Road Materials and Pavement Design

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The influence of nano-carbon from coconut shell

ash as modifier on the properties of bitumen

Siti Nur Amiera Jeffry , Ramadhansyah Putra Jaya , Norhidayah Abdul

Hassan , Haryati Yaacob , Mohd Zul Hanif Mahmud & Zaid Hazim Al-Saffar

To cite this article: Siti Nur Amiera Jeffry , Ramadhansyah Putra Jaya , Norhidayah Abdul
Hassan , Haryati Yaacob , Mohd Zul Hanif Mahmud & Zaid Hazim Al-Saffar (2020): The influence
of nano-carbon from coconut shell ash as modifier on the properties of bitumen, Road Materials
and Pavement Design, DOI: 10.1080/14680629.2020.1809502

To link to this article: https://doi.org/10.1080/14680629.2020.1809502

Published online: 26 Aug 2020.

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ROAD MATERIALS AND PAVEMENT DESIGN
https://doi.org/10.1080/14680629.2020.1809502

The influence of nano-carbon from coconut shell ash as modifier

on the properties of bitumen
Siti Nur Amiera Jeffrya , Ramadhansyah Putra Jaya b , Norhidayah Abdul Hassanc , Haryati
Yaacobc , Mohd Zul Hanif Mahmudc and Zaid Hazim Al-Saffarc
a Department of Irrigation and Drainage Sarawak, Wisma Seberkas, Kuching, Malaysia; b Department of Civil
Engineering, College of Engineering, Universiti Malaysia Pahang, Gambang, Malaysia; c School of Civil Engineering,
Faculty of Engineering, Universiti Teknologi Malaysia, Johor Bahru, Malaysia

ABSTRACT ARTICLE HISTORY

Nanomaterials are small-sized materials between 1 and 100 nm which pro- Received 16 March 2020
duce a greater surface area than common size materials. Coconut shell is Accepted 6 August 2020
one of the potential agricultural wastes to be used as nanomaterial due KEYWORDS
to its high strength and hardness. However, poor adhesion bonding was Nano-carbon; coconut shell
the problem of using this agricultural waste material as a modifier in the ash; bitumen; physical;
bitumen matrix. Therefore, in this study nanocarbon from coconut shell rheological
ash (NCA) was produced as bitumen modifier. NCA was produced and
characterised using various techniques prior to be utilised at 0.0%, 1.5%,
3.0%, 4.5%, 6.0% and 7.5% by weight of bitumen PEN 60/70. The rheolog-
ical test, using a dynamic shear rheometer (DSR), was performed on the
unaged, rolling thin film oven and pressure ageing vessel samples. Sub-
sequently, X-ray diffraction and atomic force microscopy were performed
on the unaged samples. The DSR results revealed that NCA improved the
rutting and fatigue cracking parameter of the bitumen. Also, the observa-
tions from microstructure properties showed that NCA delayed the ageing
of the bitumen, produced a homogenous structure and increased the cohe-
sion and adhesion properties of the bitumen. As a result, a strong bonding
between the NCA and bitumen was formed and the properties of bitumen
were altered.

1. Introduction
The use of additives to modify the bitumen has significantly increased because the properties of the
conventional bitumen are insufficient to accommodate the high traffic loads. Previously, numerous
additives have been used as bitumen modifiers in order to reinforce the bitumen and improve the
properties. The additives include polymers, industrial by-products, waste materials and agricultural
waste materials (Brown et al., 2009; Choudhary et al., 2020 Hunter et al., 2015; Shafigh et al., 2014).
Due to higher demands of traffic loads and greater influence by the temperature, stronger bitumen
properties are, therefore, needed. Since most of the additives are in micro-scale, the nano-scaled mate-
rials have recently garnered considerable attention as bitumen modifiers (Ali et al., 2017; Ashish &
Singh, 2019; Hamedi, 2017; Shafabakhsh et al., 2020; Wu & Tahri, 2019) owing to their smaller size
and larger surface area compared to materials in micro-size. The large surface area of the nanomate-
rial could help in improving the bonding between the modifier and bitumen matrix. Consequently,
the properties of bitumen can be improved and long-term effects on pavement performance can be

CONTACT Ramadhansyah Putra Jaya ramadhansyah@ump.edu.my

© 2020 Informa UK Limited, trading as Taylor & Francis Group

2 S. N. A. JEFFRY ET AL.

produced (Azarhoosh et al., 2018). In the range of 1 μm or 1000 nm to 0.1 nm, materials are classi-
fied as nanomaterials. However, the novel and unique properties of materials are developed at the
nanoscale in the range of 1–100 nm due to their small size (Hornyak et al., 2008; Jeffry et al., 2018a).
To be more specific, nanomaterial is a material with at least one dimension within 1–100 nm (Fuente
& Grazu, 2012; Li et al., 2017). Owing to the large surface area, the nanomaterials exhibit higher reac-
tivity than other common-sized particles (National Nanotechnology Initiative, 2010). This is because
the greater surface area of the nanomaterials increases the exposure and the frequency of collision
with surrounding materials, thereby an increase in the rate of reaction leads to strong interfacial
interaction between materials (Abdullah et al., 2015). One of the benefits of the greater surface area
is that it helps in accommodating excellent adhesion with the matrix. Nano-scale research requires
detailed understanding in terms of sciences (chemistry) in which the composition, properties, struc-
ture and interrelationship of materials are important to be examined (Steyn, 2011). Furthermore, the
compatibility of the nanomaterials in the bitumen must be evaluated to ensure the effectiveness
of the materials in terms of stiffness and temperature susceptibility when they are applied as pave-
ment materials. Basic engineering property tests are not sufficient to explore the compatibility of the
different materials (Steyn, 2011). Hence, numerous advanced techniques have been conducted by pre-
vious researchers to characterise the nanomaterials and their behaviour in the bitumen and asphalt
mixture.
You et al. (2011) used X-ray diffraction (XRD) to determine the rate dispersion of nanoclay in the
bitumen modification. It was revealed that XRD patterns of the control bitumen and the nanoclay-
modified bitumen were similar. This indicated that the nanoclay was uniformly dispersed in the
bitumen matrix. Nazzal et al. (2013) reported similar findings in which the nanoclay was well dis-
persed and uniformly distributed in the bitumen matrix which was performed by the XRD. Apart from
that, Nazzal et al. (2013) investigated the effect of nanoclay in bitumen PG 70-22 using atomic force
microscopy (AFM). After 4% of nanoclay was added in the bitumen, higher interaction occurred due to
higher contra between the dispersed phase and the bitumen matrix. It was also indicated that the dis-
persed domains were stiffer after the incorporation of nanoclay in the bitumen which could improve
the mechanical properties of the modified bitumen compared to the control bitumen. A previous
study by Zhang et al. (2011) stated that the dimensions of the bee-like structures were decreased after
the bitumen was modified with organo-montmorillonite (OMMT). This indicated high dispersion of the
nanomaterial in the bitumen matrix and the reduction of surface roughness which help to increase the
adhesion property (Azahar et al., 2017; Dourado et al., 2012).
Very few studies using nanomaterials from agricultural wastes on the modification of bitumen have
been found. Of all agricultural wastes, coconut shell is seen as having the potential as nanomaterial
in bitumen modification due to its strength and good quality in various construction materials, for
example concrete, mortar and cement paste. Also, it is very economical as large amounts are avail-
able as agricultural waste material. Previous studies (Jeffry, Jaya, et al., 2016; Kanojia & Jain, 2017;
Norhafizah et al., 2016; Prasath Kumar et al., 2019; Ramadhansyah et al., 2016; Ramadhansyah et al.,
2020) showed that coconut shell particles improved the strength and hardness of construction mate-
rials since it is a strong and rigid material. Coconut shell also has been used as a bitumen modifier,
but the research studies focused on the micro-scale (Abdullah et al., 2015; Jeffry et al., 2018b). The
results showed significant improvement in the properties of bitumen; however, the number of tests
conducted was very limited. Therefore, this paper focuses on the microstructure properties of bitumen
modified using nanocarbon from coconut shell ash. The microstructure tests conducted include field
emission scanning electron microscopy (FESEM), XRD and AFM.

2. Materials, sample preparations and experimental work

Bitumen and raw coconut shell were the main materials used in this study. The conventional bitu-
men PEN 60/70 was supplied by Chevron Company. The properties are shown in Table 1. Meanwhile,
coconut shell was collected from a market in Johor, Malaysia.
 ROAD MATERIALS AND PAVEMENT DESIGN 3

Table 1. Properties of bitumen PEN 60/70.

Properties tests Results Requirements Standard
Penetration at 25°C (dmm) 60.9 60–70 ASTM D5/D5M (ASTM D5/D5M, 2013)
Softening point (°C) 49.0 49–56 ASTM D36/36M (ASTM D36/D36M, 2014)
Viscosity at 135°C (Pa·s) 0.5 < 3 Pa.s ASTM D4402/D4402M (ASTM D4402/D4402M, 2015)
Rutting parameter, G*/sinδ (kPa) at 64°C 1.685 > 1 kPa ASTM D7175 (ASTM D7175, 2015)
Specific gravity 1.030 - ASTM D70 (ASTM D70, 2018)

2.1. Production of nanocarbon coconut shell ash

The fibre of the coconut shell was cleaned and then crushed to smaller sizes using an aggregate crusher
machine. After that, the crushed coconut shell was burned at an optimum temperature of 450°C for
5 min in a small furnace. The burning parameters were obtained from thermogravimetric analysis
(TGA) and past studies (Jeffry, Putra Jaya, et al., 2016; Ouyang et al., 2013; Zhao, Huang, Shu, et al.,
2014; Zhao, Huang, Ye, et al., 2014). Next, the charcoal that was produced after the burning process
was crushed again to finer sizes using a Los Angeles Abrasion machine which carried out 300 rota-
tions for approximately 15 min. The crushed charcoal was then sieved using a mechanical sieve shaker
in order to obtain charcoal sieve size of less than 75 µm. After few trial and error of grinding using a
ball mill, it was found that the 15 h of grinding achieved the nanometer size of particles. The whole
experimental process of production of nanocarbon coconut shell ash (NCA) is shown in Figure 1.

2.2. Characterisation tests of NCA

The properties of NCA were then examined such as the size, structure, morphology, chemical elements
and compositions in the subsequent sections.

2.2.1. Particle size analysis

Particle size analyser (PSA) (Malvern Zeta-sizer Nano-ZSP ZEN 5600) was used to analyse the particle
size distribution of the ground charcoal. The dynamic light scattering technique was used in this test
which can measure particle sizes in the range of 0.3 nm to 10 μm. The test required only a small amount
of samples with concentrations ranging from 0.1 mg/mL to 40% w/v of the sample. Distilled water was
used to dilute the sample for 24 h in order for the sample to disperse adequately.

2.2.2. Field emission scanning electron microscopy

FESEM is typically used to analyse the surfaces of the material which include morphology, chemical ele-
ments, crystalline structure and orientation of materials making up the sample. The energy-dispersive
X-ray (EDX) was equipped with FESEM to detect the chemical elements of the sample. In this study,
FESEM (Hitachi SU8000) was used to analyse the morphology and chemical elements of the ground
charcoal. For the sample preparation, the sample was coated with platinum using the coating machine.
Then, the sample was placed on the metal stub whereby carbon conductive paste was used to attach
the powder sample (ground charcoal) on the metal stub. After that, the metal stub was placed on the
sample holder prior to imaging observation.

2.2.3. Transmission electron microscopy

Transmission electron microscopy (TEM) was used to further analyse NCA that was obtained from PSA.
TEM (Hitachi HT7700) was used in this study. It was used to get a higher resolution image and mag-
nification of the particles. This instrument can visualise and analyse a sample in the range of 1 μm to
1 nm. In this test, a small amount of the particles was suspended in a solvent (iso-propanol) prior to
sonicating. The sonication took about 15–30 s in order to disperse the particles. One or two drops of
the dispersed particles were then placed on a copper grid and were left to dry. The image of the sample
was then analysed.
4 S. N. A. JEFFRY ET AL.

Figure 1. Experimental process of production of NCA.

2.2.4. Chemical element

As coconut shell undergoes biomass combustion, the characteristics are determined using the prox-
imate and ultimate analysis. Thermogravimetry analyser TGA-IR (TGA Q500 FTIR) and elemental anal-
yser (Elementar) were used to analyse the NCA. Both analyses determine the chemical compositions of
the NCA. The proximate analysis provides the moisture, ash, volatile and fixed carbon, while the ulti-
mate analysis gives more comprehensive chemical elements which are carbon, hydrogen, nitrogen,
sulphur and oxygen.

2.2.5. BET single point and specific gravity

The specific surface area (SSA) of the NCA sample was determined using a BET single point test
(Micromeritics PulseChemisorb 2705). This test was carried out in accordance with ASTM D4567-03
(2013). In this test, the surface area of the NCA sample was determined by the physical adsorption of
 ROAD MATERIALS AND PAVEMENT DESIGN 5

nitrogen gas on the surface of the sample. The determination of the dead volume was also included
by admitting the non-adsorbed gas, which is helium. The amount of adsorbed gas that correlates to
the surface area of the particles, including the pores, was then measured.
The specific gravity of NCA was obtained by gas pycnometric (Micromeritics Accupyc II TEC). Gas
displacement method was used to perform this test. Helium gas was used as the displacement medium
to measure the volume. About 1 g of the NCA sample was sealed in the chamber of known volume.
Then, the gas was admitted into the sample chamber until the gas filled the chamber evenly. After that,
the gas flowed into the second empty chamber which then computed the volume of the sample. The
density was determined by dividing the sample mass with the computed volume, wherein the density
result was automatically displayed on the monitor, which also includes the specific gravity result.

2.2.6. X-ray diffraction

XRD is a non-destructive technique to find the crystal structure of the unknown material, measure the
average spacings between layers or rows of atoms, determine the orientation of a single crystal or
grain and determine the atomic arrangement. In this study, XRD was used to identify the arrangement
of the atoms and uniformity of the NCA. Slurry of powder sample, i.e. NCA, was prepared with distilled
water. The water was then allowed to evaporate until the slurry was smeared onto the glass slide. Then
the test was carried out using Rigaku SmartLab equipment.

2.3. Bitumen modification process

The blending of NCA in the bitumen was performed at the content of 0.0% (as control sample), 1.5%,
3.0%, 4.5%, 6.0% and 7.5% NCA by weight of the bitumen. The modification only required small
amounts of the NCA in consideration of the dispersion and material cost. A gap of 1.5% was chosen in
order to examine the sensitivity of the NCA content in the bitumen. The blending process of bitumen
and NCA was conducted by using a high shear mixer. The blending was carried out at the speeds of
1500 rpm for 60 min at 160°C. A speed of 1500 rpm was used to ensure that the NCA was well dispersed
in the bitumen. Blending was conducted at 160°C because it is sufficiently fluid at this temperature.
Approximately 60 min of mixing was used to ensure adequate mixing between the NCA and bitumen
to produce a homogeneous binder (Fang et al., 2013). Overall, these parameters were chosen to ensure
the particles disperse well in the bitumen matrix and minimise the ageing in order to come out with
homogenous bitumen mixing.

2.4. Rheological property tests on NCA-modified bitumen

Dynamic shear rheometer (DSR) test was used to measure the rheological properties of NCA-modified
bitumen. The test was conducted in accordance with ASTM D7175 (2015). The viscoelastic behaviour
of bitumen was determined by the complex shear modulus G* and phase angle δ at intermediate to
high temperature. G* and δ values depend on the test temperature and frequency of loading. The
rutting and fatigue cracking performances of the asphalt pavements were analysed from G*/sin δ
and G*.sin δ, respectively. In this study, the test was conducted from 46°C to 82°C at an increment
of 6°C for the rutting performance and 40–22°C at a decrement of 3°C for the fatigue cracking perfor-
mance. At high temperature, the unaged and rolling thin film oven (RTFO) samples were tested using
a 1 mm-thick plate and 25 mm-diameter top plates. Meanwhile, at lower temperature, the pressure
ageing vessel (PAV) sample is stiffer and the measurement of phase angle (δ) is quite small thus, 2mm-
thick plate and 8 mm diameter top plates were used so that the measured phase angle (δ) can be
obtained.

2.5. Microstructure property tests on NCA-modified bitumen

XRD and AFM were used to investigate the microstructure properties of the NCA-modified bitumen.
6 S. N. A. JEFFRY ET AL.

Figure 2. Cumulative particle size distribution of ground charcoal.

2.5.1. X-ray diffraction

XRD was also used to identify the arrangement of the atoms and uniformity of the control and NCA-
modified bitumen. Prior to the testing, a thin film bitumen sample was prepared onto the glass slide
with a diameter of 1 cm.

2.5.2. Atomic force microscopy

AFM can measure the properties of materials at the atomic scale. Generally, AFM operates by scanning
the sample surface at an ambient temperature. Three types of interaction mode in AFM are contact
mode, tapping mode and non-contact mode. The type of mode used depends on the characteristics
and the hardness/stickiness of the sample. In this study, tapping mode was used since it is usually used
for soft samples such as polymers and thin film. For the bitumen sample preparation, the sample was
prepared on the glass slide with a diameter around 1 cm and a thickness of less than 4 mm.

3. Result, analysis and discussion

3.1. Characteristics of NCA
3.1.1. Particle size analyser
PSA was used to determine the size distribution of the ground charcoal. Figure 2 shows the particle
size distribution obtained from PSA. It can be seen the particle size distribution of 15 h was less than
100 nm for 100%. The size of particles at 50% and 90% distribution was 59 and 68 nm, respectively.
Meanwhile, the average particle size was 57.7 nm. Meanwhile, the particle size distributions of 5, 10
and 20 h exceeded 100 nm. The average particle sizes for 5, 10, 15 and 20 h were 282.7, 211.0, 57.7 and
149.2 nm, respectively. The distributions of the particle sizes can be seen decreased with an increase
in grinding time and then increased at 20 h.

3.1.2. Field emission scanning electron microscopy

Figure 3 presents the images of the morphologies of the particles size ground at 5, 10, 15 and 20 h
at a magnification of 2k and a scale of 30 μm. It can be seen that the particle size distribution of the
samples decreased with the increase of grinding time until 15 h and then increased for 20 h of grinding
time. These results coincide with the PSA test in which increasing the grinding time will not decrease
the average particle size significantly. This is because the particles have reached the breakage limits
and achieved the optimum grinding time.
 ROAD MATERIALS AND PAVEMENT DESIGN 7

Figure 3. Particle distribution of ground charcoal: (a) 5 h; (b) 10 h; (c) 15 h and (d) 20 h.

As can be seen in Figure 3(a), the particle breakage for 5 h sample was lower than other samples
due to its large, irregular and elongated shape. Higher particle breakage was then observed when the
10 h sample attained smaller particle distribution and irregular shaped, as shown in Figure 3(b). Sub-
sequently, very fine particles were achieved with uniform distribution as a result of greater particle
breakage for the 15 h sample, as presented in Figure 3(c). Then, it was found that the particle distri-
bution for the 20 h sample in Figure 3(d) was slightly larger than the 15 h sample with few irregular
shapes. The higher grinding time leads to agglomeration of particle sizes, which might be the cause
of increased average particle sizes for the 20 h sample. The particle distribution is very important in
order to provide more surface area for adhesion purposes. Furthermore, the formation of nano-sized
particles from the uniform distribution of 15 h particles can provide more surface area for bitumen
matrix reinforcement. The uniform distribution of the 15 h particles is, therefore, significant in order to
produce optimum characteristics of nanomaterial.
FESEM was then used to examine the morphology of NCA. As shown in Figure 4, the particles were
magnified to 15k. The particles appear to have smooth and porous surfaces with numerous broken
pieces. According to Zhao, Huang, Ye, et al. (2014), the strong adhesion between bitumen and car-
bon could be attributed to the porous structure of the charcoal. Hence, this surface structure can help
provide an extensive bonding between the nanoparticles and bitumen matrix.
Subsequently, Figure 5 presents the chemical elements of the particles which were observed by
energy-dispersive X-ray spectroscopy (EDX). The percentages of chemical elements were detected on
the surface of the sample regardless of the whole structure. Notably, higher percentage of carbon was
recorded by EDX compared to percentage of carbon detected by the elementar because EDX only
detected elements present on the surface of NCA. Based on the result, the sample recorded carbon
element with 86.2%. Other chemical elements detected were oxygen (11.3%), nitrogen (2%) and potas-
sium (0.5%). Also, the presence of elements from group 1 of the periodic table, including hydrogen,
cannot be detected by EDX because those elements are too light.
8 S. N. A. JEFFRY ET AL.

Figure 4. Surface morphology at 15k magnification of NCA.

Figure 5. EDX of NCA.

3.1.3. Transmission electron microscopy

The confirmation of the nano-sized particles produced by 15 h grinding time was measured through
high-resolution image using TEM, as shown in Figure 6(a). The image was taken at 100 nm scale. As
can be seen, the particles showed round and irregular shaped, with all three dimensions within the
range of 1–100 nm. The image also presented different shades because of particles overlap, which
darkened certain parts of the particles. Figure 6(b) shows the larger images of the particles size in red
circle, where the particles size were in the range of 17–50 nm, which is in agreement with the particle
size distribution obtained from PSA. These outcomes supported the 15 h grinding using the charcoal
passing 75-μm sieve size for producing NCA.

3.1.4. Chemical elements, SSA and specific gravity

The results of chemical elements, SSA and specific gravity of the NCA are shown in Table 2. The ele-
mental composition of NCA recorded the carbon content of 77%. The second highest was oxygen with
19.5% followed by hydrogen, nitrogen and sulphur which came in small percentages. These results
 ROAD MATERIALS AND PAVEMENT DESIGN 9

Figure 6. TEM images of NCA particles.

Table 2. Properties of NCA.

Chemical properties (%)
Carbon 77.4
Hydrogen 2.70
Nitrogen 0.24
Sulphur 0.13
Oxygen 19.53
Physical properties
Specific surface area (m2 /g) 112.74
Specific gravity 1.267

agree with the study conducted by Ouyang et al. (2013) and Rout (2013). The elemental composition
of the produced NCA was comparable to the elements of conventional bitumen. The approximate
chemical composition of NCA and the bitumen could help to increase the performance of the bitumen
due to its carbonaceous properties (Zhao, Huang, Shu, et al., 2014; Zhao, Huang, Ye, et al., 2014).
The SSA of NCA that was obtained from the BET single point test was 112.74 m2 /g. This result is
comparable with studies carried out by Abdul Rajak et al. (2015) and Shafabakhsh and Ani (2015) in
which the SSA obtained was higher than 100 m2 /g for nanoparticles in the range of 20–90 nm. High
surface area of nanoparticles could accommodate high adhesion with the bitumen matrix, therefore
improving the bonding and increasing the strength of the bitumen. Meanwhile, the specific gravity
of NCA was 1.267, which was higher than the specific gravity of bitumen. Based on the SSA and spe-
cific gravity of NCA, a volume-specific surface area (VSSA) was then computed about 142.84 m2 /cm3 .
European Commission (2011) stated that nanomaterials could be classified if the VSSA is higher than
60 m2 /cm3 . Hence, NCA is in agreement with the statement as a nanomaterial in this study.

3.1.5. X-ray diffraction

Figure 7 illustrates the NCA pattern produced by XRD. The arrangement of the NCA atoms can be
seen recorded in the amorphous structure in which the diffraction did not occur during the testing.
The amorphous pattern occurred because the atoms of NCA did not have an ordered structure that
was contributed by the nature of carbon element. For NCA, high carbon formation was attributed to
the decomposition of the coconut shell components, which are hemicelluloses, cellulose and lignin
(Ouyang et al., 2013; Rout, 2013). There exists one narrow peak at 27° 2-theta with the d-spacing of
3.246 which was iron hydroxide sulphate (Fe(SO4 )2H). The presence of the peak in the amorphous
structure could be due to the contamination by the steel balls during the grinding process. The
existence of the peak also showed that the material has an ordered structured known as crystalline
10 S. N. A. JEFFRY ET AL.

Figure 7. XRD pattern of NCA.

structure. However, NCA was categorised as amorphous structure despite minor contamination by
the crystalline structure. This structure could help in high nanoparticle dispersion in the bitumen
matrix.

3.2. Rheological properties of NCA-modified bitumen

The rheological properties of unaged, RTFO and PAV samples for control and NCA-modified bitumen
were analysed.

3.2.1. Unaged samples

Figure 8 illustrates the visco-elastic properties of control and NCA-modified bitumen. As can be seen,
the complex modulus (G*) of the NCA-modified bitumen was higher than the control bitumen. The
outcomes showed that the modified samples were stiffer and have higher resistance to rutting than
the control sample. On the other hand, the phase angle, δ of the modified samples resulted in lower
degrees than the control sample. The lower amount indicated the modified bitumen responded and
recovered quickly after being loaded. Also, the upper performance grade (PG) recorded by the NCA-
modified bitumen was 76°C higher than the control bitumen, which failed at 70°C.
This finding showed that the elasticity of the modified samples was higher than that of the control
sample. Thereby, the stiffness of the modified bitumen was increased which led to higher resistance
to rutting. This could be attributed to NCA particles which reinforced the bitumen matrix by creat-
ing strong bonding between the particles. Meanwhile, an observation among the modified samples
showed that 6.0% NCA has the highest G* and the lowest δ. When the NCA was increased to 7.5% NCA,
the G* reduced and δ increased, which might be due to excessive NCA content.
This analysis showed that NCA improved the stiffness and elasticity of the bitumen which produce
higher resistance to rutting. Desirable G* and δ values were produced when the optimum NCA was
reached. This improvement could be related to the high surface area of the nanosized particles which
established strong interfacial interaction between the particles of NCA and the bitumen matrix. The
adhesion characteristic of the particles was improved significantly due to strong bonding between the
particles. Those mechanisms reinforced the bitumen matrix and enhanced the stiffness and elasticity
of the bitumen which improved the performance of rutting.
 ROAD MATERIALS AND PAVEMENT DESIGN 11

Figure 8. Visco-elasticity of unaged samples.

Figure 9. Visco-elasticity of RTFO samples.

3.2.2. RTFO samples

Further analysis was carried out using the RTFO samples to simulate the short-term ageing of the sam-
ples which occur during the mixing and compaction of the hot mix asphalt. Figure 9 presents the
RTFO results for the G* and δ values for the control and NCA-modified samples. The results obviously
showed higher values of the complex modulus (G*) than the unaged samples. In this analysis, the con-
trol sample obtained higher G* value and lower δ value than the NCA-modified samples. This result
was in contrast with the unaged samples previously because the stiffness and elasticity of the modified
samples were reduced.
This is thought to be due to NCA delaying the ageing process of the bitumen. Reduction of the
oxidation of bitumen can be an advantage for the long-term performance of the asphalt pavement.
Besides that, both control and NCA-modified samples still performed until 70°C prior to failure at 76°C.
12 S. N. A. JEFFRY ET AL.

Figure 10. Visco-elasticity of PAV samples.

Among the NCA samples, 4.0% NCA showed the highest G* and the lowest δ, while 3.0% NCA recorded
the lowest G* and the highest δ values. No significant difference was observed between the G* and δ
of the 6.0% and 7.5% NCA samples, respectively. At this stage, 6.0% NCA was performed at moderate
level.
As mentioned earlier, NCA seems to retard the ageing process of the bitumen since the stiffness of
the control sample was higher and the phase angle was lower than the NCA-modified samples. This
process could be attributed to the particles of NCA, which reduce the oxidation process by distributing
the heat in the bitumen. The large surface area of the NCA absorbs and distributes the heat relative
to the control bitumen, which stands alone in absorbing the heat at a higher rate than the modified
bitumen, thereby causing the bitumen to age quickly, which produces stiffer bitumen. Since RTFO
sample represents an early stage of ageing prior to long-term ageing, excessively stiff bitumen at this
stage can lead to higher stiffness during the service life of the pavement. Therefore, NCA particles have
the ability to reduce the ageing of the bitumen.

3.2.3. PAV samples

The analysis of the long-term ageing was carried out using the PAV samples. It is used to simulate the
ageing during the service life of the asphalt pavement. The results of G* and δ are shown in Figure 10.
It was found that the G* value for 6.0% and 7.5% NCA was lower, while 1.5%, 3.0% and 4.5% NCA were
higher than the control sample. Also, the δ can be seen decreasing to lower than 45° as the temperature
decreased. The 4.5% NCA sample possessed the lowest δ, while 3.0% NCA recorded the highest δ,
which was contrary to the trend in G*. Also, 6.0% and 7.5% NCA have higher δ than the control sample.
It was noted that the performance of the PAV samples was different from that of the unaged and
RTFO samples. For this analysis, too high G* value and too low δ value could lead to pavement distress
which is fatigue cracking. Based on these results, the stiffness of the 6.0% and 7.5% NCA was lower
than the control sample when the temperature was decreased. At the same time, the elasticity also
decreased due to δ approaching higher degrees. It can be seen that 1.5%, 3.0% and 4.5% NCA exhibited
stiffer bitumen which caused failure at earlier temperature than the control sample, 6.0% and 7.5%
NCA.
As previously discussed, the NCA particles attracted more particles of bitumen due to its large sur-
face area and reinforced the bitumen matrix by creating strong bonding between those particles. It
then increased the cohesiveness of the bitumen and produced stiffer bitumen than the control sample.
 ROAD MATERIALS AND PAVEMENT DESIGN 13

Figure 11. XRD patterns for control and NCA-modified samples.

However, during the service life of the pavement, bitumen tends to stiffen due to oxidation, leading
to fatigue cracking at a lower temperature. Nevertheless, the results in this study could be due to the
absorbed heat in the NCA-modified bitumen during high temperature was stored longer than in the
control sample. Thus, during the decrement of test temperature, the NCA slowly released the heat
and the heat loss under equilibrium condition, which helps in maintaining the viscoelasticity of the
bitumen, instead of rapidly releasing the heat and stiffening the bitumen. A higher content of NCA,
namely 6.0% and 7.5%, can retard the ageing process effectively compared with 1.5%, 3.0% and 4.5%
NCA sample due to particles of NCA accumulated more on the surface than distribute homogenously
in the bitumen to release the heat. The large surface area of the NCA delayed the heat loss especially
when more amounts were added, wherein 6.0% and 7.5% NCA have a higher capacity to store the
heat. As a result, 6.0% and 7.5% NCA have a higher resistance to fatigue cracking than the control and
other modified samples.

3.3. X-ray diffraction

Figure 11 illustrates the pattern of the control and NCA samples which was obtained from the XRD test.
As can be seen, the amorphous pattern was observed in the control sample as well as NCA samples. The
existence of a broad peak at 19.8° 2-theta with d-spacing of 4.48 in the control sample showed that less
diffraction had occurred. This indicated that the beam did not detect any arrangement of the ordered
structure during the testing. Since bitumen is an organic material majorly composed of hydrocarbon, it
did not have an ordered structure. This is logically acceptable since bitumen is a viscoelastic material
that varies with temperature. A similar arrangement of bitumen structure has been found in other
studies (Nazzal et al., 2013; You et al., 2011).
The same atom arrangements were observed in the pattern of NCA samples in which amorphous
patterns were recorded. The peaks were presented at approximately 18.8–19.9° 2-theta with the d-
spacing of 4.52–4.71 for the NCA samples. The broad peaks already showed that less diffraction was
detected. Based on the same pattern produced by the NCA samples, it can be seen that the incor-
poration of the NCA into the bitumen has produced a homogenous state of mixing, in which the
14 S. N. A. JEFFRY ET AL.

Figure 12. Topography of control and modified samples.

atoms of NCA were well dispersed and distributed uniformly in the bitumen matrix. Since NCA also
recorded a similar pattern with the conventional bitumen, it increased the compatibility between NCA
and bitumen matrix, thus, increased the cohesion property of the bitumen. This analysis proved that
the method used to blend the bitumen is effective where uniform modified bitumen was produced.

3.4. Atomic force microscopy

AFM produced a topography image of bitumen. Bitumen topography is composed of three phases,
namely, bee structure (consists of peaks and valleys), dispersed domain (dark colour region) and flat
matrix (light colour region). Figure 12 shows the topography images of the control and NCA-modified
samples. As can be seen, all the three phases existed in the control and the modified samples.
After the addition of NCA, the number of bee structures of the modified samples was increased
with the decreasing of the size compared to the control sample. As shown, the larger bee structure
led to the presence of larger black region. Among all NCA samples, 6.0% NCA showed the smallest
bee structures. Other than that, no additional structure appeared in the NCA samples. Overall, it was
noticed that the topography images of the control and NCA samples were almost identical, which
indicated that the NCA dispersed uniformly in the bitumen matrix. This might be attributed to the
high interfacial interaction between the NCA and the bitumen.
Consequently, the formation of bee structures affects the performance of the bitumen because its
influences the adhesion property of bitumen (Azahar et al., 2017; De Oliveira et al., 2012). As mentioned
before, the bee structure consists of peaks and valleys which contributed to the surface roughness
and affected the adhesiveness of the bitumen. A detailed measurement of the bee structures found in
the topography images is presented in Figure 13. The graphs showed values of total roughness (RT ),
average roughness (Ra ) and root mean square roughness (Rq ) of the control and NCA-modified sam-
ples. Similar trends have been observed in the three types of roughness, with NCA-modified samples
showing lower roughness than the control sample.
The trend decreased with the increase of NCA content until 6.0% NCA and then increased to 7.5%
NCA. Hence, 6.0% NCA exhibited optimum surface roughness. The size reduction of bee structures
 ROAD MATERIALS AND PAVEMENT DESIGN 15

Figure 13. Surface roughness of control and NCA-modified samples.

resulted in less surface roughness of the bitumen whereby a decrease of surface roughness leads to
an increase of adhesion characteristic. Less surface roughness could create a proper coating of the
bitumen matrix with the aggregates, which then improve the bonding and strength of the materi-
als. Also, the surface roughness is strongly influenced particularly by Rq , because Rq considered the
peaks and valleys of the surface. Peaks prevent the bonding between two different materials, thereby
reducing adhesion at the peak location (De Oliveira et al., 2012).

4. Conclusions
Based on the NCA characteristics, NCA could offer a high surface area to accommodate the particles of
bitumen in order to increase the bonding between the particles and reinforce the bitumen. Besides,
the high element of carbon and strong chemical functional groups exhibited by NCA can increase the
compatibility with the bitumen matrix and enhance the properties of bitumen. The assessment from
DSR for the unaged, short-term aged and long-term aged samples indicated that the NCA enhanced
the rheological properties of the bitumen in terms of rutting and fatigue cracking. The results were sup-
ported by the microstructure tests in which the NCA dispersed homogeneously in the bitumen matrix
which was observed using XRD. Thus, it leads to the enhancement of the cohesion property of the
bitumen. Also, the NCA samples have lower surface roughness than the control sample, as detected by
AFM. This low surface roughness could improve the adhesion property of the bitumen. This occurred
owing to the very small sizes of the nano-sized particle i.e. NCA which provided a high surface area
to reinforce the bitumen. The high surface area increased the exposure and frequency of collision.
Consequently, the rate of reaction increased and led to the strong interfacial interaction between the
NCA and the bitumen matrix. Thereafter, it enhanced the cohesive and adhesive properties of the
bitumen.

Acknowledgements
The support provided by the Malaysian Ministry of Higher Education, Universiti Malaysia Pahang and Universiti Teknologi
Malaysia in the form of a research grant for this study is highly appreciated.

Disclosure statement
No potential conflict of interest was reported by the author(s).
16 S. N. A. JEFFRY ET AL.

Funding
The support provided by the Malaysian Ministry of Higher Education, Universiti Malaysia Pahang and Universiti Teknologi
Malaysia in the form of a research grant for this study is highly appreciated.

ORCID
Ramadhansyah Putra Jaya http://orcid.org/0000-0002-5255-9856

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