Construction and Building Materials 240 (2020) 117921

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Construction and Building Materials

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Effect of activated carbon obtained from vinasse and marc on the

rheological and mechanical characteristics of the bitumen binders and
hot mix asphalts
Elif Sß eyma Seyrek a, Erkut Yalçin a, Mehmet Yilmaz a,⇑, Baha Vural Kök a, Hasan Arslanoğlu b
a
Firat University, Faculty of Engineering, Department of Civil Engineering, Elazığ, Turkey
b
Ahi Evran University, Department of Chemical and Process Engineering, Kırsßehir, Turkey

h i g h l i g h t s

Effects of the AC modification on the rheological characteristics of the bitumens were examined.

HMA properties including the activated carbon modified binders were investigated.

Activated carbon increased stiffness and high temperature resistance of bituminous binder.

AC improved stability, stiffness, resistance against the fatigue cracking, and permanent deformation of mixes.

Using AC in the bitumen modification adversely affected the resistance against the moisture-induced damage in HMAs.

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

Article history: This study examined the effect of the activated carbon, obtained from marc and vinasse agricultural
Received 16 October 2019 wastes and used in the bitumen modification, on the rheological characteristics of bitumen binders
Received in revised form 25 November 2019 and mechanical properties of hot mix asphalt. For this purpose, the activated carbon, obtained from
Accepted 19 December 2019
vinasse generated at distillation step in the alcohol production from molasses together with grape marc,
was used. The activated carbon was added to neat bitumen (PG 58–16) in 3 different ratios (5%, 10%, and
15% by weight of neat binder). The following tests were applied to the neat and modified bitumen: BBR
Keywords:
(bending beam rheometer), DSR (dynamic shear rheometer), rotational viscosity, softening point, and
Activated carbon
Bitumen modification
penetration. The HMA samples were prepared using the neat and modified binders. The following tests
Vinasse were applied to the HMA samples: Marshall stability and flow, resistance against the damage induced
Marc by moisture, indirect tensile stiffness modulus, cyclic creep, and indirect tensile fatigue. Considering
Asphalt performance the binder test results, it was determined that using the activated carbon in the bituminous modification
increased the stiffness and high-temperature performance of the bituminous binders, while the low-
temperature performance was not affected much. Based on the mixture tests, it was found that using
the activated carbon modified bitumen increased the Marshall stability, stiffness, resistance against the
fatigue cracking, and permanent deformation of mixes. On the other hand, the use of activated carbon
in bitumen modification adversely affected the resistance against the moisture-induced damage.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
The flexible pavements are composed of subbase, base, and
overlays (binder and wear) built on a compacted floor with a lay-
ered structure. Although the flexible pavements seem to be very
simple structures; in fact, they are very complex (maybe the most
⇑ Corresponding author.
ß eyma Seyrek), erkutyalcin@firat.
E-mail addresses: elifseyrek@firat.edu.tr (E. S
edu.tr (E. Yalçin), mehmetyilmaz@firat.edu.tr (M. Yilmaz), bvural@firat.edu.tr
(B. Vural Kök), hasan.arslanoglu@ahievran.edu.tr (H. Arslanoğlu).
complex of all civil engineering structures) [1]. Due to the techno-
logical and economic developments, the increasing number of
vehicles and axle loads and the climatic conditions as well cause
great damages in the flexible pavements [2]. In the flexible pave-
ments, the surface courses are the most exposed part to the envi-
ronmental and traffic stresses (especially hot mix asphalt wear
layer).
The hot mix asphalt (HMA) includes the consumption of a large
amount of natural (such as aggregate) and produced (such as bitu-
men) construction materials. The bituminous binders are produced

https://doi.org/10.1016/j.conbuildmat.2019.117921
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921
by means of refining the petroleum which is not a renewable nat-
ural resource. The world has 50 years of petroleum reserves left [3]
and this situation causes environmental and economic concerns.
Therefore, the alternative/new materials and methods have been
examined for improving the pavements’ service life and thus
reduce the amount of consumed materials [4].
A large amount of by-product is generated from the agriculture,
construction and demolition, industrial and domestic sources.
These by-products are considered waste unless there is a means
to use/recycle these materials. Waste materials cause the health,
environmental, and economic problems. Use of by-products in
road constructions can provide a way to preserve the natural
resources, to save energy, to decrease the greenhouse gas emis-
sions and the costs incurred for the storage areas and construction
[5].
Various waste materials (such as tire rubber, shingle, polymers)
are used as asphalt additives [6–10]. Pyrolysis, that is, carboniza-
tion refers to the thermos-chemical degradation seen in the
organic materials at high temperatures in the environment free
of oxygen. By means of the degradation in question, the products
in three states of matter (solid, liquid, and gas phases) are
obtained. The liquid and solid products obtained by means of
pyrolysis are called bio-oil and bio-char, respectively [11]. Acti-
vated carbon can be obtained by applying some additional treat-
ments to bio-char. Numerous studies have been conducted on
using carbon-based materials as bitumen or mixture additive to
improve the rheological behavior of bituminous binders and
mechanical properties of HMAs [12–22]. Bio-char and activated
carbon increase resistance to rutting parameters [12–13], stiffness
[14], aging resistance [15–17], and decrease thermal susceptibility
[18] of bituminous binders. Additionally, mixtures with activated
carbon modified binders have positive effects in terms of self-
healing with induction and microwave [19,20], ice-melting perfor-
mance [21], stability, stiffness and indirect tensile strength [22].
Vinasse and marc are the waste materials generated during the
production of alcohol from molasses. 12–15 L of vinasse are gener-
ated during the production of 1 L of alcohol [23]. Disposal of the
slurry with high organic matter load causes the water
contamination.
Activated carbon (AC) obtained from vinasse and marc can be
utilized as a cost-efficient adsorbent in the environmental applica-
tions for controlling the air and water pollution [24–25]. Using the
activated carbons obtained from the wastes as a bitumen additive
in a different area will be beneficial in terms of environment, econ-
omy, and performance. Therefore, in this study, the effects of acti-
vated carbon obtained from vinasse and marc on rheological
behavior of bitumen binders and the mechanical chracteristics of
HMAs were investigated in detail.
2. Materials and sample preparation
Concentrated vinasse was obtained from Eskisßehir Sugar Fac-
tory Alcohol Production Facilities and marc from Elazığ Sivrice
Eskibağlar Wine Factory. Washing, drying, grinding, and sieving
pretreatments of marc were carried out in a previous study [24].
A 50 mesh particle size calibrated sample was homogenously
mixed in a blender with a weighing ratio of 1:2 at 22000 rpm for
3 min of rapid stirring. After 6 h, the samples were taken into
85 mL porcelain crucible and placed in an oven at 100 °C. Pyrolysis
was carried out for 120 min in a 600 °C oven with 300 mL/min
nitrogen gas. For pyrolysis, the samples were placed in the oven
at room temperature and the nitrogen gas was introduced for
10 min. The oven was started to heat, reaching a temperature of
600 °C in 15 min. After the treatment, the samples taken from
the oven were cooled in a vacuum desiccator. The pyrolysis
products were milled and sieved through a 200 mesh
(<0.075 mm) sieve. The samples were extracted with water by
shaking at 200 rpm for 120 min at room temperature (23–27 °C)
(water/pyrolysis product ratio of 10). The solid samples remaining
from the extraction were mixed with 2 M HCl solution (10 times
the pyrolysis product obtained) with agitation for 12 h. The solid
separated from the liquid by filtration through Gooch crucible
was subjected to washing to neutrality and washed with pure
water until the AgCl3 of the samples did not form AgCl3 solution
and the solid activated carbon obtained finally was dried at
100 °C for 12 h [24]. The characteristics of the activated carbon uti-
lized in the study were given in the Table 1 and the SEM images
were given in the Fig. 1.
The PG 58–16 (B 160/220) class bitumen procured from Turkish
Petroleum Refineries (TÜPRAS ß ) was utilized as the main binder.
The modified bitumens were obtained by the addition of activated
carbon at the ratios (neat bitumen/main binder) of 5%, 10%, and
15%. In the preparation of the modified binders, the neat bitumen
and additives were underwent a process of mixing for 60 min at
160 °C using a mixer at 1,000 revolutions per minute (rpm). Binder
test results of neat bitumen (B 160/220), 5% (MB5%AC), 10% (MB10%
AC) and 15% activated carbon modified bitumen (MB15%AC) were
given in the Table 2. As can be seen from the values for the soften-
ing point and penetration, the stiffness of binders increased with
the use of additives. From DSR tests, it was determined that all bin-
ders met the Superpave rutting parameter (G*/sin d) specification
requirement (1000 Pa at minimum) at 52 °C and 58 °C. Neat bitu-
men and 5% activated carbon modified bitumen did not meet this
criterion at 64 °C. Therefore, the performance grade high tempera-
ture value of these two binders was determined to be PG 58. 10%
and 15% activated carbon modified bitumens met the specification
criterion at 64 °C but not at 70 °C. Based on these results, the per-
formance grade high temperature value of 10% and 15% activated
carbon modified bitumen was determined as PG 64. When the rut-
ting parameters were evaluated, it was determined that the mod-
ified bitumen containing neat bitumen and 5% activated carbon
behaved similarly. Compared to the neat binder, the use of 10%
and 15% activated carbon caused a significant increase in the rut-
ting parameter. Based on the DSR tests carried out on RTFOT resi-
dues, it was determined that the Superpave rutting parameter (G*/
sin d) specification (min 2200 Pa) was fulfilled at the temperatures
determined from the original binders. The BBR test was carried out
at 6 and 12 °C. All of the binders met the stiffness and m-value
Superpave specification requirements at 6 °C. However, the bin-
ders did not meet the m-value specification requirement (min
0.300) at 12 °C. Therefore, the performance grades for the neat
and the 5% activated carbon modified bitumens were determined
as PG 58–16. On the other hand, the performance grades for 10%
and 15% activated carbon modified bitumens were determined as
PG 64–16.
Because the bituminous binders should have viscosity values of
0.17 ± 0.02 Pas (170 ± 20 cP) during mixing with the aggregate and
0.28 ± 0.03 Pas (280 ± 30 cP) during laying out [26]; two tempera-
tures, that is, 135 °C and 165 °C were used in the rotational vis-
cometer tests applied to the neat and modified binders.
Viscosity-temperature graphs plotted with the obtained results
were used to specify the temperatures for the mixing and com-
paction. The rotational viscometer test findings were presented
in the Table 3. As seen in the table, the viscosity values increased
in parallel to the additive use. The use of additives contributed to
the increase in the binder stiffness thanks to the increase in the
proportion of rigid particles. It was determined basen on the vis-
cosity test results that all the binders met the pumpability Super-
pave specification limit (max 3000 cP).
The limestone aggregates were utilized in the mix samples. Its
characteristics and gradation were provided in the Table 4. The
 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921 3

Table 1
Properties of used activated carbon [24].

(Pyrolysis conditions :S/C = 2, Pyrolysis temperature: 600 °C, Pyrolysis time : 120 min , Acid stabilization : 2 N HCl, s Liquid / solid ratio = 10, Drying Temperature:
100 °C).
Property Value
Visible density (g/cm3) 0.7814
3
Actual density (g/cm ) 1.7223
2
BET surface area (Micro + Meso)((m /g) 498.4
Micropore surface area (m2/g) 379.1
Mesopore surface area (m2/g) 119.3
Langmuir surface area (m2/g) 658.2
1
Pore volume (Micro + Meso)(cm3/g) 0.2463
3
Micropore volume (cm /g) 0.1757
Mesopore volume (cm3/g) 0.0706
2
Diameter of pore (Å) 22.7
Particle size [Weighted average (D[4,3]), lm] 19.489
Particle size [d(0.1), lm] 4.398
Particle size [d(0.5), lm] 16.820
Particle size [d(0.9), lm] 38.417
Ash (%) 5.1
Volatile matter (%) 28.70
Fixed carbon (%) 66.20
Elemental analysis
C H N S O
63.5 2.38 3.70 0.60 24.72

Fig. 1. SEM images of the obtained activated carbon (Pyrolysis conditions:S/C = 2, Pyrolysis temperature: °C, Pyrolysis time: 120 min, Acid stabilization: 2 N HCl, s Liquid /
solid ratio = 10, Drying Temperature: 100 °C).

dense–graded asphalt mix samples having a 19-mm aggregate size
at maximum were prepared and the optimum rate for the bitumen
content was determined to be 4.9% for the control mixes, and this
rate was applied to the other mixes. The volumetric characteristics
of all mixes were given in the Table 5. As can be seen in the Table 5,
all the mixes met the Superpave specification limits of volumetric
properties.
3. Mixture tests
3.1. Marshall stability and flow test
The Marshall stability and flow test was carried out for the HMA
samples prepared using the neat (PG 58 – 16) and 3 different mod-
ified bitumens (MB5%AC, MB10%AC and MB15%AC). A total of 12 sam-
ples, 3 of each mixture type, were submerged in 60 °C water for
40 min in compliance with EN 12697–34 standard, and were then
broken at 50.8 mm/min loading speed [27]. The Marshall stability
values for the mixes were given in the Fig. 2. The values represent
the averages for the three samples.
As understood from the Fig. 2, the Marshall stability value
(MSV) increased with the additive usage. Compared to the neat
mix, the MSV of the mixes increased by 2.81%, 5.01%, and 6.81%
in the mixtures prepared using the MB5%AC, MB10%AC and MB15%AC
modified bitumen, respectively. This showed that using the acti-
vated carbon in bitumen modification would positively affect the
strength of hot mix asphalts. When the flow values, the deforma-
tions at the maximum load seen in the Fig. 2, were examined, it
was found that the flow values showed a regular decrease as the
additive content increased. Compared to the neat mix, the flow val-
ues of the mixtures decreased by 4.86%, 10.98%, and 11.67% in mix-
tures prepared using the MB5%AC, MB10%AC and MB15%AC modified
bitumen, respectively. Bitumen and activated carbon have a similar
structure since they contain a high content of carbon. Therefore,
due to the increase of the binder stiffness by the use of solid acti-
vated carbon in bitumen modification, the stability values of the
mixtures were increased while the flow values were decreased.
The Marshall Quotient (MQ) value was calculated according to
the ratio of mixture stability (kN) values to the flow (mm) values
[28]. MQ values for the conditioned/unconditioned mixes were
provided in the Fig. 3.
4 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921

Table 2
Binder test results.

B 160/220 MB5%AC MB10%AC MB15%AC

Penetration test (EN 1426) results
176.7 115.7 113.0 82.2
Softening point test (EN 1427) results
43.7 45.75 47.1 49.95
DSR test results
Temp.(°C) G*/sind (kPa) (specification limit min. 1 kPa)
B 160/220 MB5%AC MB10%AC MB15%AC
52 2.394 2.286 5.541 6.725
58 1.199 1.064 2.617 3.156
64 0.537 0.554 1.250 1.578
G*/sin d (kPa) RTFOT residue (specification limit min. 2.2 kPa)
52 9.430 10.661 23.510 25.480
58 4.063 4.711 10.410 11.630
64 1.934 2.317 4.834 5.134
70 0.959 1.067 2.216 2.632
G*.sin d (kPa) PAV residue (specification limit max. 5000 kPa)
22 1660 1549 4043 4893
25 1015 1046 1664 2200
28 901 819 1028 1537
BBR test results
Temp.(°C) m-value (specification limit min. 0.300)
B 160/220 MB5%AC MB10%AC MB15%AC
6 0.341 0.330 0.312 0.305
12 0.244 0.276 0.264 0.247
Creep stiffness (Mpa) (specification limit max. 300 MPa)
6 27.6502 27.3470 30.6910 37.6427
12 34.1147 44.0825 54.3567 64.4146
Performance grades (PG)
58–16 58–16 64–16 64–16

Table 3
Rotational viscosity test results.

Properties Standard B 160/220 MB5%AC MB10%AC MB15%AC

Viscosity (cP, 135 °C) ASTM D4402 275 387.5 475 625
Viscosity (cP, 165 °C) 100 137.5 165.5 212.5
Modification index(gmodified /gneat, 135 °C) – – 1.41 1.73 2.27
Modification index (gmodified /gneat, 165 °C) – – 1.38 1.66 2.13
Mixing temperature range (°C) – 144.8–151.7 153.6–160.3 161.8–168.5 168.0–174.5
Compaction temperature range (°C) – 130.4–136.7 139.6–145.7 147.8–153.9 154.3–160.3

Table 4
Combined aggregate gradation and physical properties of the aggregate.

Used gradation
Sieve size (mm) 19 12.5 9.5 4.75 2.36 1.18 0.600 0.300 0.150 0.075
Total cumulative passing (%) 100 95 88 65 39 24 18 14 10 6
Physical properties of the aggregate
Properties Standard Specification limits Coarse Fine Filler
Abrasion loss (%) (Los Angeles) ASTM D 131 Max 30 29.2 – –
Abrasion loss (%) (Micro deval) ASTM D 6928 Max 15 17.4 – –
Frost action (%) (with Na2SO4) ASTM C 88 Max 18 16.7 – –
Methylene blue (gr/kg) ASTM C 837 Max 1.5 0.5 – –
Specific gravity (g/cm3) ASTM C127 2.626 – –
Specific gravity (g/cm3) ASTM C128 – 2.661 –
Specific gravity (g/cm3) ASTM D854 – – 2.689

Table 5
Volumetric properties of pure and modified mixtures.

Mixture properties Specification Limits Binder type

B 160/220 MB5%AC MB10%AC MB15%AC
Volume of air voids (Va, %) 4.0 ± 0.5 4.32 4.08 4.41 4.32
Voids in the mineral aggregate (VMA, %) min. 14.0 14.46 14.15 14.37 14.42
Voids filled with asphalt (VFA, %) 65–75 70.13 71.17 69.34 70.07
 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921 5

14.00 4.00
Stability Flow
3.80
13.80
3.60
13.60

Marshall stability, kN
3.40
13.40
3.20

Flow, mm
13.20 3.00

2.80
13.00
2.60
12.80
2.40
12.60
2.20

12.40 2.00
0 5 10 15
Activated carbon content, %
Fig. 2. Marshall stability and flow values of mixtures.

5.0
4.5
4.0
Marshall quotient (MQ), kN

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0 5 10 15
Activated carbon content, %
Fig. 3. Variation of Marshall quotient (MQ) values with AC content.

As understood from the Fig. 3, the MQ value, which is an indi-
cator of the resistance of HMAs against the permanent deformation
[28], increased with the additive usage. The MQ values of the mixes
prepared using the MB5%AC, MB10%AC, and MB15%AC were 8.06%,
17.96%, and 20.93% higher compared to the neat mix, respectively.
It was also found that HMAs’ resistance against the permanent
deformation increased significantly by using the activated carbon
in bitumen modification.
3.2. The test of resistance to the damage induced by moisture
The AASHTO T283 standard [29] was the basis of the test used
to rank the moisture-induced damage resistance rates of mixes
prepared using a neat binder and 3 different modified bitumens
(MB5%AC, MB10%AC and MB15%AC). Here, 6 samples of each binder
with a 7 ± 0.5% air void were prepared. The samples prepared in
the 4.9% bitumen content were subjected to a heating in an oven
at 60 °C for 16 h and then for two hours at the compaction temper-
ature according to short-term aging procedure. The compacted
samples were left for cooling under the ambient temperature.
The volumetric properties of the mixtures were determined the
following day. Six samples were divided into 2 groups each of
which had similar void rates. Three samples (1st group) were kept
in water at 25 °C for 2 h, and then were broken by applying
50.8 mm/min load on a plane perpendicular to the compaction sur-
face. The samples of the other group were vacuumed and saturated
with water to fill the voids at a water rate of 70–80%. Samples with
void rates that differed from 7 ± 0.5% and whose voids were filled
with more than 80% water were eliminated, and new samples were
prepared to replace these. The water-saturated samples were cov-
ered with stretch film to prevent a change in the saturation levels
and then were exposed to the conditioning process. In this process,
samples were initially stored in a freezer at 18 °C for a 16-hour
period of time, and then in water at 60 °C water for a 24-hour per-
iod of time. Later on, likewise the unconditioned samples, the sam-
ples were kept in water at 25 °C for a minimum of 2 h and were
then broken under a 50.8 mm/min load. Based upon the max load
level at the failure, the indirect tensile strength (ITS), expressed in
kPa, was computed using the formula below:
ITS ¼ 2  F=ðp  L  DÞ ð1Þ
6 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921
here, F refers to the peak value for vertical load (kN); L to the
average thickness of test sample (m); and D to sample diameter
(m). ITS values for the unconditioned/conditioned mixes were
given in the Fig. 4.
As understood from the Fig. 4, the minimum tensile strength
before conditioning was observed in the mixes prepared with neat
bitumen, and the highest value was observed in the mixes pre-
pared with 15% activated carbon modified bitumen. The values
for the tensile strength in the mixes with MB5%AC, MB10%AC, and
MB15%AC modified bitumen were 12.0%, 1.2% and 29.6% higher com-
pared to neat mix, respectively. Tensile strength values of the
mixes decreased due to conditioning. After conditioning, it was
found that the mixture with neat binder had the highest value
and the mixture with 10% activated carbon modified bitumen
had the lowest value. After the samples were conditioned, it was
determined that the tensile strength value of the mix with neat
binder was 1.8%, 29.7%, and 17.9% higher than those of mixes with
modified bitumen containing 5%, 10%, and 15% activated carbon,
respectively. This indicated that conditioning had a negative effect
on the tensile strength values of the mixes with activated carbon
modified bitumens.
The tensile strength ratio (TSR) value, an indicator of the resis-
tance of the mixtures against moisture-induced damage, was com-
puted using the following equation:
TSR ¼ 100  ðITScond: =ITSuncond: Þ
here, ITScond refers to the ITS of the conditioned samples and
ITSuncond refers to the ITS of the unconditioned samples. A tensile
strength ratio value of 80% has been considered as the min. thresh-
old for the HMAs as per the Superpave design procedure. TSR val-
ues of the mixes were also provided in the Fig. 4.
As shown in Fig. 4, as the activated carbon content used in bitu-
men modification increased, the TSR values decreased. It was
found that the mixture with the neat binder had the highest TSR
and the hot mix asphalt prepared with 15% activated carbon mod-
ified bitumen had the lowest TSR. Only the mixture with the neat
binder yielded 80% TSR. When compared to the neat mix, the TSR
values of the mixtures decreased by 12.4%, 30.5% and 36.7% in
the mixtures with MB5%AC, MB10%AC and MB15%AC modified bitumen,
respectively. This may be caused by the hydrophobic nature of
activated carbon, which has a plant-based origin. Similar results
were shown when using activated carbon obtained from hazelnut
800
700
Tensile strength (TS), kPa
600
500
400
300
200
100
0 0
0 5
Acvitated carbon content, %
Fig. 4. TS and TSR values of mixtures.
shells in bitumen modification [22]. Based on these results, it was
determined that using the activated carbon in modification of bitu-
men adversely affected the resistance of HMAs to the damage
induced by moisture.
3.3. Indirect tensile stiffness modulus (ITSM) test
ITSM values of HMAs were determined based on the standard
BS DD 213 [30]. Using the Universal Testing Machine (UTM), the
ITSM test was applied to the samples at 25 °C. They were put in
the UTM conditioning cabin 3 h prior to the test so as to ensure
that they completely reached the desired test temperature. Then,
the sample name, sample height, estimated stiffness value, esti-
mated Poisson’s ratio, load increase time, and target deformation
values were entered in the test software. In the study, the esti-
mated Poisson’s ratio, load increase time, and target deformation
were selected as 0.35, 124 ms, and 5 lm, respectively [30]. ITSM,
that is, Sm was defined as follows and expressed in MPa:
Sm ¼ F  ðR þ 0:27Þ=ðL  HÞ ð3Þ
here, F refers to the peak of vertical repeated load (N), H to the
average amplitude of horizontal deformation (mm) obtained from
applying load pulse from 5 applications, L to the average thickness
of the test sample (mm), and R to the Poisson’s ratio. Because the
ITSM is a nondestructive experiment, the samples utilized in the
ð2Þ
ITSM test were then utilized in indirect tensile fatigue tests. A total
of three specimens of mixes with each binder were subjected to
the ITSM experiment. After having been exposed to the test, each
sample was rotated 90°and the experiment was repeated. In cases
where the difference between the two ITSM values obtained in
these two tests was higher than 10%, the sample was again rotated
90°and a third measurement was taken. In cases where the differ-
ence between the two ITSM values obtained in these two tests was
lower than 10%, the average of these figures was accepted as the
ITSM value for the specimen. The effects of additive use on ITSM
values were given in Fig. 5.
As indicated in Fig. 5, using activated carbon in bitumen modi-
fication increased the ITSM values. Although the effect of 5% acti-
vated carbon was low, the use of 10% AC and 15% AC
significantly increased the stiffness modulus. It was determined
that using 5%, 10% and 15% activated carbon in bitumen modifica-
tion increased the stiffness modulus values of HMAs by 45.9%,
90
Unconditioned Conditioned
TSR 80
Tensile strength ratio (TSR), %
70
60
50
40
30
20
10
10 15
 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921 7

700

600

500
ITSM, MPa
400

300

200

100

0
0 5 10 15
Activated carbon content, %
Fig. 5. Variation of ITSM values with activated carbon content.

241.4%, and 330.2% compared to the neat mix, respectively. It was
also found that the use of 10% and 15% activated carbon in bitumen
modification significantly increased the stiffness modulus of
HMAs. The inter-particle and inter-molecular interactions between
bitumen and activated carbon may cause increases in stiffness of
the bitumen and HMA.
3.4. Indirect tensile fatigue test
The indirect tensile fatigue (ITF) tests were carried out in the
controlled stress mode as per the BS DD ABF standard [31]. The
tests were conducted at 25 °C; and 200 kPa stress level was used
in the study. Loading period (1.5 sec), loading effect time (0.124
sec), stress level, specimen diameter and height were entered in
the UTM software and the test was started. The ITF test was main-
tained until the specimens broke. Based on the finding data
obtained from the stress-controlled fatigue tests, the representa-
tive load repetition number-deformation level graph was plotted
and given in the Fig. 6. The material’s response to the fatigue load-
ing could be classified into 3 phases. In the first phase, an excessive
amount of deformation is observed because of the void formation
and then the axial deformation decreases. In the second phase, a
deformation occurs at a constant level and an approximate linear
change is observed. In the third phase, the crack propagation starts
in parallel with the increase in the deformation levels [32]. The
accumulated deformation versus load-cycle at a stress level of
200 kPa was showed in the Fig. 7.
In the indirect tensile fatigue tests, the software provided the
load repetition numbers within specific intervals and correspond-
ing amounts of deformation in mm. The final values obtained
showed maximum load repetition count (Nmax) where the speci-
men cracked and the deformations occured at the maximum load
repetition count (dmax). The data obtained were entered into Excel
program. Graphs were then plotted and II and III sections for the
load repetition number – deformation graphs were determined.
A line was plotted through the II and III sections and the line equa-
tions were obtained. Equations for the II and III sections were
equaled to each other and the fatigue values (Nf), which were the
intersection points of these equations, were obtained [33]. Later
on, using the data obtained from the software, the deformation

4.5

4 δmax
3.5
Terary
Deformation, mm

3 stage
Secondary δf
2.5
Primary stage
2
stage
1.5

0.5

0
0 500 1000 1500 2000 2500 3000 3500 4000

Load cycle number Nf Nmax

Fig. 6. A representative deformation-load repetition number relationship of asphalt mixtures.
8 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921

4.0

3.5

3.0
Deformation, mm
2.5

2.0
Neat
1.5
5% AC
1.0
10% AC
0.5
15% AC
0.0
0 500 1000 1500 2000 2500
Load cycle number
Fig. 7. The variation of deformation with load repetition number at 200 kPa stress level.

values (df) corresponding to Nf value were identified. Variations in
Nf and Nmax values of the mixtures according to additive type are
displayed in Fig. 8.
Crack propagation rate (rp) refers to the load repetition number
required to cause a deformation of 1 mm from the fatigue life to
the maximum load cycle number. The crack propagation rate was
computed using the following equation:
r p ¼ ðNmax  Nf Þ=ðdmax  df Þ
where rp refers to the rate of crack-propagation (cycle number/
mm), df to the total deformation at maximum load cycle number
(mm), and finally df to the total deformation at fatigue life (mm).
There is an inverse proportion between the crack propagation ratio
and rate; therefore, as the rp increases, the crack propagation ratio
decreases and vice versa. The crack propagation rates (rp) of the
mixes were also shown in Fig. 8.
When the Fig. 8, which displayed the variations on load repeti-
tion numbers with additive use, was examined, it was seen that
the neat mixture provided the lowest value, while the highest val-
ues were observed in the mixes prepared with 15% activated carbon
modified bitumen. The HMAs’ fatigue life significantly increased
with the use of additives and as the amount of the additives were
increased, the improvement in fatigue life increased regularly. Nf
and Nmax values were similarly changed. The fatigue life (Nf) values
of HMAs prepared with 5%, 10% and 15% activated carbon modified
bitumens were 2.06, 2.82, and 3.58 times more than those of the
mixes prepared with neat binder, respectively. Furthermore, the
ð4Þ
use of activated carbon in bitumen modification increased the crack
propagation rates. It was found that the mix with the neat binder
yielded the lowest value and the mixtures prepared using 10% acti-
vated carbon modified bitumen yielded the highest value. The crack
propagation rate of the mixture prepared with 15% activated carbon
modified bitumen was lower than that of the mix with 10% acti-
vated carbon modified bitumen due to the fact that this mixture
was more rigid and the crack progressed faster. The crack propaga-
tion rate (rp) values of HMAs prepared with 5%, 10% and 15% acti-
vated carbon modified bitumens were 1.24, 1.80, and 1.70 times
higher than those of the mixes with the neat binder, respectively.

2500 180

Nf 160
2000 Nmax 140
Load cycle number

rp 120
rp, cycle/mm

1500
100

80
1000
60

500 40

20

0 0
0 5 10 15
Acvated carbon content, %
Fig. 8. Nf, Nmax and rp values of mixtures.
 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921
3.5. Cyclic creep test
The cyclic creep test has been one of the most widely used test
for determining the HMAs’ resistance to the permanent deforma-
tion. The test is carried out using UTM and a constant load is
applied in a dynamic way at a given periodical rate to a cylindrical
sample. The plastic/elastic strains caused by the load cycles are
specified by means of LVDTs attached (in a vertical position) on
the metal plate fixed on the specimen’s surface. The creep modulus
can be computed using the following formulas [34];
ec ¼ ðL3n  L1Þ=G
r ¼ F=A
Ec ¼ r=ec
In the formulas above, ec refers to the plastic strain in total (%),
Ec to the creep modulus (MPa), G to the sample’s initial height
(mm), L1 to the initial reference displacement of LVDT (mm), L3n
to the displacement level before the application of (n + 1)th load
pulse (mm) (plastic), rto the max. vertical strain (kPa), F to the
max. vertical load (N), and A to the sample’s cross-section area
(cm2). As can be understood from the Equation[7], there is an
inverse proportion between the plastic strain’s levels and the creep
modulus values. Therefore, it could be interpreted that a HMA
sample having a high level of creep modulus would show a high
level of resistance to the permanent deformation.
The flow number (FN) also shows the HMAs’ resistance against
the permanent deformation. Similar to the one obtained by means
of the fatigue test, a curve showing the deformation versus the load
cycle number could be generated as a result of the cyclic creep test.
The point where the transition starts from the second phase to the
third phase in the curve is accepted as FN. FN can also be computed
from the peak value of the load-cycle vs. creep modulus  load-
cycle plot [35]. It was found that the FNs computed using the sec-
ond method were more able to be repeated compared to the first
method, that is, the slope method. Therefore, the second method
was used in this study for computing the FN values.
Cyclic creep tests were carried out at 50 °C for determining the
HMAs’ resistance to the permanent deformation. The stress levels
were determined as 400 kPa. The loading-period and the load-
rise-time were determined to be 1.0 s and 500 ms, respectively.
4.5
4.0 Neat
3.5 5% AC
3.0 10% AC
2.5 15% AC
2.0
1.5
1.0
0.5
0.0
0 2000
Fig. 9. Ɛc – load cycle number relation of mixtures.
9
Before the test was started, a static preloading was conducted on
the samples at 10 kPa stress level for 90 s. The tests were continued
until the permanent strain (Ɛc) values of samples reached 4% or
load repetition values reached 8,000 cycles. Three samples of each
type of mixture were tested. The variations of ec and Ec at 400 kPa
stress level up to the 8,000th cycle or 4% permanent strain were
given in Fig. 9.
As can be seen in Fig. 9 4% permanent strain occurred before
8000 load repetitions in the mixtures prepared with neat binder,
5% and 10% activated carbon modified bitumen. The number of
load cycle numbers caused by 4% permanent strain of the mixtures
ð5Þ
prepared with 5% and 10% activated carbon modified bitumen
were significantly higher than the neat mixture. 4525 load repeti-
ð6Þ
tions were applied to the mixtures prepared with neat binder for
4% permanent strain, 6995 load repetitions (1.55 times higher than
ð7Þ
neat mixture) to those with 5% activated carbon modified bitumen,
and 7749 load repetitions (1.71 times higher than neat mixture) to
those with 10% activated carbon modified bitumen. In the mixes
with modified bitumen containing 15% activated carbon, even in
8000 load repetitions, the 3rd zone was not passed and a very
low permanent strain occurred compared to other mixtures. In
order to compare all mixtures, the Ɛc values at 4000 load cycle
number versus the permanent strain values were compared for
all mixes (Fig. 10). The values in the figure are the average of the
values from 3 samples.
As can be seen in Fig. 10 showing determined flow number val-
ues, the permanent strain values decreased regularly as the
amount of the additive increased. The Ɛc values of the mixes pre-
pared with 5%, 10% and 15% activated carbon modified bitumen
were 1.90 times, 2.18 times and 2.89 times lower than the Ɛc values
of the mixes with the neat binder. This showed that using the acti-
vated carbon as an additive significantly increased the resistance
against the permanent deformation. The flow numbers increased
regularly with the use of additives. The flow number values of
the mixtures increased by 55.9%, 72,2%, and 149,0% in mixtures
prepared with MB5%AC, MB10%AC, and MB15%AC modified bitumen,
respectively when compared to the neat mixture. Cyclic creep test
results showed that using the activated carbon as a bitumen addi-
tive significantly increases the HMAs’ resistance to the permanent
deformation. The bitumen viscosity mainly depends on its consti-
tutive components and the interactions between these. The pres-
ence of foreign solid particles such as activated carbon in the
4000 6000 8000 10000
Load cycle number
10 E. Sßeyma Seyrek et al. / Construction and Building Materials 240 (2020) 117921
3 7000
Ɛc values at 4.000 load cycle
number
2.5
Flow number
Permanent strain (Ɛc), % 2
1.5
1
0.5
0 0
0 5
Acvated carbon content, %
Fig. 10. Ɛc at 4.000 load cycle number and flow number values of mixtures.
bitumen matrix contributes to the enhancement of the bitumen
viscosity. The improvement of the viscosity leads to an increase
in the rutting resistance of the HMAs [18].
4. Conclusion
In this study, the activated carbon obtained from the vinasse
and the marc was added to the bituminous binder in 3 different
ratios (5%, 10% and 15% by weight of bitumen) and the its effect
as an additive on rheological characteristics of the bitumen binders
and mechanical characteristics of HMAs were examined. Five dif-
ferent tests (Marshall stability and flow, ITS, ITSM, ITF, and cyclic
creep tests) were applied to HMA specimens as well as the conven-
tional and Superpave binder tests. Findings were summarized as
follows:
As a result of penetration, viscosity and softening point tests, it
was found that the penetration value of bituminous binders
decreased with the use of activated carbon in bitumen modifica-
tion, while the softening point and viscosity values increased. This
showed that using the activated carbon in bitumen modification
increased the stiffness of the binders.
From the DSR test results, it was found that the bitumen bin-
ders’ resistance against the rutting was increased with the use of
activated carbon. BBR test results showed that although the stiff-
ness rose as the additive content increased and all the modified
binders were found to have the same low temperature perfor-
mance level as the neat binder.
Marshall stability and flow test results showed that using the
activated carbon in bitumen modification increased the stability
values but decreased the flow values. The best Marshall stability
results were obtained from the HMAs with 15% activated carbon
modified bitumen and the lowest stability results were obtained
from the mixes with the neat binder. The use of activated carbon
in bitumen modification increased the Marshall quotient values.
Tensile strength values increased continuously with the use of
activated carbon in bitumen modification before conditioning.
After conditioning, tensile strengths of the modified mixes
decreased. Tensile strength ratio values indicated that using the
activated carbon in bitumen modification decreased the HMAs’
resistance to the moisture induced damage.
Using activated carbon in bitumen modification significantly
increased the indirect tensile stiffness modulus and fatigue lifes
6000
5000
Flow number
4000
3000
2000
1000
10 15
of HMAs. The mixture with 10% activated carbon modified bitumen
had the highest resistance to fatigue crack progression, while the
mix with the neat binder had the lowest. Cyclic creep test results
were compatible with DSR and MQ values and it was determined
that HMA’s resistance against the permanent deformation signifi-
cantly increased with the use of activated carbon in bitumen
modification.
When all the test results were evaluated, the use of activated
carbon obtained from vinasse and marc in bitumen modification
increased the bitumen stiffness and high temperature performance
of bituminous binders. Furthermore, Marshall stability, stiffness,
resistance to fatigue cracks, and permanent deformation formation
of the mixes were positively affected from the activated carbon
usage. Activated carbon addition to bitumen adversely affected
only the resistance to moisture-induced damage. In order to elim-
inate this disadvantage, it was thought that using the activated car-
bon in bitumen modification together with materials which
increase the resistance against moisture-induced damage of HMAs
(e.g. hydrated lime) may be beneficial. Furthermore, determination
of the storage stability of modified binders and the evaluation of
the low temperature performance of the mixtures will be benefi-
cial for the use of activated carbon as an additive in HMAs.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This study was carried out within the scope of Fırat University
Scientific Research Projects program (FUBAP) Research Project
MF.18.61. We gratefully acknowledge the financial support pro-
vided by FUBAP.
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