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Engineering properties of asphalt binders

containing nanoclay and chemical warm-mix
asphalt additives

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DOI: 10.1016/j.conbuildmat.2016.02.089

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 Construction and Building Materials 112 (2016) 232–240

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Engineering properties of asphalt binders containing nanoclay

and chemical warm-mix asphalt additives
Mohd Ezree Abdullah a, Kemas Ahmad Zamhari a, Mohd Rosli Hainin b,⇑, Ebenezer Akin Oluwasola b,
Norhidayah Abdul Hassan b, Nur Izzi Md. Yusoff c
a
Faculty of Civil and Environmental Engineering, UniversitiTun Hussein Onn, Johor, Malaysia
b
Dept. of Geotechnics and Transportation Engineering, Faculty of Civil Engineering, UniversitiTeknologi Malaysia, Johor, Malaysia
c
Dept. of Civil and Structural Engineering, Universiti Kebangsaan Malaysia, Selangor, Malaysia

h i g h l i g h t s

 We investigate nanoclays and a chemical WMA additive for possible WMA application.
⁄
 Nanoclays modified binders increased the G /sin d values and failure temperatures.
 The NCMB B4% could potentially become a new WMA binder.

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

Article history: In the effort to promote the construction of green pavement the asphalt concrete industry has been mak-
Received 2 October 2015 ing consistent effort to use warm-mix asphalt (WMA) in their construction. The objective of this study
Received in revised form 29 December 2015 was to improve the properties of the asphalt binders through the addition of nanoclays and chemical
Accepted 17 February 2016
WMA additive. An asphalt binder of 80/100 penetration grade was modified with different percentages
Available online 2 March 2016
of Nanoclay A (montmorillonite clay surface modified with 35–45 wt.% dimethyl dialkyl (C14–C18)
amine), Nanoclay B (montmorillonite clay surface modified with 35–45 wt.% octadecylamine, and
Keywords:
0.5–5.0 wt.% aminopropyl-triethoxysilane), and chemical WMA additive (fatty polyamines polymer
Green pavement
Warm mix asphalt
non-ionic component). After modification, the asphalt binders were named Nanoclay A modified asphalt
Nanoclay binder (NCMB A), Nanoclay B modified asphalt binder (NCMB B), and chemical WMA modified asphalt
Chemical additive binder (CWAA). The rheological characteristics of the unmodified and modified asphalt binders were
Rutting evaluated using the rotational viscosity, dynamic shear rheometer, and bending beam rheometer tests.
Fatigue Results of the tests showed that NCMB B and CWAA significantly reduced mixing and compaction tem-
peratures. However, only NCMB B showed a significant increase in rutting and fatigue resistance when
compared with base asphalt binder. A change in chemical bond was also observed in the tested binders
after long-term aging, which suggests that the addition of modifier could delay the aging process.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction several pavement distresses that affect the performance of asphalt

Asphalt binder is an element that acts as a binding agent in
asphalt pavements. Most asphalt binders are manufactured from
crude oil. Asphalt binders are traditionally regarded as a colloidal
system made up of asphaltenes micelles covered with a stabilising
phase of polar resins, which form an interface with a continuous
oily maltenic medium. It also influences pavement performance
under various loading and weather conditions as well as low and
high on-site operating temperatures [1–4]. However, there are
⇑ Corresponding author.
E-mail address: mrosli@utm.my (M.R. Hainin).
binder, namely high-temperature rutting (or permanent deforma-
tion), medium-temperature fatigue, moisture damage, and low-
temperature cracking damage, all of which could decrease the
quality of asphalt pavements. Therefore, base asphalt binders need
to be modified to enhance their properties for better performance
[5,6].
Previous studies have shown that, compared with unmodified
base binder, the addition of modifier tend to enhance its physical
and rheological properties, depending on the types and dose of
the modifier utilized [7–11]. An ideal modifier should be able to
sustain asphalt binder’s resistance to multiple types of distresses.
From an engineering point of view, an ideal asphalt binder should

http://dx.doi.org/10.1016/j.conbuildmat.2016.02.089
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
 M.E. Abdullah et al. / Construction and Building Materials 112 (2016) 232–240 233

provide resistance to rutting at high temperature, fatigue at inter-
mediate temperature, and thermal cracking at low temperature.
Additionally, existing plants need to be modified slightly so that
the modified asphalt binder could achieve the targeted viscosity
and could be easily blended with aggregates at a particular tem-
perature. The modified asphalt binder should remain homogenous
during storage to ensure its stability and hence yield similar results
as in laboratory experiments [7,12,13].
Over the last decade, the use of warm-mix asphalt (WMA) has
gained increasing popularity among authorities and pavement
industry as this technology reduce emissions and fuel consumption
during the production and construction of asphalt mixes without
significantly affecting the properties of the mixes. Previous studies
on the production of WMA mix focused on modifying base asphalt
binders through the addition WMA additives [14–17]. Currently,
the modification of base asphalt binders with WMA additives could
be done through three different processes, namely through the
foaming process, the addition of organic additives, and the addition
of chemical additives. Studies have shown that the use of WMA
technology has significantly improved the performance of pave-
ments [11,18].
Other researchers have shown that the physical and mechanical
properties of base asphalt binder could also be improved through
through the Superpave asphalt binder tests, surface energy test,
and storage stability test. The performance characteristics of NCMB
will then be compared with a chemical WMA modified asphalt bin-
der (CWAA), an existing product that is widely available in the
market.
2. Experimental design
2.1. Materials
The base asphalt binder used in this study was obtained from Kemaman Bitu-
men Company, Malaysia. Table 1 shows the characteristics of the base asphalt bin-
der used in this study, which conforms with the Malaysian Standard MS 124
requirement [25] for an asphalt binder of 80/100 penetration grade and Superpave
requirement [26] for a performance grade of PG 64-28. Three types of modifiers,
namely Nanoclay A, Nanoclay B, and chemical WMA additive with varying percent-
ages were used to modify the base asphalt binder. The chemical WMA additive is an
established additive and is currently used by the asphalt industry as a modifier in
the production of WMA mixes.
Nanoclay A and Nanoclay B modifiers were initially evaluated to identify their
potential use as WMA modifiers. The physical properties of these modifiers are pre-
sented in Table 2. The chemical compositions of the modifiers used are described in
greater details in Table 3. The chemical WMA additive has a totally different chem-
ical composition compared to the nanoclays. The percentage of chemical composi-
tion for Nanoclay A and Nanoclay B are slightly different with the exception of ferric
oxide.

modification with nanoclay. The engineering properties of modi-

fied asphalt binders and mixes were also significantly improved, 2.2. Sample preparation

particularly in terms of their stiffness, storage stability, rutting
resistance, thermal cracking resistance, and aging resistance
[2,13,19–24]. However, no intensive studies have been done to
evaluate the effects of nanoclay as WMA additive based on the per-
formance of asphalt binders and mixes. Due to availability of
numerous types of nanoclays in the market, each one with differ-
ent properties, there is a need to identify the possibility of using
nanoclay as a WMA additive in the future. This material could sig-
nificantly reduce the mixing and compaction temperatures of
asphalt mixes without compromising its performance. Therefore,
the objective of this study is to evaluate the performance of nan-
oclay modified asphalt binder (NCMB) as a new WMA binder
The physical and rheological properties of modified asphalt binders were deter-
mined to evaluate the effectiveness and potential of WMA additives, which would
then be selected for the production of WMA mixes. In the sample modification pro-
cess, 400 g of base asphalt binder was heated in an iron container until it became
fluid under a medium shear mixer using the Silverson-L4RT at a speed of
2000 rpm. When the temperature reached 155 ± 5 °C, the chemical WMA additive
was gradually added (10 g/20 s) at 1%, 2%, 3% and 4% (by weight of asphalt binder)
for 10 min. On the other hand, Nanoclay A with 3%, 4%, and 5% (by weight of asphalt
binder) was gradually added (5 g/30 s) into the melted asphalt binder under a high
shear mixer of 5500 rpm for 30 min. A similar procedure was used for Nanoclay B.
After the processes have been completed, the modified asphalt binders were cate-
gorized as Nanoclay A modified asphalt binder (NCMB A), Nanoclay B modified
asphalt binder (NCMB B), and chemical WMAmodified asphalt binder (CWAA).
The experimental flowchart is shown in Fig. 1.

Table 1
Characteristics of base asphalt binder.

Characteristics Method Result Requirement

Penetration at 25 °C, 100 g 5 s, 0.1 mm MS 541 93.7 80–100
Softening Point, °C MS 687 48.7 45–52
Solubility in trichloroethylene, % wt. ASTM D2042 99.53 Min. 99.00
Ductility at 25 °C, 5 cm per min, cm ASTM D113 100+ Min. 100
Retained penetration after thin-film oven test, % ASTM D5 52.1 Min. 47.0
Drop in penetration after heating, % ASTM D5 15.8 Max. 20.0
Flash Point, °C AASHTO T48 308 Min. 230
Loss on heating,% wt. AASHTO T240 0.090 Max. 1.000
Viscosity at 135 °C, Pa s ASTM D4402 0.48 Max. 3.00
Original G⁄/sin d at 64 °C @ 10 rad, kPa AASHTO TP5 1.63 Min. 1.00
RTFO Residue G⁄/sin d at 6 °C @ 10 rad, kPa AASHTO TP5 6.08 Min. 2.20
PAV Residue G⁄sin d at 64 °C @ 10 rad, kPa AASHTO TP5 2897 Max. 5000
PAV Residue Stiffness at 18 °C @ 60 s, MPa AASHTO TP1 120 Max. 300
PAV Residue m-value at 18 °C @ 60 s, MPa AASHTO TP1 0.344 Min. 0.300

Table 2
The physical properties of modifiers.

Properties Chemical WMA additive [27] Nanoclay A Nanoclay B

Ingredients Fatty polyamines Montmorillonite clay surface modified Montmorillonite clay surface modified with
Polymer with 35–45 wt.% dimethyl dialkyl 35–45 wt.% Octadecylamine and 0.5–5.0 wt.%
Non-ionic component (C14–C18) amine aminopropyl-triethoxysilane
Physical state Solid Powder Powder
Color Brown Gray white Gray white
Odour Amine like Amine like Amine like
Solubility Insoluble in cold water Water soluble Water soluble
234 M.E. Abdullah et al. / Construction and Building Materials 112 (2016) 232–240

Table 3 (PAV) test [33]. The RTFO Model N759 was used to simulate short-term aging as
The chemical properties of modifiers. stipulated in ASTM D2872, while the PAV Model PR9300 was used to simulate
long-term aging of the asphalt binders as described in ASTM D2872.
Chemical composition Chemical Nanoclay Nanoclay
WMA A (%) B (%)
additive (%) 2.3.4. Rheological characterization
A stress-controlled HAAKE dynamic shear rheometer (DSR) was used to deter-
Carbon dioxide (CO2) – 0.10 0.10 mine the mechanical properties of unmodified and modified asphalt binders. The
Silicon oxide (SiO2) – 67.60 67.70 DSR tests were conducted at temperatures ranging from 18 to 82 °C and at a loading
Aluminium oxide (Al2O3) – 22.40 23.30 frequency of 1.59 Hz (10 rad/s) within the linear viscoelastic (LVE) response. A fre-
Ferric oxide (Fe2O3) – 6.30 3.78 quency of 1.59 Hz is typically used to simulate the shearing action corresponding to
Magnesium oxide (MgO) – 2.17 3.03 a traffic speed of about 90 km/h, which is a standard speed limit for federal high-
Chlorine (Cl) – 0.51 0.79 ways [34,35]. The test was performed in accordance with ASTM D 7175.
Titanium dioxide (TiO2) – 0.20 0.48 For the evaluation of rutting resistance, each binder (1 mm testing gap and
Calcium oxide (CaO) – 0.19 0.26 25 mm diameter plates) was measured in terms of its complex shear modulus
Potassium oxide (K2O) – 0.13 0.21 (G⁄) and phase angle (d) values, starting at 64 °C (PG 64-28) until failure, in accor-
Sulfur (S) 0.025 – – dance with the Superpave mix design specifications [36]. The high service temper-
Ethane (CH2) 99.100 – – ature of the binders were set as the temperature at which the G⁄/sin d was greater
Iron (Fe) 0.004 – – than 1.0 kPa and 2.2 kPa for unaged and short-term aged binder respectively [37].
Potassium (K) 0.007 – – These parameters could be used to describe the rutting resistance of the tested
Magnesium (Mg) 0.323 – – asphalt binders.
Phosphorus (P) 0.043 – – For the evaluation of fatigue resistance, each binder (2 mm testing gap and
Silicon (Si) 0.437 – – 8 mm diameter plates) was measured in terms of its complex shear modulus (G⁄)
Aluminium (Al) 0.010 – – and phase angle (d) values, beginning at 18 °C (PG 64-28) until failure, in accor-
Calcium (Ca) 0.016 – – dance with the Superpave mix design specifications [38]. The high and low service
temperatures of the asphalt binders were set as the temperature at which the bin-
der’s G⁄sin d after PAV aged binder condition did not exceed 5000 kPa. This param-
2.3. Testing method eter indicates the performance of asphalt binder in terms of fatigue cracking at the
intermediate service temperature [33,38–40].
2.3.1. Evaluation of physical properties
The physical properties of unmodified and modified asphalt binders were mea- 2.3.5. Bending beam rheometer (BBR) test
sured using the softening point and penetration tests in accordance with the ASTM The creep test with a bending beam rheometer (BBR) was used to evaluate low
D5 [28] and ASTM D36 [29] respectively. The Brookfield viscometer was used to temperature stiffness and relaxation properties of asphalt binders. In this study,
measure the viscosity of the asphalt binders between 120 and 180 °C, in accordance creep tests were conducted in accordance with ASTM D6648 [41] at a testing tem-
with ASTM D4402 [30]. perature of 18 °C, using the BBR equipment and the accompanying software ver-
sion 3.21. The asphalt binders were prepared according to a specific beam shape
2.3.2. Storage stability test (125 mm long, 12.5 mm wide, and 6.25 mm thick) before being submerged in a
A hot storage test was conducted to evaluate the stability of high temperature fluid bath, which was controlled at a set test temperature for 60 min. The beam
storage of the modified asphalt binders. A 25 mm-diameter, 140 mm-high alu- was supported at both ends by stainless steel half rounds, 102 mm apart. A constant
minium tube was filled with 50 g hot asphalt binder and placed vertically in an weight of 100 g was then loaded at the mid-point of the beam under normal gravity
oven at 163 °C for 48 h. The tube was then taken out and cooled in a refrigerator conditions and deflections were measured at 8, 15, 30, 60, 120 and 240 s. The soft-
at 7 °C for four hours. Finally, the tube was cut into three equal sections and the ware automatically calculated the stiffness of the beam, which is also known as
top and bottom sections of the asphalt binder were further evaluated with the soft- creep stiffness (S) and creep rate (m) of the binders, at 60 s loading time. The creep
ening point test. If the difference in the softening point values between the top and rate, or m-value, represents the rate at which binder stiffness changes with time at
the bottom sections of the tube was less than 2.2 °C, then the sample could be low temperatures.
regarded as a storage stable blend [31].
2.3.6. Surface free energy test
2.3.3. Aging method The potential of moisture-induced damage for asphalt mixes could be predicted
To simulate aging during the in-service life of a pavement, the asphalt binders based on the cohesion and adhesion of mixtures using a surface free energy (SFE)
were exposed to artificial short-term and long-term aging procedures using the test [42–47]. In this study, the Standard Digital Contact Angle Goniometer with
Rolling Thin Film Oven (RTFO) test [32], followed by the Pressure Aging Vessel DROPImage Standard Software was used to determine the SFE between distilled

Fig. 1. Experimental flow chart.

 M.E. Abdullah et al. / Construction and Building Materials 112 (2016) 232–240
water as a probe liquid and a solid surface of thin layer asphalt binder based on the
contact angle values. SFE can be defined as the energy required to expand the sur-
face phase of asphalt binders and distilled water [42,43,47,48]. Using the sessile
drop device, 2 lL of distilled water was dispensed over an asphalt binder with a
smooth horizontal surface. The contact angle was measured as soon as the water
touched the sample using a high-resolution digital camera and the real time SFE
of the binder’s was computed using the provided software. The SFE values obtained
using this equipment were similar to the Sessile drop method outlined in the
NCHRP-104 procedure [46]. A higher SFE indicates good adhesion between the
asphalt binder and the aggregate [49–51].
3. Results and discussion
3.1. Penetration and softening point tests
The physical properties of the unmodified and modified asphalt
binders were evaluated using the penetration test, softening point
test, penetration index (PI), and penetration-viscosity number
(PVN). As shown in Table 4, the addition of NCMB A and NCMB B
reduced penetration and increased softening point value; however,
the effect produced by NCMB A was larger compared with the
effect of NCMB B. In contrast, CWAA showed a different trend,
wherein the penetration was increased and softening point
decreased when the percentage of chemical WMA additive was
increased. However, changes in penetration and softening point
were smaller for CWAA 1% and CWAA 2%.
In addition, the temperature susceptibility of the modified
asphalt binder samples was calculated in terms of PI using the
results obtained from the penetration and softening point tests.
Temperature susceptibility is defined as the change in the consis-
tency parameter as a function of temperature [3]. The temperature
susceptibility of asphalt binders could also be determined based on
PVN. Higher values of PI and PVN represent lower temperature sus-
ceptibility, which provide better resistance to cracking and rutting
of asphalt mixes [52,53]. As shown in Table 4, PI increased when
the softening point or penetration increases. In this study, the PI
and PVN values of the control asphalt binder were 0.11 and
0.02 respectively. However, the PI values increased for NCMB A
and NCMB B but decreased for CWAA. Additionally, the modified
asphalt binders show an almost similar trend in PVN values. There-
fore, asphalt mixes containing nanoclay yields higher PI and PVN
values, which could cause the mixtures to be more resistant to
thermal cracking and rutting.
3.2. Rotational viscosity test
The rotational viscometer (RV) test was used to evaluate the dif-
ference in viscous behavior, which is considered to be one of the
most important properties of asphalt binders. Fig. 2 shows the vis-
cosity results of different percentages of modifiers for CWAA,
NCMB A, and NCMB B at different temperature settings. The results
clearly show that CWAA and NCMB B decreased the viscosity of the
asphalt binder compared to base asphalt binder. However, the
Table 4
Physical test data for unmodified and modified binders.
Binder type Penetration (dmm) Softening point (°C)
Control 93.7 48.7
CWAA 1% 94.3 48.4
CWAA 2% 94.7 48.1
CWAA 3% 97.6 47.7
CWAA 4% 99.6 47.1
NCMB A3% 78.9 54.6
NCMB A4% 71.8 59.6
NCMB A5% 66.5 60.0
NCMB B3% 88.7 51.2
NCMB B4% 84.6 51.6
NCMB B5% 82.0 52.7
235
viscosity of NCMB A increased in comparison to base asphalt
binder; viscosity also increased as the percentages of Nanoclay A
was increased. Even though both modifiers were produced from
the same nanoclay material, the surface treatment during the syn-
thesis process for both modifiers was different. According to Yao
et al. [24], the decrease in viscosity of the NCMBs could be due
to the effect of octadecylamine and aminopropyl-triethoxysilane
modification during the surface treatment process. The chemical
treatment contributes to a homogeneous lubricating effect and
reduces the particles agglomeration phenomenon to create better
dispersion during the blending process with the base asphalt bin-
der. Therefore, this modification process could reduce the viscosity
of the modified asphalt binders.
On the other hand, the increased viscosity of NCMB A could be
due to the formation of its exfoliated structure that has thicker par-
ticle agglomeration. This phenomenon might have prevented the
movement of asphalt binder’s molecule chains. A typical viscos-
ity–temperature chart was normally used to determine the pro-
posed mixing and compaction temperatures of the mix. However
previous researchers have stated that the use of this chart is not
feasible, particularly for asphalt binders modified with WMA addi-
tives [55–58]. In certain cases, the additives might change the bin-
der’s characteristics, and therefore it is not appropriate to use the
viscosity–temperature chart to predict mixing and compaction
temperatures. Consequently the effectiveness of WMA additives
was evaluated further based on the specimens of WMA mixes,
which were prepared at lower mixing and compaction tempera-
tures. Evaluation is usually conducted at temperatures ranging
from 20 to 50 °C lower than the conventional hot-mix asphalt
(HMA) mixes.
3.3. Storage stability
The storage stability test was conducted to ensure that the
blending process was effective and that the modified asphalt bin-
ders would remain stable during storage. Fig. 3 shows a compar-
ison between the unmodified and modified asphalt binders in
terms of their storage stability. In general, increasing the percent-
age of modifiers will increase the difference in the softening point
values between the top and the bottom sections. However, the dif-
ference between the top and bottom sections of the aluminium
tube for all samples was less than 2.2 °C. Hence, the modified
asphalt binder could be regarded as a storage stable blend, which
is a very important parameter in terms of the initial properties of
modified asphalt binders, especially during storage, transportation,
and application at asphalt mixes plant [31].
3.4. Rutting resistance
In the Superpave binder specifications, G⁄/sin d is used to
define the rutting resistance of an asphalt binder at high
Viscosity at 135 °C (Pa s) Penetration index PVN
0.48 0.11 0.02
0.45 0.05 0.11
0.42 0.03 0.21
0.41 0.06 0.21
0.34 0.16 0.48
0.85 1.10 0.62
0.97 1.92 0.69
1.15 1.80 0.84
0.51 0.62 0.01
0.47 0.57 0.17
0.45 0.76 0.27
236 M.E. Abdullah et al. / Construction and Building Materials 112 (2016) 232–240

10
Control
CWAA 1%
CWAA 2%
CWAA 3%
CWAA 4%
NCMB A 3%
NCMB A 4%
NCMB A 5%
NCMB B 3%

Viscosity, Pa s
NCMB B 4%
NCMB B 5%
1

Compaction Temperature Range

Mixing Temperature Range

0.1
110 120 130 140 150 160 170 180
Temperature, οC

Fig. 2. Rotational viscosity test results for the based and modified binders.

0.50
Difference S.P value of top and bottom

0.40

0.30
(οC)

0.20

0.10

0.00
Control CWAA CWAA CWAA CWAA NCMB NCMB NCMB NCMB NCMB NCMB
1% 2% 3% 4% A 3% A 4% A 5% B 3% B 4% B 5%

Fig. 3. Storage stability test result for both the control and modified asphalt binders.

3500
16000
3000 14000

2500 12000
G*/sin (Pa)
G*/sin (Pa)

10000
2000
8000
1500
6000
1000
4000
500 2000

0 0

(a) unaged (b) short term aged

Fig. 4. G⁄/sin d value of (a) unaged and (b) short-term aged asphalt binder at 64 °C.

temperature [9,39,40,59]. As shown in Fig. 4, the G⁄/sin d values aging of NCMB A and NCMB B increased when compared with
for all asphalt binders are higher than 1.0 kPa (unaged base asphalt binder. However, the G⁄/sin d for unaged and RTFO
condition) and 2.2 kPa (RTFO aging condition) at 64 °C testing aging values for CWAA decreased as the percentages of
condition. Based on both conditions, all modified asphalt chemical WMA additive increase. Although there was a slight
binders meet the Superpave specification requirement at the decrease, CWAA still showed the same PG grade as base
selected testing temperatures. The G⁄/sin d for unaged and RTFO asphalt binder.
 M.E. Abdullah et al. / Construction and Building Materials 112 (2016) 232–240
76
Failure Temperature ( C)
74
72
70
68
66
64
62
60
(a) unaged
Fig. 5. High failure temperature of (a) un-aged and (b) short-term aged asphalt binders.
3.5. Failure temperature
The failure temperature of asphalt binders was calculated based
on the recorded data of rutting resistance test for unaged and
short-term aged conditions. Failure temperature was determined
through interpolation as the temperature at which the G⁄/sin d
value is less than the required value at testing temperature. The
higher failure temperature values showed that asphalt binders
were less susceptible to permanent deformation at high tempera-
tures [39,54]. The binders were considered to have failed after
the value of G⁄/sin d reached below 1.0 kPa and 2.2 kPa for the
unaged and short-term aged binder respectively. Fig. 5(a and b)
shows the high failure temperature of unmodified and modified
asphalt binders in both unaged and short-term aged conditions.
As shown in this figure, the failure temperature for NCMB A and
NCMB B increased when compared with the control sample. The
trends for both conditions were almost similar and the increasing
failure temperatures of all binders were almost similar with a
range of difference of approximately six degrees (one PG grade).
NCMB A and CWAA showed the highest and lowest failure temper-
atures respectively. Compared to CWAA, the failure temperature
was higher when the percentage of nanoclay in the base asphalt
binder was increased.
3.6. Fatigue resistance
In this study, the SHRP Report A369 [60] was used as a guideline
in determining‘ the characteristics of asphalt binders in terms of
fatigue resistance ability. The SHRP report stated that faster shear-
ing energy loss under relative loads indicates a higher G⁄sin d value.
In other words, lower values of G⁄sin d at 10 rad/s is generally con-
sidered desirable from the fatigue cracking resistance point of view
[39,40,54,61]. The G⁄sin d values of asphalt binders containing
3500
3000
2500
G*sin (kPa)
2000
1500
1000
500
0
Control CWAA CWAA CWAA CWAA NCMB NCMB NCMB NCMB NCMB NCMB
1%
⁄
Fig. 6. G sin d of RTFO + PAV aging asphalt binders containing different percentages of modifiers at 25 °C.
237
80
Failure Temperature ( C)
78
76
74
72
70
68
66
64
62
(b) short term unaged
additives after being conditioned (RTFO + PAV residual) were
determined using the DSR at 25 °C and the results are shown in
Fig. 6. The G⁄sin d values of PG 64-28 binders decreased steadily
as the percentage of chemical WMA additive increase and this
result contradicts the trend for NCMB in which the G⁄sin d values
increased as the percentage of nanoclays increase.
The results indicated that the CWAA, NCMB B3%, and NCMB B4%
significantly reduced the G⁄sin d values compared with the control
sample and NCBM A. Therefore, it is predicted that the CWAA and
NCMB B could have a higher resistance to fatigue cracking at inter-
mediate temperatures compared to the control sample. This could
be due to the effect of the chemical reaction between CWAA and
NCMB B with the base asphalt binder, making the binder less stiff
and more elastic.
3.7. Thermal cracking
The BBR test was performed to determine the deflections of the
binder or its creep stiffness under constant load at low tempera-
tures. The obtained creep stiffness represents the behavior of
asphalt binders in terms of thermal cracking resistance under
low temperature conditions. According to the Superpave specifica-
tion [26], the maximum value for creep stiffness is 300 MPa and
the minimum value for the m-value is 0.300 at test temperature.
Therefore, the decrease in creep stiffness is expected to result in
smaller tensile stress in asphalt binder and reduce the tendency
for low temperature cracking [22,54].
The stiffness (S) and m-values of unmodified and modified
asphalt binders are shown in Fig. 7. In general, stiffness increased
steadily when the percentage of chemical WMA additive for CWAA
was increased. Although NCMB B showed a similar trend, the vari-
ation of stiffness value between NCMB B3% and NCMB B4% is not
apparent. The value increased for NCMB B5%. As for NCMB A, the
2% 3% 4% A 3% A 4% A 5% B 3% B 4% B 5%
238 M.E. Abdullah et al. / Construction and Building Materials 112 (2016) 232–240

180

160

140
0.400

120
0.350
Stiffness (Mpa)

100 0.300

80 0.250

m-value
0.200
60
0.150
40
0.100

20
0.050

0 0.000

Control
CWAA 1%
CWAA 2%
CWAA 3%
CWAA 4%

NCMB B 3%
NCMB B 4%
NCMB B 5%
NCMB A 3%
NCMB A 4%
NCMB A 5%
(a) Stiffness (b) m-value
Fig. 7. (a) Stiffness and (b) m-value of aging asphalt binder containing different percentages of modifiers at 18 °C

stiffness value decreased when the percentage of Nanoclay A in
the mixture was increased. The m-value decreased when the
amount of modifiers in CWAA and NCMB B was increased. This is
in contrast with the NCMB A where the m-value increased
concurrent with the amount of Nanoclay A in the asphalt mix.
However, NCMB A 3% and NCMB A 4% showed only a slight
variation in the m-value.
Based on Fig. 7, it is obvious that, with the exception of CWAA
3%, CWAA 4%, and NCMB B 5%, all other binders meet the
Superpave requirements when tested at 18 °C. The results also
showed that CWAA, NCMB A, and NCMB B retained a low
temperature grade similar to the control binder. This finding
indicates that the modified asphalt binders did not increase the
low temperature grade but significantly increase stiffness and
decrease the m-value compared with the control sample.
3.8. Surface free energy
The surface free energy (SFE) values obtained from the software
are shown in Fig. 8. It is apparent from the graph that the values of
modified asphalt binders indicate higher SFE when compared with
unmodified binders. The changes in SFE values vary depending on
the types of modifiers used and their percentages. The amount of
modifiers in CWAA and NCMB did have an effect when the modi-
fied asphalt binder and the SFE increased concurrently with the
increase in the percentages of modifiers in CWAA and NCMB.
NCMB B4% showed the highest SFE while the unmodified asphalt
binder recorded the lowest SFE.
Additionally, the modifiers consist of amine, which is a basic
chemical to promote better adhesion between acidic asphalt
binder and acidic aggregate such as granite. Literature indicates

35

30
Surface Energy (mJ/m²)

25

20

15

10

0
Control CWAA CWAA CWAA CWAA NCMB NCMB NCMB NCMB NCMB NCMB
1% 2% 3% 4% A 3% A 4% A 5% B 3% B 4% B 5%

Fig. 8. Surface energy of unaged asphalt binders containing different percentages of modifiers.
 M.E. Abdullah et al. / Construction and Building Materials 112 (2016) 232–240
that amines consist of a long hydrocarbon chain and amine
group. The amine group reacts with the aggregate surface while
the hydrocarbon portion (hydrophobic) is directed into the
asphalt binder. As a result, a strong bond between aggregate
and asphalt binder would form due to the long hydrocarbon
chain, which acted as a link between the hydrophilic aggregate
and hydrophobic asphalt binder surfaces [51,62–65]. Therefore,
these factors could increase the adhesion between the asphalt
binder and its aggregates. Thus, in most cases, modified
asphalt binders will increase an asphalt mix’s resistance to
moisture-induced damage.
4. Conclusions
This research was conducted to assess the effects of asphalt bin-
ders containing several types of additives based on a series of
related testing. The results indicate that NCMB B has a similar char-
acteristic when compared with CWAA, an established WMA addi-
tive in the market. In addition, the following conclusions could
be drawn:
(i) The NCMB A and NCMB B reduced penetration and increased
softening point, in which the NCMB A showed a larger effect
of the two. In contrast, CWAA showed a different trend
wherein its penetration increased and its softening point
decreased when the percentage of chemical WMA additive
was increased.
(ii) The PI values for NCMB A and NCMB B increased while the PI
values for CWAA decreased. Additionally, modified asphalt
binders showed an almost similar trend in PVN values.
Therefore, asphalt binders containing nanoclay results in
higher PI and PVN values, which could increase the
resistance of the asphalt mixes to thermal cracking and
rutting.
(iii) The use of CWAA and NCMB B reduced viscosity values
while NCMBA significantly increased viscosity value when
compared with base asphalt binder.
(iv) The storage stability test was conducted to ensure that the
blending processes were effective and the modified binders
would be stable during storage. Results showed that all
modified binders meet the specifications and could be
regarded as a storage stable blend.
(v) The G⁄/sin d value and failure temperature values of NCMB A
and NCMB B were significantly increased, which indicates
higher elasticity and increased rutting resistance compared
to base asphalt binder. On the other hand, the G⁄/sin d and
failure temperature values of CWAA were reduced, although
the PG grade remained the same as the base asphalt binder’s
PG grade.
(vi) The results indicate a decrease in the value of G⁄sin d of
CWAA and NCMB B compared with based asphalt binder.
However, the G⁄sin d values of NCMB A increased. It is pre-
dicted that the CWAA and NCMB B could have better resis-
tance to fatigue cracking at intermediate temperatures
compared to base asphalt binder.
(vii) CWAA, NCMB A, and NCMB B showed a significant increase
in stiffness and reduced m-values when compared with base
asphalt binder. This indicates that the addition of modifiers
resulted in slightly lesser resistance to low temperature
cracking.
(viii) The modified asphalt binders exhibited significantly higher
SFE when compared with unmodified asphalt binder and
could have good adhesion between aggregates. Therefore,
modified asphalt binders could potentially be good at
increasing the resistance of asphalt mixes to moisture-
induced damage.
239
(ix) NCMB B4% could potentially become a new WMA binder in
comparison to CWAA.
Acknowledgement
The authors would like to appreciate the support from the Min-
istry of Higher Education in form of research grant (FRGS) Vote
1458 and also Universiti Teknologi Malaysia for RUG grant Vote
TIER 1 06H58.
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