x10 -3
Sulfoxide index

SO modified binders show less

increase in sulfoxide index
than unmodified binders
2.0x10 -3

1.0x10 -3

0.0
Unaged RTFO PAV

Fig. 4 Sulfoxide indices of binders

64 Page 8 of 15 Materials and Structures (2020) 53:64

(a) (b) (a) 1163 (b) 1745

SO
SO

A
A
Absorbance

RTFO (A)
RTFO (A)
SO

PAV (A) A
PAV (A) RTFO (A)

PAV (A)
Ao
Ao
Ao

RTFO (Ao)

RTFO (Ao) RTFO (Ao)

PAV (Ao)
PAV (Ao)
PAV (Ao)

800 1200 1600 2000 2400 2800 3200 3600 4000 650 780 910 1040 1170 1300 1430 1560 1600 1700 1800 1900 2000

Wavenumber cm -1

Fig. 5 FTIR spectra of SO and binder label A and Ao

(a) (b) (a) 1163 (b) 1745

SO SO

B
B
Absorbance

RTFO (B)
RTFO (B)
SO

PAV (B)
B
PAV (B)
RTFO (B)

Bo PAV (B)

Bo
Bo
RTFO (Bo)

RTFO (Bo)
PAV (Bo) RTFO (Bo)
PAV (Bo)
PAV (Bo)

800 1200 1600 2000 2400 2800 3200 3600 4000 650 780 910 1040 1170 1300 1430 1560 1600 1700 1800 1900 2000
-1
Wavenumber cm

Fig. 6 FTIR spectra of SO and binder label B and Bo

Materials and Structures (2020) 53:64 Page 9 of 15 64

(a) 1745
(b) (a) 1163 (b)

SO
SO

C
C
Absorbance

RTFO (C) RTFO(C)

SO

PAV (C) C
PAV(C)
RTFO(C)

PAV (C)
Co
Co
Co

RTFO (Co)

RTFO(Co) RTFO(Co)
PAV (Co)
PAV(Co)
PAV(Co)

800 1200 1600 2000 2400 2800 3200 3600 4000 650 780 910 1040 1170 1300 1430 1560 1600 1700 1800 1900 2000

Wavenumber cm-1

Fig. 7 FTIR spectra of SO and binder label C and Co

the production of an ester. The esterification process
not only retards the oxidation mechanism but also
suppress the volatilization process of light molecules
present in the asphalt binder. Figure 8 shows the
reaction of asphalt binder functional group (carboxylic
acid) and SO functional group (a-tocopherol) to
produce an ester.
3.6 Fatigue parameters
Figure 9 shows that the use of SO decreases the average
fatige parameter of binders A, B and C by 52%, 55%
and 58%, respectively. The decrease in fatigue param-
eter indicates the increase of fatigue resistance of
asphalt binders. This observation is also similar with the
outcomes of other reserachers [23, 26, 32]. Therefore, it
was concluded that the additoin of SO increased the
fatigue resistance of all tested binders. The SO showed
best performance with binder C.
3.7 Glover-Row diagram
Glover-Rowe parameter was applied to define the
damage zone containing the two thresholds of damage
namely damage onset and significant cracking [46].
The onset of damage zone was taken as G*cosd2/
sind = 180 kPa and significant cracking threshold was
considered as G*cosd2/sind = 450 kPa. Figure 10
shows the variation of SO modifed and unmodified
binders with respect to the Glower Rowe thresholsds
of cracking onset and significant cracking at different
aging conditions. Normally, the aging causes asphalt
binders to travel closer to damage zones [26] but even
at longe term aging (PAV aging) the SO modified
binders show their position far away from damage
zone. This observation indicates the longevity of SO
modified binders. The use of SO decreased the G* and
increased the d, which showed the softening effect of
SO. Figure 10 shows that the addition of the SO in
asphalt binders A, B and C increases the fatigue
cracking resistance and decreases the damage. The
similar behavior of decrease in G* due to addition of
oil in asphalt binders was also reported by other study
[28]. The unmodified binders show closeness to the
damage zone on long term aging in Fig. 10. The SO
showed better performance with binder C.
64 Page 10 of 15 Materials and Structures (2020) 53:64

Molecular structure of carboxylic functional group

of binder Molecular structure of α-tocopherol functional group
SO

-H2O

Molecular structure of α-tocopherol functional group

of SO
Molecular structure of anhydride functional group

-H2O

Molecular structure of ester functional group

Fig. 8 Ester formation from carboxylic functional group of binder and alpha tocopherol functional group of SO

3.8 Master curve C1 ðT  Tr Þ

log aT ¼  ð7Þ
C 2 þ ð T  Tr Þ
Equation (7) [47] is used to calculate the shift factors
for the development of master curve at reference where aT, C1, C2, T and Tr are the shift factor,
temperature of 18 °C. empirical constants, test temperature and reference
temperature, respectively. Figure 11 indicates that the
Materials and Structures (2020) 53:64 Page 11 of 15 64

Fig. 9 Comparison of 1E+08

fatigue parameter of binders

1E+07

Fatigue parameter (Pa)

1E+06 Intermediate temperature line
as specified by Superpave
G*sin δ = 5000 kPa

SO modified binders show

1E+05 decrease in fatigue parameter

A Ao B Bo C Co
1E+04
6 12 18 24 30 36
o
Temperature ( C)

Fig. 10 Glover Rowe 1E+05

diagram for binders A and
Ao Block cracking zone

1E+04
Damage zone
Aging
PAV

RTFO
PAV
log G* (Pa)

unaged
1E+03
No block cracking zone
RTFO

unaged

SO modified binders show more

fatigue cracking resistance
than unmodified binders

1E+02

A 180 kPa 450 kPa Ao

1E+01
0 10 20 30 40 50 60 70 80 90
Phase angle (degree)

addition of SO decreases average complex modulus
(G*) of binder A by 44%. The decrease in G* is due
to the addition of SO is more at higher temperatures
and lower frequencies. The shifting of curves
towards higher values of G* at higher frequencies
and lower temperatures due to aging was less in SO
modified binder Ao. This observation supports the
antiaging behavior of SO in asphalt binder Ao. The
other studies also reported the similar observations
[7, 23, 26, 29, 48]
64 Page 12 of 15 Materials and Structures (2020) 53:64

1E+07

SO modified binders show decrease in G*

1E+06

G* increases as rate of
1E+05 loading increases
Complex modulus (Pa)

2.0
1E+04
1.5
Reference temperature, 18 oC
1.0
G* decreases as rate
0.5
of loading decreases

log (a T)
1E+03
0.0

-0.5

-1.0
1E+02
-1.5
A RTFO (A) PAV (A)
-2.0 Ao RTFO (Ao) PAV (Ao)

-2.5
1E+01 5 10 15 20 25 30 35 40
o
Temperature ( C)
A Ao RTFO (A) RTFO (Ao) PAV (A) PAV (Ao)
1E+00
1E-05 1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 1E+03 1E+04 1E+05 1E+06

Reduced frequency, fR (Hz)

Fig. 11 Master curve for binders A and Ao

Figure 12 shows fatigue lives of binders A, B and C produced an ester in which a-tocopherol present in the
at 18 °C. The addition of the SO increased fatigue life SO acted as an antioxidant agent. The use of SO
of binders A, B and C by 28%, 32% and 37%, improved fatigue performance and increased rutting
respectively. The other researcher conducted the susceptibility of all binders. The improvement in
similar studies [7, 23, 26, 31, 32]. fatigue performance of asphalt binders due to addtion
of SO was also testified by Glower-Rowe diagram.
Possible reason may be due to esterification of SO and
4 Conclusions aphalt binders. The master curves showed that the
addition of 5% mass of SO decreased complex
In this study, the effect of sunflower oil (SO) on the modulus of asphalt binder. Additionally, the SO
performance characteristics of asphalt binders were increased the fatigue life of asphalt binders. The SO
investigated through different techniques. The storage as an additive in asphalt binders with better fatigue
stability tests revealed the thermal stability of all SO performance will be a good candidate in pavement and
modified binders. The carbonyl index and sulfoxide buildings construction. The sunflower derived mate-
analysis depicted that the addition of SO improved the rials have been used in food products. The SO could be
antiaging behavior of the tested asphalt binders. FTIR used as an alternative material in the modification of
analysis showed an induction of new peaks of asphalt binders.
esterification at wavenumber 1163 cm-1 and
1745 cm-1. The reaction of asphalt binders with SO
Materials and Structures (2020) 53:64
Fig. 12 Cycles to failure at 1E+06
test temperature of 18 °C for
binders
1E+05
1E+04
Nf
SO modified binders show
1E+03 more fatigue life than
unmodified binders
1E+02
A Ao
1E+01
1 10
Compliance with ethical standards
Conflict of interest The authors declare that they have no
conflict of interest.
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