applied

sciences
Article
The Effect of Addition of Antioxidant
1,2-dihydro-2,2,4-trimethyl-quinoline on
Characteristics of Crepe Rubber Modified Asphalt in
Short Term Aging and Long Term Aging Conditions
Bahruddin Ibrahim 1, * , Arya Wiranata 1 and Alfian Malik 2
1 Chemical Engineering Department, Engineering Faculty, University of Riau, Pekanbaru 28923, Indonesia;
arya.wiranata7066@grad.unri.ac.id
2 Civil Engineering Department, Engineering Faculty, University of Riau, Pekanbaru 28923, Indonesia;
ALFmalik@gmail.com
* Correspondence: bahruddin@lecturer.unri.ac.id




Received: 16 September 2020; Accepted: 13 October 2020; Published: 16 October 2020


Abstract: The use of natural rubber to resist bitumen is usually prone to degradation and aging.
One method to overcome this problem is the addition of antioxidants. This study aims to determine the
effect of the addition of antioxidants 1,2-dihydro-2,2,4-trimethyl-quinoline (TMQ) on natural rubber
modified asphalt crepe rubber and its performance in short-term and long-term aging conditions.
The modified rubber asphalt mixture’s manufacture begins by melting the crepe rubber at 200 ◦ C
before being mixed in asphalt at 165 ◦ C. Addition of antioxidant TMQ during the stirring process
of the mixture of asphalt and melted rubber. The crepe rubber content was 8, 10, and 12% w/w,
while the TMQ content was 1, 2, and 3% w/w of the total sample weight. The modified asphalt
samples’ characterization included penetration, softening point, weight loss after a rolling thin film
oven test (RTFOT), penetration after RTFOT, and Marshall test. Review of the performance of asphalt
under short-term aging conditions using a dynamic shear rheometer (DSR). Evaluation of asphalt
performance under long-term aging conditions using Fourier-transform infrared spectroscopy (FTIR).
The results showed that the fact that the best-modified asphalt product was the addition of 10%
crepe rubber and 2% TMQ. The best-modified asphalt characteristics have penetration 68.70 dmm,
softening point 55.45 ◦ C, weight loss only 0.0579%, penetration after RTFOT 59.60, Marshall stability
1403.96 kg with optimum asphalt content of 5.50%, and rutting factor (G*/Sinδ) 6.91 kPa and 16.1 kPa
before and after RTFOT. Overall, the modified crepe rubber asphalt can improve the performance of
the asphalt in terms of durability. Simultaneously, the antioxidant TMQ works very well in increasing
the resistance of bitumen to aging in the conditions of short-term aging and long-term aging.

Keywords: asphalt rubber; crepe rubber; Marshall stability; rolling thin film oven test;
1,2-dihydro-2,2,4-trimethyl-quinoline

1. Introduction
The uncontrolled growth of land transportation in many developing countries causes many
problems, such as traffic jams due to bad roads to accommodate the number of vehicles. One of the
developing countries with a high level of congestion is Indonesia. Traffic congestion with a long tempo
puts a significant burden on road construction and damages the pavement structure of asphalt roads.
Other factors that support the damage to asphalt roads are premature aging caused by standing water,
humidity, heat, UV, oxidation, and low asphalt quality [1,2]. This results in higher road maintenance
costs. The solution to reducing the high maintenance costs of paved roads is to review road construction

Appl. Sci. 2020, 10, 7236; doi:10.3390/app10207236 www.mdpi.com/journal/applsci

Appl. Sci. 2020, 10, 7236 2 of 23

and improve asphalt quality through a modification process. The use of natural rubber modified
asphalt can produce more resistant to high traffic loads and prevent the asphalt from aging prematurely.
Asphalt modification by adding additives is a common practice to improve the quality of the
asphalt binder. The additive criteria for asphalt mixtures must produce stability and high softening
points, increase flexibility, increase durability, increase the bonding power of asphalt to aggregates,
and prevent the asphalt’s premature aging. Indonesia has many options for additives mixed in asphalt,
such as plastic waste, styrofoam waste, used tire waste, natural rubber, etc. Natural rubber is the most
potential material as an additive to the asphalt mixture from the many available additives. The natural
rubber has advantages in lower rubber asphalt production costs, very large quantities of available and
better quality than crumb rubber from used tires. It does not cause emissions after being used as an
asphalt additive.
The natural rubber used can be latex, solid rubber, or engineering rubber. The development of
natural rubber in other sectors is a must, such as an additive for asphalt modification. The development
of natural rubber as an additive to modified asphalt must be carried out immediately, especially for
several natural rubber producing countries that have experienced a decline in natural rubber prices.
The growing use of natural rubber for modified asphalt is a solution to the decline in natural rubber
prices in recent years.
Several studies have conducted using crumb rubber (CR) from used tires as an additive to asphalt
mixtures. They use CR from desulphurization, and non-desulphurization used tires with a size of
40 mesh as a mixture on 90 dmm penetration asphalt. CR is mixed as much as 20% at a mixing
temperature of 180–190 ◦ C with a stirring time of 1 h. The test results showed that the addition of
CR without desulphurization increased viscosity and storage stability compared to desulphurization.
However, the use of CR desulphurization provides several disadvantages, including higher density
and high mixing temperature, poor storage stability, and requires large amounts of bitumen for field
applications [3].
The addition of 20% w/w Crumb rubber (CR) from used tire rubber with desulphurization treatment
and a 40 mesh size positively impacts modified asphalt’s rheological properties. The desulphurization
process makes CR dissolve more easily in asphalt compared to mixing CR directly into the asphalt.
However, CR directly has a higher softening point than asphalt with a desulphurization CR mixture.
The addition of CR by desulphurization treatment showed lower viscosity and better storage stability
when compared to adding CR directly in asphalt. Asphalt, with the addition of CR desulphurization,
requires a higher production temperature, which is the main drawback of this process [4].
The use of 4% w/w styrene butadiene styrene (SBS) and 20% w/w CR from used tires with a size of
40 mesh and 80–10 mesh has a positive effect on modified asphalt rheology. The addition of CR results
in better resistance to permanent deformation, rutting resistance, anti-fatigue, crack resistance, moisture
susceptibility, and better storage stability than modified bitumen with SBS. However, CR mixing
requires a high temperature and stirring speed compared to asphalt mixtures with SBS [5]. CR with a
size of 30 mesh produces modified asphalt that is more stable. CR and asphalt were mixed at 170 ◦ C
with a stirring time of 1 h. The test results show that the addition of CR with a size of 30 mesh has
better performance at low to moderate temperatures but less good on storage stability [6].
Apart from CR from used tires as an asphalt additive, natural rubber (NR) is another alternative
additive for asphalt modification. The rubber used can be latex, cup lump (CL), technical rubber (such
as crumb rubber), or used rubber from used tires. The use of latex with a dry rubber content >60%
recommendation for asphalt modification additives. This latex can reduce the sensitivity of bitumen
to temperature, increase resistance during use, and even distribute rubber in the mixture. Still, this
process requires a large amount of latex and a long pre-treatment [7]. CL’s addition increased the
asphalt’s softening point but significantly decreased its penetration and ductility [8]. Use of block
skim rubber (BSR) and crumb rubber standard Indonesian rubber (SIR 20), cemented in open mills.
This mastication treatment can reduce the Mooney viscosity, speed up mixing time, and increase the
Appl. Sci. 2020, 10, 7236 3 of 23

asphalt’s softening point [9]. The use of activated rubber from used tires as an asphalt additive also
increased asphalt softening points [10].
The polymer as an asphalt additive has several disadvantages, including degradation, oxidation,
and susceptibility to free radicals in rubber, which accelerate asphalt aging. Many studies with various
other additives have reported minimizing the aging of rubber modified asphalt [2]. The addition
of 4–6% w/w nano-silica and 4% w/w diatomite gives an effect as an oxidation inhibitor. It protects
the bitumen from oxygen, but the increased cohesion after adding nano-silica and diatomite makes
the asphalt susceptible to rutting and fatigue [11]. The use of 1–2% w/w Irganox 1010 and Dilauryl
Thiodipropionate (DLTP) tends to make the asphalt binder soft so that the asphalt sensitivity to low
temperatures decreases, and the asphalt is prone to rutting [12]. Many additives have been used and
studied to inhibit the oxidation of polymer asphalt mixtures. Still, the addition of other additives has
an impact on reducing the mechanical performance of polymer bitumen.
The use of solid rubber, such as crumb rubber, will take a very long time in the mixing process,
so a depolymerization process by chewing is required [9]. Mastication is the process of changing the
physical properties of rubber from elastic to plastic. During mastication, the finished polymer chain
breaking is due to shear forces by the rolling mill. This process results in a decrease in the molecular
weight and viscosity of the rubber. The most efficient mastication process is carried out at temperatures
below 60–70 ◦ C and above 120–130 ◦ C [13]. The mastication process can take place faster by adding a
plasticizer as a rubber softener. Asphalt is used as a plasticizer to save rubber asphalt production costs.
Compounds derived from hydrocarbon oil are very suitable for use as plasticizers for natural rubber
types. Asphalt is a hydrocarbon oil compound, so it is ideal for plasticizers for natural rubber [14].
Based on these studies, there are several conclusions that the modification of asphalt using various
types of natural rubber has a positive effect on improving the quality of asphalt. But the use of natural
rubber is also susceptible to degradation, oxidation, and the formation of free radicals, which accelerate
the premature aging of the asphalt. Based on this study, this study aims to make asphalt with high
durability, resistance to low or moderate temperatures, resistance to rutting, and to prevent premature
aging of asphalt. This study used solid natural rubber crepe rubber with the addition of antioxidants
1,2-dihydro-2,2,4-trimethyl-quinoline (TMQ). This research will study the effect of adding crepe rubber
and antioxidant TMQ on modified asphalt characteristics.

2. Material and Method

2.1. Material
This study uses the main ingredient, namely, Asphalt Penetration Grade (Pen Grade) 60/70, with
the specifications according to Table 1, PT’s production. Pertamina (Persero). The additive used for this
study uses natural rubber, which is processed by itself from the raw ingredients of cup lump to crepe
rubber. The cup lump used came from rubber plantations in Kampar Regency, Riau Province, and other
additives used were Antioxidant TMQ. Aggregates used in this study use processed aggregates from
PT. Virajaya Riau Putra, Riau Province. The aggregate specifications used can be seen in Table 2.

Table 1. Specifications for asphalt penetration grade (pen grade) 60/70.

Parameter Test Standard Result

Penetration at 25 ◦ C (dmm) ASTM D5 70.2
Softening point (◦ C) ASTM D36 48
Weight loss by Thin Film Oven Test (TFOT) (%) ASTM D6 0.365
Penetration after Thin Film Oven Test (TFOT) (dmm) ASTM D5 64.7
Ductility (cm) ASTM D113 110
Marshall stability (kg) ASTM D6927 1179.25
Appl. Sci. 2020, 10, 7236 4 of 23

Table 2. Aggregate composition of Marshall stability testing.

Aggregate Composition (%)

Coarse aggregate 15
Medium aggregate 30
Fine aggregate 53
Filler cement 2

2.2. Method
A. Preparation of Crepe Rubber

The first is to wash the cup lump in running water to remove the dirt that sticks to the cup’s lump
surface. Cup lump milled using a creeper machine to reduce the moisture content of the cup lump.
During the grinding process, the cup lump is flowed with water to remove dirt that did not come off
during the first washing process. After the cup lump is sheet-shaped, the cup lump sheet is cut into
pieces and washed again to remove dirt inside the rubber. Clean cup lumps are placed in the open roll
mill machine in cold operating conditions to form crepe rubber sheets. The crepe rubber sheet is dried
in an open space without being exposed to sunlight for 7–14 days for the drying process to obtain dry
rubber content (DRC) > 95%.

B. Making Modified Asphalt Samples

Modified asphalt samples begin with weighing the asphalt, crepe rubber, and TMQ antioxidants
with the ratio, as shown in Table 3. First, cut a sheet of crepe rubber with a size of 1 cm × 1 cm.
Next, melt the crepe rubber pieces at 200 ◦ C and add asphalt with a 1:1 ratio to speed up the melting
process. Asphalt and crepe rubber dissolved were mixed by melting method at 165 ◦ C with stirring at
300 rpm for 30 min. The asphalt sample was then rested before being tested for the modified asphalt
characterization and the sample code shown in Table 3.

Table 3. Modified asphalt sample ratio.

Content (%)
Sample Asphalt
Asphalt Crepe Rubber TMQ
Pen Grade 60/70 100 0 0
A1 91 8 1
A2 90 8 2
A3 89 8 3
B1 89 10 1
B2 88 10 2
B3 87 10 3
C1 87 12 1
C2 86 12 2
C3 85 12 3

C. Aging Method

The asphalt aging process takes a very long time. Simulation is a solution to speed up the
aging process of asphalt to get actual results. Simulations to obtain short-term aging data used
the heating treatment on asphalt using the rolling thin film oven test (RTFOT) with ASTM D2872.
Meanwhile, long-term aging is simulated by heating the modified asphalt sample after RTFOT utilizing
an oven. The oven is set at 85 ◦ C with a heating time of eight days [15].
Appl. Sci. 2020, 10, 7236 5 of 23

2.3. Characterization of Modified Asphalt Samples

The characterization of asphalt-rubber mixture samples included penetration testing (ASTM
D5), softening point (ASTM D36), weight loss (ASTM D6/D6M), penetration after TFOT (ASTM D5),
and Marshall stability (ASTM D6927). Marshall stability testing uses the aggregate composition
shown in Table 2 with the optimum bitumen content, as seen in Table 4. The modified asphalt
characterization test results are shown in Table 4 and the Marshall stability test shown in Table 5.
Furthermore, the dynamic shear rheometer (DSR) test describes asphalt’s viscoelastic behavior after
short-term aging using RTFOT. Evaluation of modified asphalt performance after the addition of crepe
rubber and TMQ carried out DSR testing for asphalt samples of pen grade 60/70, asphalt with optimum
crepe rubber without TMQ, and asphalt with the addition of crepe rubber and TMQ at optimum
conditions. DSR testing is carried out on these samples before and after RTFOT (short term oven aging).
The Fourier-transform infrared spectroscopy (FTIR) test was carried out to determine modified asphalt
performance after long-term aging.
Appl. Sci. 2020, 10, 7236 6 of 23

Table 4. Test results of modified asphalt characteristics.

Decreased
Optimum Asphalt Weight of Loss by Penetration after
Sample Penetration (dmm) Softening Point (◦ C) Penetration after
(%) RTFOT (%) RTOFT (dmm)
TFOT (%)
Pen grade 60/70 6.00 70.20 48.00 0.365 64.70 7.83
A1 5.45 61.30 58.70 0.066 50.80 17.13
A2 5.45 63.10 57.15 0.096 53.50 15.21
A3 5.45 71.60 52.65 0.096 56.40 21.23
B1 5.50 64.70 55.80 0.063 45.90 29.06
B2 5.50 68.70 55.45 0.059 59.60 13.25
B3 5.50 74.40 53.65 0.063 53.00 28.76
C1 5.35 66.20 55.80 0.125 54.20 18.13
C2 5.35 69.70 55.60 0.065 62.50 10.33
C3 5.35 78.30 47.65 0.125 57.60 26.43
Appl. Sci. 2020, 10, x FOR PEER REVIEW 7 of 23

Appl. Sci. 2020, 10, 7236 7 of 23

Table 5. Characterization of Marshall stability.

Optimum Table 5. Characterization of Marshall stability.

Marshall VFA VIM VMA Flow MQ
Sample Asphalt
Optimum Stability
Marshall (%) (%) (%) (mm)
Flow (kg/mm)
MQ
Sample (%)
Asphalt VFA (%) VIM (%) VMA (%)
Stability (mm) (kg/mm)
A1 (%)
5.45 1336.24 68.737 4.706 15.082 3.370 396.510
A2
A1 5.45
5.45 1426.53
1336.24 67.928
68.737 5.374
4.706 16.555
15.082 3.710
3.370 384.509
396.510
A2
A3 5.45
5.45 1426.53
1363.33 67.928
68.739 5.374
4.973 16.555
15.903 3.710
3.900 384.509
349.572
A3
B1 5.45
5.50 1363.33
1354.30 68.739
77.686 4.973
3.366 15.903
15.082 3.900
3.880 349.572
349.046
B1 5.50 1354.30 77.686 3.366 15.082 3.880 349.046
B2
B2
5.50
5.50
1403.96
1403.96
75.907
75.907
3.071
3.071
15.340
15.340
3.370
3.370
416.605
416.605
B3
B3 5.50
5.50 1101.50
1101.50 77.172
77.172 3.470
3.470 15.194
15.194 3.820
3.820 288.351
288.351
C1
C1 5.35
5.35 1074.41
1074.41 70.106
70.106 4.369
4.369 14.654
14.654 3.630
3.630 295.981
295.981
C2
C2 5.35
5.35 1254.98
1254.98 72.055
72.055 4.078
4.078 14.522
14.522 3.990
3.990 314.531
314.531
C3
C3 5.35
5.35 1110.53
1110.53 70.604
70.604 4.296
4.296 14.624
14.624 4.370
4.370 254.126
254.126

3. Result and Discussion

3.1. Effects of
3.1. Effects of Crepe
Crepe Rubber
Rubber and
and TMQ
TMQ on
on Modified
Modified Asphalt
Asphalt Penetration
Penetration
Penetration
Penetration describes
describes thethe physical
physical hardness
hardness level
level of
of the
the asphalt
asphalt and
and is
is aa parameter
parameter for
for classifying
classifying
the
the quality of asphalt. Asphalt with a lower penetration value is more suitable for use in areas with
quality of asphalt. Asphalt with a lower penetration value is more suitable for use in areas with
hot climates. Asphalt with low penetration values generally has higher softening
hot climates. Asphalt with low penetration values generally has higher softening points and rutting points and rutting
resistance, thus extending
resistance, thus extending the the asphalt
asphaltlife.
life.Asphalt
Asphalttest
test results
results using
using anan automatic
automatic penetrometer
penetrometer as
as presented in Table 4. Asphalt pen grade 60/70 has an asphalt penetration
presented in Table 4. Asphalt pen grade 60/70 has an asphalt penetration value of 70.2 dmm. value of 70.2 dmm.
Modified
Modified asphalt
asphalt crepe crepe
rubber and rubber and antioxidant
antioxidant TMQ decreasedTMQ decreased and penetration
and increased increased penetration of asphalt
of asphalt compared
compared to pen grade 60/70 asphalt. Figure 1 shows that modified asphalt tends to
to pen grade 60/70 asphalt. Figure 1 shows that modified asphalt tends to increase penetration and increase penetration
and the increasing
the increasing ratioratio of crepe
of crepe rubber
rubber and and
TMQ. TMQ.
The The penetration
penetration values
values of Samples
of Samples A1, B1,
A1, A2, A2, B2,
B1, C1,
B2,
C1,
andand C2aaswhole
C2 as a whole
areare lower
lower than
than asphalt
asphalt pen
pen grade60/70,
grade 60/70,while
whilesamples
samplesA3, A3,B3,
B3,and
and C3
C3 have
have aa
higher penetration value than asphalt pen grade
higher penetration value than asphalt pen grade 60/70. 60/70.

Figure 1.
Figure 1. Penetration.
Penetration.

The lowest
lowestpenetration
penetrationvalue is in
value is sample A1 with
in sample a penetration
A1 with value of
a penetration 61.30ofdmm
value 61.30ordmm
a decrease
or a
of 12.67%offrom
decrease thefrom
12.67% 60/70
thepen grade
60/70 pen asphalt. The highest
grade asphalt. penetration
The highest is inisthe
penetration C3C3
in the sample
samplewith
witha
penetration value
a penetration of 78.30
value dmm
of 78.30 or anorincrease
dmm of 85.61%
an increase from the
of 85.61% 60/70
from thepen grade
60/70 penasphalt. In general,
grade asphalt. In
general,
the the decrease
decrease inpenetration
in asphalt asphalt penetration
is causedisby
caused by an increase
an increase in the
in the ratio ratio of
of crepe crepeinrubber
rubber in
asphalt,
Appl. Sci. 2020, 10, 7236 8 of 23

increasing the absorption capacity of the light fraction of asphalt and accelerate the distribution of
melted crepe rubber [16]. The absorption of light fractions of asphalt, such as saturate and some
aromatic compounds by crepe rubber, will physically change the crepe rubber to expand and form a
viscous gel [17].
An increase in the ratio of crepe rubber that exceeds the optimum will cause the asphalt to become
soft. The melted crepe rubber is not evenly mixed in the asphalt and accumulates on the asphalt-rubber
mixture. The accumulation of rubber changes the modified asphalt mixture’s surface to be softer
so that the penetration value increases during testing. An increase in the ratio of crepe rubber that
exceeds the optimum will cause the asphalt to become soft. The melted crepe rubber is not evenly
mixed in the asphalt and accumulates on the asphalt—rubber mixture. The accumulation of rubber
changes the modified asphalt mixture’s surface to be softer so that the penetration value increases
during testing [8].
Several factors cause the accumulation of melted crepe rubber on the asphalt surface, including the
slow stirring speed during the mixing process, which is the main cause of the accumulation of melted
crepe rubber on the surface asphalt mixture-crepe rubber. During the mixing process of asphalt with
crepe rubber, the stirring speed plays an important role in the distribution speed of melted crepe
rubber in the asphalt [8,9]. The direct use of crepe rubber takes a very long time to melt. The solution
to speed up crepe rubber’s melting process is to use high temperatures, but this has drawbacks.
The melting process of crepe rubber at 200 ◦ C for a long time can cause degradation and damage the
polymer structure of crepe rubber or asphalt. Degradation of structural damage to the crepe rubber is
undesirable because it will affect the asphalt sample’s physical properties to become softer [18].
Samples A1, A2, A3 has the same ratio but have a penetration value that increases with increasing
levels of TMQ in the mixture. The mixing temperature in the range of 165 ◦ C causes TMQ to melt and
dissolve in asphalt because the melting point of TMQ is the only 72–94 ◦ C. The physical properties of
TMQ melt are different from that of crepe rubber melt. TMQ melt has a more fluid nature, which affects
the modified asphalt mixture’s consistency to become soft. TMQ has aromatic and aliphatic molecular
structures so that TMQ melts have properties similar to maltene compounds in asphalt, which are
mostly composed of aromatic and alpha molecular structures [19]. Overall, the increase in TMQ will
increase the maltene component in the asphalt, which affects the asphalt’s physical properties to soften.
Increasing the TMQ ratio will limit the interaction of rubber in the asphalt so that the modified asphalt
becomes softer [20].

3.2. Effects of Crepe Rubber and TMQ on Modified Asphalt Softening Points
Asphalt modification with crepe rubber was declared successful if the softening point value of
modified asphalt was higher than the asphalt pen grade 60/70 soft point value [21]. The softening
point increase occurred in almost all samples except C3. Samples A1 and A2 had the highest softening
points with 58.70 ◦ C and 57.15 ◦ C, or an increase of 19–22% of asphalt pen grade 60/70. The lowest
softening point in sample C3 with a softening point value of 47.65 ◦ C is shown in Figure 2 and Table 4.
The increase in softening point is proportional to the increase in asphaltene and semi-solid (resin) levels
accompanied by a linear decrease in maltene content and decreased asphalt penetration value [22].
Asphaltene increases with increasing levels of crepe rubber in asphalt until it reaches its optimum level.
Crepe rubber in asphalt will absorb maltene to form a viscous gel, strengthening the interaction of
asphaltenes and resin.
Appl. Sci. 2020, 10, 7236 9 of 23
Appl. Sci. 2020, 10, x FOR PEER REVIEW 9 of 23

Figure
Figure 2.
2. Softening
Softening point.
point.

Asphalt’s
Asphalt’s softening
softeningpoint pointdecreases
decreaseswith withincreasing
increasingcrepecrepe rubber
rubber levels
levelsin in
modified
modifiedasphalt, as
asphalt,
shown in samples A1. B1. C1 with the same TMQ levels. The same is
as shown in samples A1. B1. C1 with the same TMQ levels. The same is seen in samples A2, B2, seen in samples A2, B2, C2, and
A3, B3, C3.
C2, and A3,The softening
B3, C3. point decreases
The softening inverselyinversely
point decreases with thewithincrease in asphalt
the increase in penetration, caused
asphalt penetration,
by accumulated
caused melt formation
by accumulated in the modified
melt formation asphaltasphalt
in the modified sample. In general.
sample. TMQ does
In general. TMQnot doesaffect
not
softening pointspoints
affect softening directly but does
directly but doesaffect asphalt
affect penetration.
asphalt penetration. TMQTMQ onlyonlyplays
playsa arole
rolein
in preventing
preventing
oxidization
oxidization of rubber or asphalt during its lifetime lifetime andand storage.
storage. Meanwhile,
Meanwhile, crepe crepe rubber
rubber plays a
significant role
roleininincreasing
increasingthe the softening
softening point
point andand rutting
rutting resistance
resistance at lowat temperatures
low temperatureswhen when
crepe
crepe
rubberrubber stabilizes
stabilizes in the in the swelling
swelling processprocess [23]. 4Table
[23]. Table shows 4 shows
the softthe soft of
points points of all samples.
all samples. B2, B3, B2,
C1,
B3,
and C1, and almost
C2 have C2 have thealmost the points
same soft same in soft 55 ◦ C in
thepoints the 55 °Crange
temperature temperature rangepenetrations
and adjacent and adjacent in
penetrations in
the 64–70 dmm range. the 64–70 dmm range.
Crepe rubber added added to the asphalt
asphalt can can increase
increase the the asphalt’s
asphalt’s weight
weight and and molecular
molecular density,
density,
affecting the test ball’s friction resistance to be more more significant
significant [24].
[24]. TheThe increase in weight and
molecular density
densityofofasphalt,
asphalt,thethe amount
amount of resin
of resin thatthat increases
increases alongalong
with with the increase
the increase inrubber
in crepe crepe
rubber
content,content,
causes an causes an increase
increase in the cohesion
in the cohesion of the asphalt,
of the asphalt, which iswhich is characterized
characterized by the
by the physical
physical
propertiesproperties of the
of the asphalt, asphalt,
namely thenamely the more
more sticky [25]. Asticky [25]. A
significant significant
decrease decrease
in softening in softening
point occurred
point
in the occurred
sample with in thethesample
additionwithof the
3% addition
TMQ (samplesof 3% TMQ A3, B3,(samples
C3). The A3, B3, C3). point
softening The softening
reductionpoint
was
reduction
due to the washigher due to the higher
penetration penetration
of asphalt of asphalt
than asphalt pen than
gradeasphalt
60/70 and penother
grade 60/70 and
samples. Tooother
high
samples.
penetration Tooindicates
high penetration indicatescohesion
that the asphalt’s that theproperties
asphalt’s cohesion properties
will decrease, and itwill decrease,
cannot hold theand it
ball
cannot hold the
when testing theball
softwhen
point.testing the soft
Increasing the point. Increasing
asphalt’s softening the asphalt’s
point softening
can increase thepoint canresistance
asphalt increase
the asphaltincrease
to rutting, resistance to rutting,
ductility, increase
thermal ductility,
stability, thermal the
and increase stability,
aging andtime.increase the aging time.

3.3. Effects
Effects of Crepe Rubber and TMQ on Short Term Aging
Aging of
of Modified
Modified Asphalt
Asphalt
The damage to the asphalt pavement during during its service
service life is mostly due to the aging asphalt
binder. Asphalt
Asphalt aging
aging contributes
contributes toto decreased
decreased durability
durability and
and service
service life
life of
of asphalt
asphalt pavements.
pavements.
Therefore, weweneed
needa atesting
testing method
method using
using thethe rolling
rolling thinthin
film film
ovenoven test (RTFOT)
test (RTFOT) to simulate
to simulate short-
term aging on asphalt. The parameters for testing short term aging in this study used an approach an
short-term aging on asphalt. The parameters for testing short term aging in this study used to
approachthe
measure to measure
weight losstheof
weight loss
asphalt of asphalt
during RTFOT during RTFOT
testing. Loss testing.
of weight Loss of weight
in asphalt caninoccur
asphalt
duecan
to
occur due
volatile to volatile compounds
compounds such as
such as aromatic aromatic components
components in asphalt in asphalt
[17]. [17].using
Testing Testing usingaims
RTFOT RTFOTto
aims to determine volatile compounds’ effect on short-term asphalt aging and asphalt’s
determine volatile compounds’ effect on short-term asphalt aging and asphalt’s sensitivity to high sensitivity
to high temperatures.
temperatures. Meanwhile,
Meanwhile, long-term
long-term aging aging is caused
is caused by by traffic
traffic loads,temperature,
loads, temperature, sunlight,
sunlight,
oxidation, and
and others
others[26].
[26]. Loss
Lossofofweight
weightofofasphalt
asphaltallowed
allowed is is
a maximum
a maximum of of
1%1% of asphalt weight
of asphalt [8].
weight
[8].
Sample B2 in Figure 3 experienced a weight loss of 0.059% during RTFOT testing or decreased
by 83.84% compared to asphalt pen grade 60/70. Overall, sample B experienced constant weight loss
Appl. Sci. 2020, 10, 7236 10 of 23

Sample B2 in Figure 3 experienced a weight loss of 0.059% during RTFOT testing or decreased
by 83.84% compared to asphalt pen grade 60/70. Overall, sample B experienced constant weight loss
compared to samples A and C. The addition of 10% crepe rubber in asphalt has the optimum condition
Appl. Sci. 2020, 10, x FOR PEER REVIEW 10 of 23
in preventing the evaporation of volatile compounds or the crepe rubber part from evaporating.
The average weighttoloss
compared of asphalt
samples A and inC. sample B is of
The addition only
10%0.061%, whileinsample
crepe rubber asphalt A hashas
the an average weight
optimum
loss of 0.086% and 0.105% for sample C. as seen in Table 4. Logically the higher thefrom
condition in preventing the evaporation of volatile compounds or the crepe rubber part rubber ratio,
evaporating. The average weight loss of asphalt in sample B is only 0.061%, while sample A has an
the smaller the weight loss that occurs after RTFOT is due to the function of crepe rubber in asphalt as
average weight loss of 0.086% and 0.105% for sample C. as seen in Table 4. Logically the higher the
a membrane that
rubber inhibits
ratio, volatile
the smaller compounds
the weight fromafter
loss that occurs evaporating [8].
RTFOT is due However,
to the function ofthis
crepestudy
rubberconcluded
that the greater theasratio
in asphalt of crepe
a membrane thatrubber
inhibitsto asphalt,
volatile the greater
compounds the weight
from evaporating [8].loss. The this
However, weight
studyloss of the
concluded
asphalt occurs due that
to thethe greater
crepe the ratio of crepe
rubber’s rubber to asphalt,
degradation duringthe greater
the RTFOT the weight
process,loss.which
The weight
results in the
loss of the asphalt occurs due to the crepe rubber’s degradation during the RTFOT process, which
loss of some of the crepe rubber mass [2].
results in the loss of some of the crepe rubber mass [2].

Figure 3. Weight of loss by RTFOT.

Figure 3. Weight of loss by RTFOT.
The loss of light components in the asphalt can reduce the penetration value and increase the
The loss of light
softening point, components
as seen in Figure in the asphalt
4A. The can reduce
penetration of samplethe B1penetration value and
after RTFOT decreased untilincrease
it the
softening reached
point, as seen in Figure
a penetration value of 4A. The penetration
45.9 dmm. of sample
All samples experienced B1 after
a decrease RTFOT decreased
in penetration between until it
10–29% from before
reached a penetration valueRTFOT.
of 45.9Thedmm.low penetration
All samples of sample B1 causes
experienced the physical
a decrease in properties
penetration of between
sample B1 after penetration to become very hard and stiff. The decrease in penetration after RTFOT
10–29% from before RTFOT. The low penetration of sample B1 causes the physical properties of sample
was due to several factors, including the asphaltene fraction, which increased along with the
B1 after penetration
evaporation of tothe
become
maltenevery hard
fraction andand
rubber stiff. The decrease
degradation, which in penetration
increased after RTFOT
in the carbonyl group. was due
to several factors,
These twoincluding
factors are the theformation
asphaltene of freefraction,
radicals by which
excess increased
heat, which is along
basedwith
on agethe evaporation
in the asphalt of the
binding and
maltene fraction network [2]. degradation, which increased in the carbonyl group. These two factors are
rubber
Concerning Figure 4A,B presents data on the percentage reduction in asphalt penetration. In
the formation of free radicals by excess heat, which is based on age in the asphalt binding network [2].
Figure 4B and Table 4, it can be seen that the addition of crepe rubber to the asphalt increases the
Concerning
percentageFigure
reduction 4A,B presents
in asphalt data onA the
penetration. percentage
significant decreasereduction in asphaltafter
in asphalt penetration penetration.
In Figure 4B andwill
RTFOT Table 4, it the
increase canasphalt
be seen thatand
strength themake
addition of crepe
the asphalt rubber
susceptible to the asphalt
to premature increases the
aging [27].
percentageThe increase in
reduction inthe percentage
asphalt decrease in A
penetration. penetration
significant of modified
decrease asphalt after RTFOT
in asphalt was caused
penetration after RTFOT
by the effect of degradation of crepe rubber compared to the loss of light fraction in the asphalt.
will increase the asphalt strength and make the asphalt susceptible to premature aging [27]. The increase
Degradation of crepe rubber plays a significant role in oxidation and increases in carbonyl groups,
in the percentage
causing andecrease
increase inin thepenetration
proportion of of modified
asphaltene andasphalt
a decrease after RTFOT
in maltene [2]. was
In thiscaused by the effect
case, crepe
of degradation
rubber of crepe rubber
accelerates compared
the asphalt aging after toRTFOT
the loss of light
because crepefraction
rubber isin thesusceptible
very asphalt. toDegradation
heat, of
oxidation,
crepe rubber plays and UV. Antioxidants
a significant role inare necessaryand
oxidation to prevent crepeinrubber
increases carbonyloxidation,
groups,which increases
causing an increase
the risk of premature aging of the asphalt. This study uses TMQ as an antioxidant. The TMQ ratio’s
in the proportion of asphaltene and a decrease in maltene [2]. In this case, crepe rubber accelerates
effect on the percentage reduction in asphalt penetration after RTFOT can be seen in Figure 4B. This
the asphalt aging
study’s afterTMQ
optimal RTFOT level because
was 2%, with crepe rubber
a decrease is very susceptible
in penetration after RTFOT of toonly
heat, oxidation,
10–15%. TMQ and UV.
Antioxidants are necessary
can prevent to prevent
rubber oxidation crepestabilizing
in 2 ways: rubber free oxidation,
radicals orwhich increases
scavenging the risk
free radicals andofthepremature
second by inhibiting peroxide formation [2].
aging of the asphalt. This study uses TMQ as an antioxidant. The TMQ ratio’s effect on the percentage
reduction in asphalt penetration after RTFOT can be seen in Figure 4B. This study’s optimal TMQ
level was 2%, with a decrease in penetration after RTFOT of only 10–15%. TMQ can prevent rubber
oxidation in 2 ways: stabilizing free radicals or scavenging free radicals and the second by inhibiting
peroxide formation [2].
Appl. Sci. 2020, 10, 7236 11 of 23
Appl. Sci. 2020, 10, x FOR PEER REVIEW 11 of 23

Figure 4. (A) Penetration after RTFOT. (B) Percentage of decreased penetration after RTFOT.
Figure 4. (A) Penetration after RTFOT. (B) Percentage of decreased penetration after RTFOT.
3.4. Effects of Crepe Rubber and TMQ on Characteristics of Modified Marshall Asphalt
3.4. Effects of Crepe Rubber and TMQ on Characteristics of Modified Marshall Asphalt
Modified crepe rubber asphalt in its application for road pavement must have the ability to
withstand
Modifiedtraffic loads
crepe betterasphalt
rubber than asphalt pen grade for
in its application 60/70
road[28]. Measuring
pavement mustmodified
have theasphalt
ability to
withstand roadtraffictraffic
loadsloads
better can be done
than by laboratory-scale
asphalt pen grade 60/70 testing with Marshall
[28]. Measuring stability
modified testing.
asphalt to
The Marshall
withstand roadstability value can
traffic loads provides
be done an by
overview of the asphalt’s
laboratory-scale ability
testing with to bind stability
Marshall aggregates and
testing.
prevent deformation.
The Marshall stabilityThe
valuemodified
provides asphalt criteria can
an overview be successful
of the if the Marshall
asphalt’s ability stability value
to bind aggregates and
of asphalt
prevent with crepe rubber
deformation. is higher
The modified than asphalt
asphalt penbe
criteria can grade 60/70. if
successful The
theaddition
Marshallofstability
crepe rubber
value to
of
asphalt in its application
with crepe rubber forisroad pavement
higher has advantages
than asphalt pen gradesuch as better
60/70. riding quality,
The addition of creperesistance
rubber to
moisture,
asphalt inhigher durability,
its application forand
roadrutting due tohas
pavement reduced temperature
advantages such assensitivity
better ridingand quality,
lower noise levels.
resistance
Figure 5higher
to moisture, showsdurability,
the increase andin rutting
the Marshall
due tostability
reducedvalue in samples
temperature A1, A2,and
sensitivity A3,lower
B1, and B2
noise
compared
levels. to pen grade 60/70 asphalt. The highest Marshall stability in samples A2 and B2 with a
valueFigure
of 1426.53 kg and
5 shows the1403.96
increase kginor the
20–21% of thestability
Marshall 60/70 pen grade
value in asphalt.
samplesInA1, thisA2,
study,
A3, the
B1, optimal
and B2
asphalt
compared content
to pen(KAO)
gradewas 5.45%
60/70 for sample
asphalt. A and 5.50%
The highest for sample
Marshall B with
stability an aggregate
in samples A2 and composition,
B2 with a
as shown
value in Table
of 1426.53 kg2.and
Samples
1403.96 B3,kgC1,
or C2, and C3
20–21% experienced
of the 60/70 penagrade
decrease in theInMarshall
asphalt. stability
this study, value
the optimal
asphalt content (KAO) was 5.45% for sample A and 5.50% for sample B with an aggregate
composition, as shown in Table 2. Samples B3, C1, C2, and C3 experienced a decrease in the Marshall
Appl. Sci. 2020, 10, 7236 12 of 23

Appl. Sci. 2020, 10, x FOR PEER REVIEW 12 of 23

of asphalt pen grade 60/70 due to the penetration of the asphalt in the sample, which approaches
stability value of asphalt pen grade 60/70 due to the penetration of the asphalt in the sample, which
and exceeds the asphalt
approaches pen grade
and exceeds 60/70.
the asphalt pen The
gradeshift
60/70.in the
The penetration
shift value
in the penetration willwill
value cause
cause aachange in
Appl. Sci. 2020, 10, x FOR PEER REVIEW 12 of 23
the optimum
changeasphalt content asphalt
in the optimum for mixing.
contentThe suboptimal
for mixing. bitumen
The suboptimal content
bitumen in the
content mixture
in the mixtureaffects the
affects
cohesion and
stability the
adhesion cohesion
value and adhesion
ofproperties
asphalt properties
of the
pen grade dueoftothe
asphalt.
60/70 theasphalt.
InappropriateInappropriate
penetration ofbitumen bitumen
the asphaltoptimumoptimum
in the content
content
sample, which will cause
will cause the asphalt to be unable to bind the aggregate and easily deform or rutting permanently
the asphaltapproaches
to be unable and exceeds
to bind thethe
asphalt pen grade
aggregate and 60/70. The deform
easily shift in theorpenetration value will cause[29,30].
rutting permanently a
[29,30]. in the optimum asphalt content for mixing. The suboptimal bitumen content in the mixture
change
affects the cohesion and adhesion properties of the asphalt. Inappropriate bitumen optimum content
will cause the asphalt to be unable to bind the aggregate and easily deform or rutting permanently
[29,30].

Figure5.5.Marshall
Figure Marshall stability.
stability.
In general, crepe rubber’s addition to the modified asphalt mixture can harden the asphalt
In general, crepe rubber’s addition toMarshall
binding with aggregate and increase Figure
the modified
stability.
asphalt mixture can harden the asphalt binding
However, the addition of crepe rubber that
5. Marshall stability.
with aggregate
exceedsand increasewill
the optimum Marshall
cause thestability.
asphalt to However,
be more flexibletheand
addition of crepewhen
create instability rubber that
given a exceeds
the optimum will
load In
[31]. cause
The
general, the asphalt
addition
crepe to bestrengthen
of TMQ helps
rubber’s addition more flexible
to the the and
binding
modified ofcreate
asphalt
asphalt instability
with can
mixture aggregatewhen
harden thegiven
because TMQa load [31].
asphalt
The additiononlyofacts
binding TMQto prevent
with helpsmodified
aggregate asphalt
and increase
strengthen oxidation.
theMarshall
binding The ability
stability. ofwith
However,
of asphalt modified
the asphaltof
addition
aggregate to fill therubber
crepe
because aggregate
TMQ thatonly acts to
cavity (VFA)
exceeds affects will
the optimum the value of Marshall
cause the asphalt tostability.
be more The compacted
flexible and createasphalt mixture’s
instability cavities
when given a
prevent modified asphalt
significantly
oxidation. The ability of modified asphalt to fill the aggregate cavity (VFA)
load [31]. Theaffect the asphalt’s
addition stability,
of TMQ helps as shown
strengthen theinbinding
Figure 6.of The large
asphalt cavities
with allow because
aggregate cracks, which
TMQ
affects theonly
value
lead to of Marshall
a decrease
acts to prevent stability.
in modified
the stability The compacted
of theoxidation.
asphalt asphalt mixture’s cavities significantly
asphalt. The ability of modified asphalt to fill the aggregate affect the
asphalt’s stability,
cavity (VFA)as shown
affects in
theFigure
value of6. Marshall
The large cavities
stability. Theallow cracks,asphalt
compacted whichmixture’s
lead to acavities
decrease in the
stability ofsignificantly
the asphalt. affect the asphalt’s stability, as shown in Figure 6. The large cavities allow cracks, which
lead to a decrease in the stability of the asphalt.

Figure 6. Cavities between aggregates in Marshall specimens.

In general, cavities that are too large after compaction will cause cracks during Marshall testing.
Figure 6 is a piece of Figure
the Marshall sample
6. Cavities betweenB2aggregates
specimen.in The red box
Marshall shows that the large cavity
specimens.
Figure 6.
between the aggregate Cavities
grains causesbetween aggregates
cracks around in Marshall
the cavity specimens.
after being loaded. Cracks that arise
causeInthe
general, cavities that are too large after compaction will cause cracks modifications.
resulting asphalt’s stability is not as high as other research asphalt The
during Marshall value
testing.
In general,
Figure 6cavities that
is a piece areMarshall
of the too large afterB2compaction
sample specimen. The will
redcause cracks
box shows thatduring
the largeMarshall
cavity testing.
Figure 6 isbetween
a piece the
of the Marshall
aggregate sample
grains B2 specimen.
causes cracks around theThe redafter
cavity boxbeing
shows that Cracks
loaded. the large
thatcavity
arise between
causegrains
the aggregate the resulting asphalt’s
causes cracksstability
around is notthe
as high as other
cavity afterresearch
beingasphalt modifications.
loaded. Cracks that The arise
value cause the

resulting asphalt’s stability is not as high as other research asphalt modifications. The value of cavities
filled with asphalt or called void filled aggregate (VFA) shows the cavity’s size in the asphalt.
VFA has a vital role in maintaining the stability of the mixture while holding loads. Table 5
and Figure 7A shows an increase in the percentage of VFA when the ratio of crepe rubber increases,
but the VFA value decreases with 12% crepe rubber. The decreased VFA percentage in sample C
 which is too small, will make the asphalt layer covering the aggregate thin and decrease the asphalt’s
adhesion properties [32]. The addition of crepe rubber and TMQ to the asphalt provides a significant
change in modified asphalt density. As shown in Figure 7D, increasing the ratio of crepe rubber and
TMQ changes the density of modified asphalt decreases, decreasing density is the cause of decreasing
VFA percentage [33]. The increase in crepe rubber and excessive TMQ also creates instability because
Appl. Sci.
the2020, 10, 7236
binding power of asphalt with aggregates is higher than that of rubber. Combining these three 13 of 23
things causes sample C to be no better than sample A in load-bearing stability. The percentage of
VFA is closely related to the percentage of Void in mixture/air void (VIM) and void mineral aggregate
with (VMA).
12% crepe rubber the
Increasing waspercentage
due to theofdecrease
VFA andin the optimum
decreasing asphalt
the VMA valuecontent,
plays a as shown
vital inthe
role in Table 4.
The decrease
asphalt mixture’s mechanical properties. In Figure 7B and Table 5, the increase in crepe rubber causes the
in the optimum asphalt content affected the aggregate filler to fill the space between
aggregates. Theinasphalt
a decrease VMA, thelevel that does
smallest VMAnot reach the
percentage in optimum can cause
sample C with a cavity,
an average as seen
of 14.6%. TheinVMA
Figure 6.
The highest
percentageVFA value
is too was
small; theobtained by experience
mixture can sample B,durability
with a 10% crepebecause
problems rubberitwith
formsan average
a thin layer VFA
on the aggregate.
of 76.922%. The average Too percentage
large a percentage
of VFA of in
VMA is alsoCnot
sample wasgood for asphalt
higher mixtures
than that because
of sample A,the
but the
stability will be very low [32].
Marshall stability sample A was higher than that of Marshall stability sample C.

Appl. Sci. 2020, 10, x FOR PEER REVIEW 14 of 23

Figure 7. Cont.
Appl. Sci.
Appl.2020, 10, 7236
Sci. 2020, 10, x FOR PEER REVIEW 14 of 23
15 of 23

Figure 7. (A)
Figure VFA.
7. (A) (B)
VFA. (B)VMA.
VMA.(C)
(C) VIM. (D)Bulk
VIM. (D) Bulkdensity
density modification
modification asphalt.
asphalt.

The decrease in Marshall

Void in mixture/Air stability
void (VIM)and the percentage
indicates the asphaltVFA of sample
tightness C was
and pore due to of
properties several factors,
asphalt.
including a smaller portion
The percentage of optimum
of VFA strongly asphalt
influences VIMcontent. The optimum
in the mixture. bitumen
The small content, which
VFA percentage valueis too
small,indicates
will makemany thevoids between
asphalt layerthe asphaltthe
covering aggregate
aggregatemixture,
thin asandshown in Figure
decrease 8A. The adhesion
the asphalt’s VIM
percentage represents the flexibility and durability of the asphalt and aggregate
properties [32]. The addition of crepe rubber and TMQ to the asphalt provides a significant change mixture. Asphalt
with a VIM
in modified valuedensity.
asphalt that is too
Aslarge
shown indicates that the
in Figure 7D,asphalt is notthe
increasing waterproof
ratio of and
crepeis susceptible
rubber andtoTMQ
oxidation and deformation when it is loaded. The VIM value that is too small also causes the mixture
changes the density of modified asphalt decreases, decreasing density is the cause of decreasing VFA
to become stiff and cracking due to the absence of cavities for the shifting aggregates. The smallest
percentage [33]. The increase in crepe rubber and excessive TMQ also creates instability because
VIM value was obtained by sample B, with an average of 3.302%, as shown in Figure 7C and Table 5.
the binding power of asphalt with aggregates is higher than that of rubber. Combining these three
The filler ratio has a significant effect on the percentage of VIM because filler has a vital role in filling
thingsthecauses sample aggregates.
voids between C to be noAdditionally,
better than sample
the filler A in load-bearing
functions to make thestability.
mixture The percentage
waterproof, as of
VFA shown
is closely related
in Figure 8B.to the percentage of Void in mixture/air void (VIM) and void mineral aggregate
(VMA). Increasing the percentage of VFA and decreasing the VMA value plays a vital role in the
asphalt mixture’s mechanical properties. In Figure 7B and Table 5, the increase in crepe rubber causes
a decrease in VMA, the smallest VMA percentage in sample C with an average of 14.6%. The VMA
percentage is too small; the mixture can experience durability problems because it forms a thin layer
on the aggregate. Too large a percentage of VMA is also not good for asphalt mixtures because the
stability will be very low [32].
Void in mixture/Air void (VIM) indicates the asphalt tightness and pore properties of asphalt.
The percentage of VFA strongly influences VIM in the mixture. The small VFA percentage value
indicates many voids between the asphalt aggregate mixture, as shown in Figure 8A. The VIM
percentage represents the flexibility and durability of the asphalt and aggregate mixture. Asphalt with
a VIM value that is too large indicates that the asphalt is not waterproof and is susceptible to oxidation
and deformation when it is loaded. The VIM value that is too small also causes the mixture to become
stiff and cracking due to the absence of cavities for the shifting aggregates. The smallest VIM value
was obtained by sample B, with an average of 3.302%, (A) as shown in Figure 7C and Table 5. The filler
ratio has a significant effect on the percentage of VIM because filler has a vital role in filling the voids
between aggregates. Additionally, the filler functions to make the mixture waterproof, as shown in
Figure 8B.
oxidation and deformation when it is loaded. The VIM value that is too small also causes the mixture
to become stiff and cracking due to the absence of cavities for the shifting aggregates. The smallest
VIM value was obtained by sample B, with an average of 3.302%, as shown in Figure 7C and Table 5.
The filler ratio has a significant effect on the percentage of VIM because filler has a vital role in filling
the
Appl.voids between
Sci. 2020, 10, 7236 aggregates. Additionally, the filler functions to make the mixture waterproof,
15 ofas
23
shown in Figure 8B.

Appl. Sci. 2020, 10, x FOR PEER REVIEW 16 of 23

(A)

(B)

Figure 8. (A) Cavities that are not filled with modified asphalt. (B) Filler which fills the voids between
Figure 8. (A) Cavities that are not filled with modified asphalt. (B) Filler which fills the voids between
the aggregates.
the aggregates.

The asphalt mixture’s stability can be influenced by several factors that significantly differ from
The asphalt mixture’s stability can be influenced by several factors that significantly differ from
other studies’ results. The factors that affect the asphalt mixture’s stability include the optimum asphalt
other studies’ results. The factors that affect the asphalt mixture’s stability include the optimum
content in the mix, the gradation and composition of the aggregate in the mix, the penetration of the
asphalt content in the mix, the gradation and composition of the aggregate in the mix, the penetration
asphalt-rubber used, the viscosity of the mixture, and the mixing and compaction temperature [34].
of the asphalt-rubber used, the viscosity of the mixture, and the mixing and compaction temperature
Increased bitumen stability provides better asphalt durability in withstanding traffic loads, increases
[34]. Increased bitumen stability provides better asphalt durability in withstanding traffic loads,
rutting resistance, reduces deformation at high temperatures, reduces fatigue resistance, and prevents
increases rutting resistance, reduces deformation at high temperatures, reduces fatigue resistance,
premature aging.
and prevents premature aging.
Based on the modified crepe rubber asphalt’s characterization results, it was found that the asphalt
Based on the modified crepe rubber asphalt’s characterization results, it was found that the
with the addition of 10% crepe rubber and 2% TMQ (sample B2) had the most optimum conditions.
asphalt with the addition of 10% crepe rubber and 2% TMQ (sample B2) had the most optimum
Therefore, sample B2 was subjected to further testing to determine the asphalt performance after
conditions. Therefore, sample B2 was subjected to further testing to determine the asphalt
short-term aging and long-term aging.
performance after short-term aging and long-term aging.
3.5. Modified Asphalt Performance at High Temperature before and after RTFOT
3.5. Modified Asphalt Performance at High Temperature before and after RTFOT
3.5.1. Rutting Factor (G*/Sinδ)
3.5.1. Rutting Factor (G*/Sinδ)
The value (G*/Sinδ) is the quotient of the modulus complex (G*) and phase angle (δ), which can
The value
describe (G*/Sinδ) is of
the performance theasphalt
quotient of therutting
against modulusat complex (G*) and phase
high temperatures. angle (δ),
Increasing thewhich can
modulus
describe the performance of asphalt against rutting at high temperatures. Increasing the modulus
complex (G*) and decreasing the phase angle (δ) is desirable to produce asphalt with high rutting
resistance. The higher the value (G*/Sinδ) shows the performance of asphalt in resisting rutting (anti-
rutting) at high temperatures is better [35]. Figure 9 shows the values (G*/Sinδ) before and after
RTFOT of asphalt pen grade 60/70, asphalt with 10% crepe rubber (B2 non-TMQ), and B2.
Appl. Sci. 2020, 10, x FOR PEER REVIEW 17 of 23

increases the asphalt mixture with aggregates to increase asphalt cohesion and adhesion
performance.
Appl. Sci. 2020, 10, 7236 16 of 23
However, the addition of TMQ (sample B2) shows that the rutting factor decreases before the
TFOT process is carried out (see Figure 9). This is because the penetration of asphalt increases as the
complex
concentration(G*) and
of TMQ decreasing the phase
in the mixture angle The
increases. (δ) isincrease
desirable to produce indicates
in penetration asphalt with highasphalt’s
that the rutting
resistance. The higher the value (G*/Sinδ) shows the performance of asphalt in
cohesion and adhesion properties decreased due to the antioxidant TMQ, which melts during mixing. resisting rutting
(anti-rutting)
TMQ antioxidant at highhastemperatures is bettersuch
physical properties [35]. as
Figure
wax,9causing
shows thethevalues (G*/Sinδ)
asphalt’s before
viscosity and after
to decrease,
RTFOT of asphalt pen grade 60/70, asphalt with 10%
and the fraction of maltene in the asphalt increases after mixing.crepe rubber (B2 non-TMQ), and B2.

Figure
Figure 9.
9. Factor
Factor rutting
rutting before
before and
and after
after RTFOT.
RTFOT.

The value
Figure of thean
9 shows rutting
increase factor (G */Sinδ)
(G*/Sinδ) afterofadding
the 60/70 10%pen grade
crepe asphalt,
rubber and B2
2%non-TMQ,
TMQ (Sample and B2
asphalt samples
non-TMQ and B2). increased
However, withit aging during
decreases with RTFOT
increasing and decreased with increasing
test temperature because the temperature.
asphalt is
The value
viscous. The(Gincrease
*/Sinδ) in after
valueRTFOT has in
(G*/Sinδ) a good
the B2appearance
non-TMQ and withB2a samples
decreaseindicates
in the value
that theof asphalt
penetrationare
properties after RFTOT.
getting harderThis indicates
after that it of
the addition is crepe
getting louderThe
rubber. after RTFOT.
highest The(G*/Sinδ)
value value (Greached
*/Sinδ)
increases
6.91 drastically
kPa before RTFOT, in sample
while asphaltB2 duepen to the
gradehigher
60/70elastic
was onlyproportion
2.86 kPa,after
andRTFOT. The increase
B2 non-TMQ was only in
the rutting
5.46 kPa. This factor in sample
is closely relatedB2 to after
the RTFOT
decreased showed that the
penetration cohesion
value and after
of asphalt adhesion of asphalt
the addition of
increased
10% crepe rapidly
rubber and due2% to TMQ
TMQ’s performance
compared to asphaltstabilizing
pen grade the 60/70.
rubberThis phase on to
is due the
theasphalt
increase and
in
preventing
cohesion andaging.
adhesionThisand result
thecorrelates
bitumen’s with the increase
resistance in Marshall stability,
to low temperatures, marked by where asphaltinwith
an increase the
the addition
softening of crepe
point value rubber
(see Figureand 2% TMQ
2). In this(sample
case, crepe B2) rubber
has a high stability
plays a role invalue (see Figure
increasing 5). High
the cohesion
stability
and indicates
adhesion of thethat the sample
asphalt. One of has high rutting
the factors affecting andbitumen’s
fatigue resistance.
resistance toHowever,
rutting and a significant
fatigue is
increase
the in value
modified (G */Sinδ)
asphalt’s is notand
cohesion expected
adhesion as this indicatesThe
properties. theaddition
bitumenof is crepe
too stiff and decreases
rubber increases the
elastic properties
asphalt mixture with of the asphalt.toAsphalt
aggregates increasewith asphaltgood ruttingand
cohesion resistance
adhesion must be rigid enough and
performance.
elastic enough to
However, thereturn
addition to itsoforiginal
TMQ (sampleshape after loadingthat
B2) shows [36].the rutting factor decreases before the
TFOTThe DSR istest
process results
carried outof (seetheFigure
asphalt 9). B2
Thisnon TMQ and
is because B2 samples of
the penetration showed
asphaltthat the asphalt
increases as the
performance after
concentration of TMQ rubberin thewas betterincreases.
mixture than thatThe of asphalt
increasepen grade 60/70.
in penetration Samplethat
indicates B2 had the best
the asphalt’s
rutting resistance
cohesion and adhesion performance
properties at decreased
elevated temperatures before RTFOT.
due to the antioxidant TMQ, However,
which melts after the RTFOT,
during mixing.
there was a significant increase in value (G*/Sinδ) to 16.1 kPa.
TMQ antioxidant has physical properties such as wax, causing the asphalt’s viscosity to decrease, Based on the rutting factor data
described,
and the results
the fraction of thisintest
of maltene the have
asphalta reasonable
increases after correlation
mixing.with the asphalt Marshall’s stability.
A highThe Marshall
value of the stability
ruttingvaluefactorindicates
(G*/Sinδ)that of the the60/70
bitumen has better
pen grade asphalt,cohesion and adhesion
B2 non-TMQ, and B2
properties
asphalt and rutting
samples increasedresistance.
with aging during RTFOT and decreased with increasing temperature.
The value (G*/Sinδ) after RTFOT has a good appearance with a decrease in the value of asphalt
3.5.2. Phase Angle
penetration (δ)
after RFTOT. This indicates that it is getting louder after RTFOT. The value (G*/Sinδ)
increases
The drastically
phase angle in (δ)
sample
shows B2 the
due strain
to the higher
versus elastic
stress proportion
results in the afterviscoelasticity
RTFOT. The increase
properties in the
of
rutting factor in sample B2 after RTFOT showed that the cohesion and
asphalt. The phase angle reflects the proportion between the elasticity and viscous in the asphalt. The adhesion of asphalt increased
rapidly due to
phase angle TMQ’s
value can performance
be 0 (δ = 0°) ifstabilizing
the material theisrubber phase and
fully elastic on thehasasphalt
a valueand preventing
of 90° (δ = 90°)aging.
if the
This result correlates with the increase in Marshall stability, where asphalt
material is fully viscous [35,37]. However, if the material is viscoelastic, the phase angle value will be with the addition of crepe
rubber
0°–90°. and
Figure2% 10 TMQ shows(sample B2) has apen
the asphalt high stability
grade 60/70 value (see Figure
samples’ phase5). High stability
angles, B2 non-TMQ,indicates andthat
B2
the sample has high
before and after RTFOT. rutting and fatigue resistance. However, a significant increase in value (G*/Sinδ) is
not expected as this indicates the bitumen is too stiff and decreases
Figure 10 shows that the phase angle decreases with the addition of crepe rubber and TMQ boththe elastic properties of the asphalt.
Asphalt
before andwithafter
goodaging.
rutting resistance
The decreasemust be rigid
in phase enough
angle afterandtheelastic enough
addition to return
of crepe rubberto its
and original
TMQ
shape after loading [36].
(Sample B2 non-TMQ and B2) was due to the increase in the elastic proportion after crepe rubber and
The DSR test results of the asphalt B2 non TMQ and B2 samples showed that the asphalt
performance after rubber was better than that of asphalt pen grade 60/70. Sample B2 had the best
Appl. Sci. 2020, 10, 7236 17 of 23

rutting resistance performance at elevated temperatures before RTFOT. However, after the RTFOT,
there was a significant increase in value (G*/Sinδ) to 16.1 kPa. Based on the rutting factor data described,
the results of this test have a reasonable correlation with the asphalt Marshall’s stability. A high
Marshall stability value indicates that the bitumen has better cohesion and adhesion properties and
rutting resistance.

3.5.2. Phase Angle (δ)

The phase angle (δ) shows the strain versus stress results in the viscoelasticity properties of asphalt.
The phase
Appl. Sci. 2020,angle reflects
10, x FOR PEERthe proportion between the elasticity and viscous in the asphalt. The 18
REVIEW phase
of 23
angle value can be 0 (δ = 0◦ ) if the material is fully elastic and has a value of 90◦ (δ = 90◦ ) if the material
is fullyAt
TMQ. viscous
58 °C,[35,37].
the phaseHowever, if asphalt
angle of the material is viscoelastic,
pen grade 60/70 was the86.6°,
phase anglethe
while value 0◦ –90
will be and
non-TMQ
◦
B2.
Figure 10had
samples shows
81.4° theand
asphalt
80.5°pen grade
phase 60/70
angles samples’
before phase
RTFOT. angles, B2
However, non-TMQ,
the andof
phase angle B2all
before and
samples
after RTFOT.
increases with increasing temperature.

Figure
Figure 10.
10. Phase
Phase angle
angle before
before and
and after
after RTFOT.
RTFOT.

After
FigureRTFOT,
10 shows allthat
samples experienced
the phase a decrease
angle decreases in the
with phase angle of
addition and increased
crepe rubberwith
and increasing
TMQ both
temperature.
before and after Theaging.
reductionTheindecrease
phase angle after aging
in phase angle isafter
duethe
to the increased
addition proportion
of crepe rubberofand
elasticity
TMQ
after RTFOT.
(Sample This has and
B2 non-TMQ a goodB2)correlation
was due towith decreasing
the increase asphalt
in the elasticpenetration
proportionafter
afterRTFOT. Visually,
crepe rubber and
the
TMQ.decrease
At 58 in◦ C,phase angleangle
the phase is dueof toasphalt
the stronger asphalt
pen grade binder
60/70 86.6◦ , while
wasnetwork, indicating that the asphalt
the non-TMQ and B2
is gettinghad
samples 81.4◦Inand
harder. 80.5◦ the
general, reduction
phase angles in phaseRTFOT.
before angle suggests
However, that
thethe addition
phase angleofofcrepe rubber
all samples
and TMQwith
increases playsincreasing
a vital role in the viscoelasticity of the asphalt [38].
temperature.
The
Afterphase
RTFOT, angleallof sampleexperienced
samples B2 decreaseda due to thein
decrease addition of TMQ,
phase angle andwhich increased
increased the elastic
with increasing
proportion in the asphalt-rubber mixture. Comparing the phase angles
temperature. The reduction in phase angle after aging is due to the increased proportion of the asphalt pen grade 60/70
of
samples.
elasticity B2 non-TMQ,
after RTFOT. This and B2,has the phase
a good angle increases
correlation with crepeasphalt
with decreasing rubberpenetration
and TMQ. The afteraddition
RTFOT.
of crepe rubber
Visually, increases
the decrease the elastic
in phase angleproportion,
is due to thewhile the increase
stronger in temperature
asphalt binder network, affects the viscous
indicating that the
ratio.
asphalt is getting harder. In general, the reduction in phase angle suggests that the addition of crepe
rubber and TMQ plays a vital role in the viscoelasticity of the asphalt [38].
3.5.3.The
Complex
phaseModulus
angle ofG* sample B2 decreased due to the addition of TMQ, which increased the
elastic
Theproportion in the asphalt-rubber
complex modulus (G*) is a parameter mixture. Comparing
to indicate the phase
the asphalt’s angles
binder of the(the
strength asphalt pen
cohesion
grade 60/70 samples. B2 non-TMQ, and B2, the phase angle increases
and adhesion properties of asphalt), which determines the resistance to deformation. The with crepe rubber and TMQ.
The addition of
combination of crepe
elasticrubber increases
and viscous the modulus
shear elastic proportion, while
reflects the the increase
bitumen’s in temperature
resistance affects
to deformation,
the viscous ratio.
which is influenced by the elastic proportion and viscosity. Therefore, the complex modulus (G *) is
a factor that needs to be considered in assessing the performance of asphalt against high temperatures
3.5.3. Complex Modulus G*
and aging.
The complex
Figure modulus
11 complex (G*) is(G*)
modulus a parameter to samples
of asphalt indicate the
penasphalt’s binder
grade 60/70. B2strength
non-TMQ,(theand
cohesion
B2 in
andconditions
the adhesion properties
before andofafter
asphalt), which
RTFOT. Thedetermines thethe
increase in resistance
complextomodulus
deformation.
valueThe combination
occurred in the
of elastic and
non-TMQ viscous
B2 and shear modulus
B2 samples compared reflects the bitumen’s
to asphalt pen graderesistance
60/70. Thetoincrease
deformation,
in the which
complex is
modulus (G*) value obtained by adding crepe rubber increases the asphalt’s elastic proportion.
However, the complex modulus of sample B2 was much higher after the addition of TMQ, which
further increased the rubber-asphalt elasticity.
ratio.

3.5.3. Complex Modulus G*

The complex modulus (G*) is a parameter to indicate the asphalt’s binder strength (the cohesion
and Sci.
Appl. adhesion properties of asphalt), which determines the resistance to deformation.18 of
2020, 10, 7236 The
23
combination of elastic and viscous shear modulus reflects the bitumen’s resistance to deformation,
which is influenced by the elastic proportion and viscosity. Therefore, the complex modulus (G *) is
influenced
a factor thatby the elastic
needs proportion in
to be considered and viscosity.
assessing theTherefore, the complex
performance of asphaltmodulus
against (G*)
highistemperatures
a factor that
needs to
and aging.be considered in assessing the performance of asphalt against high temperatures and aging.
Figure
Figure 1111 complex
complex modulus
modulus (G*)
(G*)ofofasphalt
asphaltsamples
samplespen
pengrade
grade60/70.
60/70.B2B2 non-TMQ,
non-TMQ, andand
B2 B2
in
in the conditions before and after RTFOT. The increase in the complex modulus
the conditions before and after RTFOT. The increase in the complex modulus value occurred in the value occurred
in the non-TMQ
non-TMQ B2 andB2 B2and B2 samples
samples compared compared to asphalt
to asphalt pen gradepen60/70.
gradeThe
60/70. The in
increase increase in the
the complex
complex
modulusmodulus
(G*) value (G*)obtained
value obtained by adding
by adding crepecrepe rubber
rubber increases
increases thethe asphalt’selastic
asphalt’s elasticproportion.
proportion.
However,
However, the complex modulus of sample B2 was much higher after the addition of TMQ, further
the complex modulus of sample B2 was much higher after the addition of TMQ, which which
increased the rubber-asphalt
further increased elasticity.
the rubber-asphalt elasticity.

Figure 11. Complex Modulus Before and After Aging (RTFOT).

In all samples, the complex modulus values increase with aging and decrease with increasing
temperature. The elastic proportion influences the increase in the complex modulus value after RTFOT.
Complex modulus (G*) results after RTFOT have a reasonable correlation with decreasing penetration
after RTFOT. The penetration that decreased after RTFOT indicated that the asphalt binder was getting
harder. Sample B2 had a very significant increase in the complex modulus value after RTFOT from
6.91 kPa to 16.1 kPa. The increasing elastic proportion influences this significant increase because
asphalt loses some light fractions during RTFOT. These modulus complex results are consistent with the
rutting and phase angle results, where an increase in other components increases the elastic proportion.
In contrast, an increase in temperature changes the viscous proportion to an increase [39,40].

3.6. FT-IR Modified Asphalt before and after LTOA

The performance of crepe rubber and TMQ antioxidants against long-term aging of asphalt
can be simulated using the Long Term Oven Aging (LTOA) method [41]. Furthermore, long-term
characterization using FTIR analysis in the range of wavenumbers from 4000 to 600 cm−1 . Long-term
asphalt aging is indicated by the formation of carbonyl groups (-C=O) at the wave number 1700 cm−1
and sulfoxide (-S=O) at the wave number 1030–1070 cm−1 [42,43].
Figure 12A illustrates the results of FTIR analysis for samples of asphalt pen grade 60/70. asphalt
with the addition of 10% crepe rubber (B2 non-TMQ) asphalt with the addition of crepe rubber and
2% TMQ (B2) before aging. The results showed that there were several absorption peaks at several
wavelengths including, 3670 cm−1 (Free OH), 2930 cm−1 (CH2, CH3), 1600 cm−1 (C=C), 1455 cm−1
(CH3 Deformation), 1379 cm−1 (CH3 Deformation), 1060 cm−1 (SO or CC aromatic (crepe rubber or
TMQ)), 825 cm−1 , 745 cm−1 (CH aromatic) [44,45]. The addition of crepe rubber to the asphalt did not
chemically affect the asphalt. This was evidenced by the FTIR results graph, which did not find any
new clusters. However, with asphalt with crepe rubber and TMQ, there was an increase and decrease
in the number of clusters that were not so specific. At wavenumbers 3670 and 1060 cm−1 , there is an
increase in the hydroxy group not attached to hydrogen and generally found in the form of alcohol or
phenol with the OH group sterically inhibited. It should be noted that the wavenumber 3670 cm−1 can
also indicate free OH groups and free from interaction with ions or other groups [45].
Appl. Sci. 2020,
Appl. Sci. 10, x7236
2020, 10, FOR PEER REVIEW 19 of
20 of 23
23

(A)

(B)

Figure 12. (A) FT-IR of asphalt before LTOA. (B) FT-IR asphalt after LTOA.
Appl. Sci. 2020, 10, 7236 20 of 23

While the group at wave number 1060 cm−1 shows the sulfoxide (S-O) groups of asphalt [42–44].
Naturally, asphalt has a sulfoxide group because asphalt contains a certain amount of sulfur. Due to
storage for a long time, it causes oxidation of the asphalt to form sulfoxide groups. But the addition
of crepe rubber and TMQ antioxidants in the asphalt mixture increased the number of groups at the
wavenumber of 1060 cm−1 . The increase in these groups was not due to an increase in sulfoxide groups
but increased the aromatic C-C group from crepe rubber and TMQ [46].
Figure 12B. It is an illustration of FTIR analysis results for samples of asphalt pen grade 60/70,
asphalt with the addition of 10% crepe rubber, and asphalt with the addition of crepe rubber and
2% TMQ after aging. By comparing Figure 12A,B, it is not found to include new groups in the
sample, especially the carbonyl group (1700 cm−1 ), indicating aging on the asphalt. The indication of
asphalt aging is shown in the increase of sulfoxide groups after the aging process peaked at 1060 cm−1 .
However, at the same wavenumber, it can be seen that the sample with the addition of crepe rubber
and TMQ has an increasingly steeper peak. The peak that is formed is getting steeper, indicating an
increase in the concentration of a group. In this case, the aromatic C-C group’s increase played a
significant role in the 1060 cm−1 peak’s steepening.
The increase in aromatic C-C groups tends to be caused by the degradation of crepe rubber or
TMQ during the aging process [46]. Aging of asphalt samples with a mixture of crepe rubber and
TMQ showed decreased peak sharpness at wavenumbers 825 cm−1 and 745 cm−1 (C-H aromatic).
The decrease in peaks of 825 cm−1 and 745 cm−1 showed the performance of TMQ, which suppressed
carbonyl group formation by changing the aromatic C-H groups, which were the source of radical
formation to become aromatic C-C. The increase in the carbonyl group should be directly proportional
to the increase in aromatic C-H [47]. In general, the role of TMQ in overcoming oxidation in the
rubber asphalt mixture is due to the absence of carbonyl groups in all asphalt samples after aging
using the LTOA method. This is consistent with references where TMQ plays a vital role in preventing
polymers [46,48].

4. Conclusions
The use of crepe rubber as an asphalt additive can improve the performance of asphalt pen
grade 60/70. The most noticeable improvements were load-bearing capabilities and thermal stability.
Modified asphalt has lower penetration, soft point, and high Marshall stability than pen grade 60/70
asphalt. The addition of 10% crepe rubber and 2% TMQ is the most optimum condition with the
following test results: penetration 68.70 dmm, softening point 55.45 ◦ C, weight loss only 0.0579%,
penetration after RTFOT 59.60 dmm. Marshall stability 1403.96 kg with an optimum asphalt content of
5.50% and a rutting factor (G*/Sin) of 6.91 kPa and 16.1 kPa before and after RTFOT. Increased bitumen
stability provides better asphalt durability in withstanding traffic loads, increases rutting resistance,
reduces deformation at high temperatures, reduces fatigue resistance, and prevents premature aging.
The addition of antioxidant TMQ more than 2% changed the asphalt’s physical properties to become
softer, increased penetration, and decreased Marshall stability. The performance of modified asphalt
10% crepe rubber and 2% TMQ after RTFOT increased after the addition of TMQ. The most obvious
increase was the rutting factor (G*/Sinδ) from 6.91 kPa to 16.1 kPa after RTFOT. TMQ performance is
outstanding under long-term aging conditions, where the carbonyl group is not formed (C = O) after
the addition of TMQ seen in the FT-IR results.

Author Contributions: Conceptualization, B.I.; Formal analysis, B.I. and A.W.; Investigation, A.M.; Methodology,
B.I.; Validation, A.M.; Visualization, A.W. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by DRPM Kemristek/BRIN, the Republic of Indonesia.
Conflicts of Interest: The authors declare no conflict of interest.
Appl. Sci. 2020, 10, 7236 21 of 23

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