materials

Article
An In-Depth Investigation into the Physicochemical,
Thermal, Microstructural, and Rheological Properties
of Petroleum and Natural Asphalts
Nader Nciri 1 , Jeonghyun Kim 2 , Namho Kim 2 and Namjun Cho 1, *
1 Department of Energy, Materials, and Chemical Engineering,
Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon,
Dongnam-gu, Cheonan-City, Chungnam-Province 330-708, Korea; nader.nciri@koreatech.ac.kr
2 Department of Architectural Engineering, Korea University of Technology and Education,
1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708, Korea;
jhk16@koreatech.ac.kr (J.K.); nhkim@koreatech.ac.kr (N.K.)
* Correspondence: njuncho@koreatech.ac.kr; Tel.: +82-41-560-1342

Academic Editor: Marco Morreale

Received: 14 August 2016; Accepted: 17 October 2016; Published: 21 October 2016

Abstract: Over the last decade, unexpected and sudden pavement failures have occurred in
several provinces in South Korea. Some of these failures remain unexplained, further illustrating
the gaps in our knowledge about binder chemistry. To prevent premature pavement distress
and enhance road performance, it is imperative to provide an adequate characterization of
asphalt. For this purpose, the current research aims at inspecting the chemistry, microstructure,
thermal, and physico-rheological properties of two types of asphalt, namely petroleum asphalt
(PA) and natural asphalt (NA). The binders were extensively investigated by using elemental
analysis, thin-layer chromatography with flame ionization detection (TLC-FID), matrix-assisted
laser desorption ionization time-of-fight mass spectroscopy (MALDI-TOF-MS), Fourier transform
infrared spectroscopy (FT-IR), Raman spectroscopy (RS), Nuclear magnetic resonance spectroscopy
(1 H-NMR), ultraviolet and visible spectroscopy (UV-VIS), X-ray diffraction (XRD), scanning electron
microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC),
penetration, softening point, ductility, and viscosity tests. The findings of this research have revealed
the distinct variations between the chemical compositions, microstructures, and thermo-rheological
properties of the two asphalts and provided valuable knowledge into the characteristics of the binders.
Such insight has been effective in predicting the performance or distress of road pavement. This
paper will, therefore, be of immediate interest to materials engineers in state highway agencies and
asphalt industries.

Keywords: petroleum asphalt; natural asphalt; chemical compositions; microstructures;

thermo-analytical behaviors; physico-rheological properties

1. Introduction
For enhancing the sturdiness and performance of roads, the Korean Pavement Research Program
(KPRP) was founded. The motivation behind this program was to provide safer means of passage
to both motorists and highway workers. In order to acquire higher pavement performance,
the KPRP utilizes its funds in developing the desired performance-based asphalt binder and mixture
specifications through laboratory methods. For attaining beneficial characterization and specifications
of asphalt, it is imperative to first comprehend its fundamental properties. At present, some critical
gaps have been observed in the specifications of the asphalt binders; they are not adequately recognized
as regards their chemical contribution to the pavement performance. The chemical compositions of

Materials 2016, 9, 859; doi:10.3390/ma9100859 www.mdpi.com/journal/materials

Materials 2016, 9, 859 2 of 20

the asphalts are found to control its physical characteristics in the final analysis [1,2], and yet most
scientists deny the need for chemical compositions in determining asphalt specifications.
It is a known fact that asphalts can be equipped with similar physical characteristics while differing
in terms of SARA (saturates, aromatics, resins, and asphaltenes) combinations [3]. While constructing
a highway, the materials used are dependent on their physical and rheological properties. Such
properties comprise of penetration, ductility, softening point, viscosity, etc. [4]. Nevertheless, roads
are subjected to rutting, undesirable potholes, and cracking due to the deployment of unsatisfactory
characterized binders. The inability to comprehend the binder chemistry and its relation with the
pavement performance is evident in the escalating amounts of unexpected pavement failures across
various provinces in the past few years. Also, some of these misgivings are left unexplained. Therefore,
examining and detecting the properties of the asphalt binder that result in high pavement performance
will benefit users, as the information can be exploited in determining the binders as per the performance
criteria. When applying this theory in practice, it is evident that the asphalt will have to be modified
for generating binders with consistent and reliable performance characteristics.
This research aims at revealing all the aspects of asphalt chemistry that will enable highway
agencies to develop high-quality pavement through new specifications for asphalt cement. For this
purpose, the current study will recognize the characteristics of the available materials along with the
distinct parameters in their chemical compositions that will assist in the manufacturing of the desired
asphalt cement by controlling their chemical composition. One efficient method to enhance the asphalt
is blending the available asphalt sources with additives on the basis of the knowledge acquired from
their chemical compositions. Another method is to modify the asphalt through the implementation
of designing processes, where the desired properties will be instilled in the asphalt. The knowledge
about the asphalt composition will be helpful in identifying the necessary components for modifying
the asphalt and producing an asphalt aggregate that will be superior in terms of durability and
performance in a specific environment. It will also be useful in detecting failures and constructing
solutions to rectify damage. Therefore, this research is anticipated to assist asphalt technologists and
highway engineers.
This investigation utilizes petroleum asphalt (PA) obtained from an anonymous refining company
in South Korea to examine the characteristics and specifications of the asphalt with the help of various
analytical techniques. These analytical methods are elemental analysis (EA), thin-layer chromatography
with flame ionization detection (TLC-FID), Raman spectroscopy, FT-IR spectroscopy, Nuclear magnetic
resonance spectroscopy (1 H-NMR), UV-Vis spectroscopy, scanning electron microscopy (SEM),
matrix-assisted laser desorption ionization time-of-fight mass spectroscopy (MALDI-TOF-MS), X-ray
diffraction (XRD), differential scanning calorimetry (DSC) analysis (for analyzing the glass transition
temperature (Tg )), and thermogravimetric analysis (TGA) (for estimating boiling distributions).
A battery of standard rheological techniques was also applied such as penetration, viscosity, softening
point, and ductility. In addition, structural comparisons with natural asphalt (NA) are made for
assessing the findings within the framework of enhanced materials.

2. Materials and Methods

2.1. Materials
For the purposes of the experiments, petroleum asphalt (PA) and natural asphalt (NA) were
acquired from an anonymous refining company in South Korea, and the asphalt quarry near Vernal,
UT, USA, respectively.
PA is manufactured by refining a crude oil through atmospheric distillation followed by vacuum
distillation. The atmospheric distillation is completed at temperatures in the range of 300–320 ◦ C. The
atmospheric residue is then sent to a vacuum distillation unit that operates around 320 ◦ C. Afterwards,
the bottom product (PA) was subjected to various types of chemical and physical treatments.
Materials 2016, 9, 859 3 of 20

The NA consists of a mixture of bitumen and minerals of the following composition: soluble
bitumen (56 wt %), clay minerals (8 wt %), and moisture (0 wt %). It is a sticky, black, and semisolid
liquid at room temperature. NA is extracted after heating in a furnace at 235 ◦ C.
The following methods and analysis were performed for estimating the association between the
asphalt rheological properties, composition, and microstructure. All the solvents and reagents used in
the assay procedures were analytical grade.

2.2. Analytical Methods

2.2.1. Elemental Analysis (EA)

For determining the quantity of C, H, N, O, and S in the asphaltic materials, a Thermo Fisher
Scientific™ Flash 2000 organic elemental analyzer (Thermo Fisher Scientific Inc., Darmstadt, Germany)
was utilized to perform the elemental analysis.

2.2.2. Thin-Layer Chromatography with Flame Ionization Detection Procedure (TLC-FID)

Iatroscan MK-6 analyzer (Iatron Laboratories Inc., Chiyoda, Tokyo, Japan) was utilized to
perform TLC-FID following the procedure defined in a published paper [5]. For the experiment,
80 mg of asphalt was added to 4 mL toluene to prepare a sample with a concentration of 2% (w/v).
The chromarods were then washed and stimulated in the FID-flame. Then, 1 µL of sample solution
was speckled onto the chromarods with the help of a spotter. To segregate the asphalt into the SARA
(i.e., saturates, aromatics, resins, and asphaltenes) compositions, a three-stage process was deployed.
In the first stage, the n-heptane experienced an expansion in chromarods to 100 mm. In the second
stage, the toluene/n-heptane (80/20 by volume) was expanded to 50 mm, and in the last stage the
dichloromethane/methanol (95/5 by volume) was expanded to 25 mm. Once these developments
were made, the solvents were vaporized in an oven at 80 ◦ C. After that the chromarods were scanned
in a TLC-FID analyzer (Iatron Laboratories Inc., Chiyoda, Tokyo, Japan).

2.2.3. Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass

Spectroscopy (MALDI-TOF-MS)
MALDI-TOF-MS test was applied to determine the mean molar mass values with the assistance of
a Bruker Autoflex III (Bruker Daltonik GmbH, Bremen, Germany) with an N2 (50 Hz) laser, in reflectron
mode. The target plate was positively charged at 20 kV. The mass range was scanned from 0 to 2500 m/z.
One milliliter of THF (tetrahydrofuran) was taken and the asphaltic samples were dissolved into it.
They were then speckled onto the target plate devoid of the matrix. The samples were dried once
the spotting was done and before the analysis was instigated. Dithranol (DT; 1, 8-dihydroxy-9,
10-dihydroanthracen-9-one) was used as the matrix. A delayed extraction mode, an extraction
delay time of 500 ns, a manual acquisition control, and a grid voltage of 70% were set as the
operating parameters.

2.2.4. Fourier Transform Infrared Spectroscopy (FT-IR)

KBr pellets were utilized to record the Bruker equinox 55 spectrometer (Bruker Daltonik GmbH,
Bremen, Germany) in the area of 4000–650 cm−1 for determining the FT-IR spectra of different fractions
of asphalt.

2.2.5. Raman Spectroscopy (RS)

A Nanofinder FLEX G Raman microscope (Tokyo Instruments Inc., Edogawa, Tokyo, Japan) was
utilized to conduct Raman spectroscopy by examining the results at high resolution. Prolonged scans
from 200 to 3600 cm−1 were executed using a typical exposure time and an accumulation of 3 s/20 time.
The microscope was helpful in concentrating on the excitation laser beam (green line of an argon laser
λ = 532 nm) onto the material. Twenty measurements were taken for each sample.
Materials 2016, 9, 859 4 of 20

2.2.6. Nuclear Magnetic Resonance Spectroscopy (1 H-NMR)

Qualitative proton 1 H-NMR spectroscopy analysis was conducted by deploying a Varian XL-300
NMR spectrometer (Agilent Technologies Inc., Santa Clara, CA, USA). This instrument was set at a
frequency of 300.13 MHz to perform the test for proton. The asphaltic samples were then dissolved in
Deuteriochloroform (CDCl3 ). The data for the proton was obtained by setting the acquisition time at
4.56 s and sweep width at 3591 Hz with no recycle delay. The proton spectra were referenced to the
deuterated chloroform (CDCl3 ) resonance at 7.28 ppm.

2.2.7. Ultraviolet and Visible Spectroscopy (UV-VIS)

Spectra were recorded on a JASCO V-730 spectrophotometer (JASCO International Co., Ltd.,
Hachioji, Tokyo, Japan) in the wavelength range 240-600 nm, with a bandwidth of 2 nm, a scanning
speed of 100 nm/min, and a response of 2 s. Measurements were conducted in a 1-cm quartz cuvette
at ambient temperature and pressure. Samples for optical studies were prepared by dilution of the
asphalt with a chemically pure grade dichloromethane (CH2 Cl2 ) to a final concentration of 0.001%.

2.2.8. X-ray Diffraction (XRD)

For this experiment, a high-power X-ray diffractometer (D8 Advance, Bruker AXS GmbH, Berlin,
Germany) was used at 12 kW. This instrument comprised of a rotating copper anode, a scintillation
counter, and a graphite monochromator. The asphaltic samples were subjected to this analysis, where
the diffraction patterns (5◦ ≤ 2θ ≤ 70◦ ) were recorded at room temperature using CuKα radiation
(λ = 1.54055 Å) at a scanning rate of 1 deg·min−1 and a step size of 0.02 (2θ).

2.2.9. Scanning Electron Microscopy (SEM)

A CX-100 scanning electron microscope (JEOL Ltd., Musashino, Akishima, Japan) was employed
in acquiring the morphology of the asphalt. These samples were layered with gold for 100 s in vacuum
with the help of a JFC-1600 fine coater (JEOL Ltd., Musashino, Akishima, Japan).

2.2.10. Thermogravimetric Analysis (TGA)

TA Instruments, i.e., TGA Q500 V20.13 Build 39 thermobalance (TA Instruments, Hüllhorst,
Germany) was used to conduct the thermogravimetric analysis. The test was performed under air
atmosphere. Those samples with 10 to 20 mg of mass were heated at 10 ◦ C/min from room temperature
to 700 ◦ C.

2.2.11. Differential Scanning Calorimetry (DSC)

Perkin-Elmer 7500 DSC (PerkinElmer Inc., Rodgau, Germany) was utilized to perform the DSC
tests. The instrument was adjusted at a temperature of 20 ◦ C/min against indium. Argon and helium
were utilized as the purging gases when the tests started at −60 ◦ C and −100 ◦ C. At 30 ◦ C, the samples
were kept in the sample cell and consequently cooled down to −60 ◦ C or −100 ◦ C at a cooling rate
of 200 ◦ C/min. For approximately 15 min the samples were kept at the low temperature to obtain
adequate results. Afterwards, they were heated to 100 ◦ C at a heating rate of 20 ◦ C/min. At this
temperature, the readings observed through the DSC thermogram were rendered as the first scan.
After this observation, the sample was cooled at a rate of 200 ◦ C/min from 100 ◦ C to its starting
temperature (−60 ◦ C or −100 ◦ C) and again held for about 15 min before being reheated to 100 ◦ C
at a heating rate of 20 ◦ C/min. The recording during this second heating scan was rendered as the
second scan. Perkin-Elmer’s software was then used to convert the DSC thermogram data into ASCII
format to conduct a comprehensive analysis on an IBM PS/2 computer. This research deployed a new
computer program to estimate and determine the calorimetric parameters.
Materials 2016, 9, 859 5 of 20

2.3. Determination of Rheological Properties

Penetration, viscosity, softening point, and ductility were the four tests that revealed the physical
or rheological properties of the recovered asphalt. To conduct the penetration test, a temperature of
25 ◦ C, loading weight of 100 g and needle penetrating time of 5 s were taken. These parameters were
consistent with ASTM D5-IP49, whereas the softening point test was conducted as per the ASTM D36;
ASTM D4402 was referred to for the viscosity test. A Brookfield Model DV-I viscometer (Brookfield
AMETEK, Middleborough, MA, USA) was utilized to perform the test for viscosity with a thermocel
temperature control system. The spindle deployed for determining the viscosity behavior of asphalt in
different conditions was SC-27. It was kept at a temperature of 135 ◦ C (field condition) and 180 ◦ C
(plant mixing condition). When considering the ductility test of the asphalt, ASTM D113 was used.
The ductility property is defined as the distance to which the asphalt will elongate before breaking
when two ends of the material are stretched at a particular speed and temperature. The test was
performed at a temperature 25 ◦ C with 5 cm/min speed.

3. Results and Discussion

As mentioned before, the current research aims at providing valuable insights into the chemical
compositions of the asphalts and their impact on its physical properties. This information will be
useful in generating adequate and efficient asphalt binders for road pavements. Also, this research
provides new basic tools to study asphalt chemistry. However, to assess the importance of the findings
obtained in a particular asphalt binder product are outside the scope of this work.

3.1. Elemental Analysis (EA)

Table 1 demonstrates the distinct chemical compositions of both the asphalts (PA and NA)
observed from the elemental analysis. From the analysis, it was found that asphalt constitutes higher
amounts of hydrocarbons (79.01~87.66 wt % carbon and 9.11~10.14 wt % hydrogen) and lower amounts
of heteroatoms (traces of up to 1 wt % nitrogen, traces of up to 6 wt % sulfur, and traces of up to
1.40 wt % oxygen). There is no difference between the H/C values of PA (1.38) and NA (1.38). This low
atomic H/C ratio establishes their aromatic character.

Table 1. Elemental analyses of asphaltic materials.

Asphalt
Elements and Ratios
PA NA
Carbon, wt % 87.66 79.01
Hydrogen, wt % 10.14 9.11
Nitrogen, wt % 0.44 0.95
Sulfur, wt % 6.29 0.72
Oxygen, wt % 0.29 1.38
H/C, atomic ratio 1.38 1.38
Organic matter, wt % 99.01 91.17
Inorganic matter, wt % 0.99 8.83

3.2. Thin-Layer Chromatography with Flame Ionization Detection (TLC-FID)

It should be noted that the asphalts have an exceptionally complex chemical composition. Solvent
precipitation and chromatography are two of the techniques that have been efficient for fractionation of
asphalts. For the current research, the TLC-FID technique is utilized. Figure 1 demonstrates the classic
TLC-FID chromatograms of asphalts. The four peaks visible in Figure 1 depicts the SARA compositions
(saturates, aromatics, resins, and asphaltenes). Table 2 demonstrates the generic fractions of the asphalt
material by normalizing the area. With the help of the standard composition, the colloidal instability
index (IC ) is also estimated and presented in the table.
Materials 2016, 9, 859 6 of 20
Materials 2016, 9, 859 6 of 19

Figure1.1.Iatroscan
Figure Iatroscanchromatographs
chromatographsofofPA
PAand
andNA.
NA.

The difference between the chemical compositions of PA and NA is evident in Table 2. It is

The difference between the chemical compositions of PA and NA is evident in Table 2. It is
observed that PA and NA have different values of SARA fractions, which results in varied colloidal
observed that PA and NA have different values of SARA fractions, which results in varied colloidal
instability index (IC) values. When considering the group composition, the contents of aromatics
instability index (IC ) values. When considering the group composition, the contents of aromatics
hydrocarbon (18.97 wt %) are observed to be higher in PA. On the other hand, the contents of
hydrocarbon (18.97 wt %) are observed to be higher in PA. On the other hand, the contents of saturates
saturates (4.40 wt %) in PA are observed to be lower than NA.
(4.40 wt %) in PA are observed to be lower than NA.
Table 2. TLC-FID generic fractions of asphaltic materials.
Table 2. TLC-FID generic fractions of asphaltic materials.
Saturates Aromatics Resins Asphaltenes
Asphalt IC †
Asphalt wt % wt %
Saturates wt % wt %
Aromatics wt %
Resins wt % wt % wt %
Asphaltenes IC †

PA
PA
4.40
4.40
18.97
18.97
23.55
23.55
53.07
53.07
1.35
1.35
NA
NA 14.17
14.17 13.92
13.92 23.36
23.36 48.52
48.52 1.68
1.68
I IC==(Saturates
†† C + Asphaltenes)/(Resins
(Saturates + Asphaltenes)/(Resins + Aromatics).
+ Aromatics).

Whenconsidering
When consideringthe thestability
stabilityaspect,
aspect,it itisisobserved
observed that
that PAPA
is is slightly
slightly more
more stable
stable than
than NANA as
as it
it has
has a low
a low IC Ivalue.
C value. As seen in Table 2, the values of saturates and asphaltenes are low in PA, which
As seen in Table 2, the values of saturates and asphaltenes are low in PA, which
is why it has acquiredhigher
is why it has acquired higherstability.
stability.Also,
Also,the thereason
reasonbehind
behindits
itsstability
stabilityisisthat
thatPAPAhas
hassuperior
superior
peptizability due to the smaller aggregation of asphaltenes’
peptizability due to the smaller aggregation of asphaltenes’ micelle. micelle.
Otherwise,the
Otherwise, thesaturates
saturatesand
andasphaltenes
asphaltenesare arethe
thelowest
lowestand
andhighest
highestpolarity
polaritycomponents
componentsof ofan
an
asphalt, respectively, and the solubility of the asphaltenes in a colloidal system is enhanced by the
asphalt, respectively, and the solubility of the asphaltenes in a colloidal system is enhanced by the
presence of intermediate polarity species such as aromatics and resins. Thus, the higher the IC, the
presence of intermediate polarity species such as aromatics and resins. Thus, the higher the IC , the less
less stable the overall system is.
stable the overall system is.

3.3. Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectroscopy (MALDI-TOF-MS)

Molar mass is one attribute of a molecule that results in its solubility. With the increase in molar
mass of molecules with a similar structure, their solubility decreases. When the asphalt fractions are
Materials 2016, 9, 859 7 of 20

3.3. Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectroscopy (MALDI-TOF-MS)

Molar mass is one attribute of a molecule that results in its solubility. With the increase in7 of
Materials 2016, 9, 859
molar
19
mass of molecules with a similar structure, their solubility decreases. When the asphalt fractions are
separated,
separated, it isit observed
is observedthatthat
those thatthat
those are are
highly insoluble
highly insoluble have higher
have molar
higher mass.
molar TheThe
mass. classic mass
classic
spectra
mass for bothfor
spectra PAboth
and NA
PA andare illustrated in Figure
NA are illustrated in2.Figure
Due to 2. the
Dueoligomeric nature of
to the oligomeric the asphalts,
nature of the
they are segregated
asphalts, into four regions:
they are segregated into fourmonomers from m/z
regions: monomers 200m/z
from to 400, dimers
200 to from m/z
400, dimers from400m/zto 650,
400
to 650,
trimers fromtrimers
m/z from650 tom/z
950,650
and to tetramers
950, and tetramers
from m/z from 950 tom/z 950 The
1600. to 1600. The present
samples samplessignificant
present
significant
signal intensity signal
up tointensity
48.38 × up 4 ~63.16
10to 48.38 ×10
×10 4 a.u. ×10
4~63.16
It is4 a.u. It is revealed
revealed from thefrom the MALDI-TOF-MS
MALDI-TOF-MS analysis
analysis
that the PAthat the PA is comprised
is comprised of molecules of molecules
with higher withmolar
highermassmolar mass
(328 Da) (328 Da)NA,
than thanwhich
NA, which
had 252hadDa.
252 Da. These results are obtained from the comparison of PA and NA
These results are obtained from the comparison of PA and NA bitumens and are presented in Figure 2.bitumens and are presented
Theinreason
Figure behind
2. The reason behind is
these results these results is
attributed toattributed
the highertoheteroatom
the higher heteroatom
content and content
lowerandH/C lower
ration
H/C ration in PA. On the other hand, when compared with the
in PA. On the other hand, when compared with the asphalt fractions, PA has high aromatics and asphalt fractions, PA has high
lowaromatics
saturates. and low saturates.

Figure
Figure 2. 2.MALDI-TOF-MS
MALDI-TOF-MSspectra
spectraof
of PA
PA and
and NA and respective
respectiveaverage
averagemolar
molarmasses.
masses.

3.4.3.4. FT-IR
FT-IR Analysis
Analysis
In analytical chemistry, FT-IR is found to be one of the most flexible and resourceful techniques.
In analytical chemistry, FT-IR is found to be one of the most flexible and resourceful techniques.
It is efficient at providing valuable information about the chemical functional groups of asphalts in
It is efficient at providing valuable information about the chemical functional groups of asphalts in
complex solids [6]. Figure 3 demonstrates the infrared spectra of PA and NA. For the scenario of NA,
complex solids [6]. Figure 3 demonstrates the infrared spectra of PA and NA. For the scenario of
the characteristics of IR spectra of clay minerals are clearly visible in Figure 3, where Si‒OH and
NA, the characteristics of IR spectra of clay minerals are clearly visible−1 in Figure 3, where Si-OH and
absorbed water on clay are illustrated through the band near 3650 cm . In Figure 3, the broad band
around 1600 cm−1 is assigned to the ring vibration of aromatic compounds. Whereas the band at 1083
cm−1 represents the anti-symmetric unfolded vibration of Si‒O‒Si [7], the other bands are detected
within the range of 1000 and 650 cm−1, which represent the characteristics of clay materials.
Materials 2016, 9, 859 8 of 20

absorbed water on clay are illustrated through the band near 3650 cm−1 . In Figure 3, the broad band
around 1600 cm−1 is assigned to the ring vibration of aromatic compounds. Whereas the band at
1083 cm−1 represents the anti-symmetric unfolded vibration of Si-O-Si [7], the other bands are detected
Materials
within the2016,
range of 1000 and 650 cm−1 , which represent the characteristics of clay materials. 8 of 19
9, 859

All of the asphaltic samples’ spectra exhibit similar stretching vibrations of classic CH2 , which is
All of the asphaltic samples’ spectra exhibit similar stretching vibrations of classic CH2, which is
demonstrated by the peaks within the range of 2854–2932 cm−1−1 .
demonstrated by the peaks within the range of 2854–2932 cm .
The peak due to carbonyl C=O group (i.e., carboxylates, ketones, and/or anhydrides) near
The
−1 ispeak due to carbonyl C=O group (i.e., carboxylates, ketones, and/or anhydrides) near 1700
1700 cm prominent in the spectrum of NA and appears with no or a very weak intensity in the
cm-1 is prominent in the spectrum of NA and appears with no or a very weak intensity in the
spectrum of PA; indicating that NA was much more severely oxidized than PA after a prolonged
spectrum of PA; indicating that NA was much more severely oxidized than PA after a prolonged
exposure
exposure to atmosphericair.
to atmospheric air.This
Thisobservation
observation is is fully in line
fully in line with
withthe
theresults
resultsofofelemental
elemental analysis
analysis
(NA(NAoxygen
oxygen 1.38
1.38wtwt%;%;PAPA oxygen
oxygen0.29
0.29wt
wt%).
%).
The band at 1034 cm −1 may result from the sulfoxide S=O stretching vibrations. Also, the peaks
The band at 1034 cm may result from the sulfoxide S=O stretching vibrations. Also, the peaks
−1

at 872 cmcm −1 ,−1810 cm−−1 1 −1 may relate to the out-of-plane bending vibrations of C-H in
at 872 , 810 cm ,, andand 748748 cm
cm−1 may relate to the out-of-plane bending vibrations of C‒H in
phenyl [8].[8].The −1 in the PA spectrum can be associated with long,
phenyl Thesharp
sharppeak
peaklocated
located at
at 722
722 cm
cm−1 in the PA spectrum can be associated with long,
straight-chain
straight-chainmethylene.
methylene. Overall,
Overall, the NANA contains
containspolarpolargroups
groupssuch
suchasascarbonyl
carbonyl and
and some
some clay
clay
minerals
minerals as observed
as observed from the the
from IR spectrum. It isItalso
IR spectrum. constituted
is also of minor
constituted complex
of minor components,
complex which
components,
which
have havechemical
distinct distinct chemical
functional functional
groups.groups.
Absorbance (%)

Clay minerals

Clay minerals

NA

PA

4000 3500 3000 2500 2000 1500 1000

-1
Wavenumber (cm )

Figure3.3. FT-IR
Figure FT-IR spectra
spectra of
of NA
NA and
andPA.
PA.

3.5. Raman Spectroscopy (RS)

3.5. Raman Spectroscopy (RS)
One of the most influential and efficient methods for characterizing asphaltic materials is
One spectroscopy
Raman of the most [9,10].
influential and efficient
This method methods
is, therefore, for characterizing
applied here to analyze asphaltic materials
the characteristics of is
Raman spectroscopy [9,10]. This method is, therefore, applied here to
PA and compare it with NA. The same has been demonstrated in Figure 4, which presents the analyze the characteristics
of Raman
PA andspectrum
comparewithin
it withtheNA. The same
Raman has been
shift range demonstrated
of 200~3600 cm−1. Thisin spectrum
Figure 4, demonstrated
which presents twothe
Raman spectrum within the Raman shift range of 200~3600 cm −1 . This spectrum demonstrated
first-order characteristic bands of all the asphaltic materials. The first is the D (defect) band at
two first-order characteristic
1344.98~1348.79 cm−1 and the bands
secondof is
allthe
theGasphaltic
(graphite)materials. The first is the cm
band at 1577.90~1607.50 D (defect) band at
−1 of graphitic

1344.98~1348.79 − 1
cm theand the second is the G (graphite) band at 1577.90~1607.50 −1 of graphitic
cmdefects
carbon. Whereas emergence of the D band is due to disordered structures or in the
carbon.
carbon,Whereas the emergence
the G band of the
originates from theDtangential
band is due to disordered
stretching structures
vibrations or defects
of the aromatic C‒Cin the carbon,
bonds. It
theisGobserved
band originates
from Figure from the in
4 that, tangential
NA, the Dstretching
and G bandsvibrations of than
are feebler the aromatic
those of PA.C-CIt bonds. It is
is inferred
from this
observed revelation
from Figure 4that
that,NA has worse
in NA, the D andorderG than
bandsPA.
areThe analysis
feebler than results
those ofofPA.
TLC-FID and
It is inferred
elemental
from analysisthat
this revelation dataNA showed that order
has worse NA has thana high concentration
PA. The of saturates
analysis results (14.17and
of TLC-FID wt elemental
%) and
analysis data showed that NA has a high concentration of saturates (14.17 wt %) and about carbon.
about 1.38 wt % oxygen, where the higher amounts of oxygen atoms are bound to aliphatic 1.38 wt %
Therefore, as is evident from these analyses, the higher oxygen content and aliphatic structure have
resulted in higher disorder in the structure of NA as compared to PA.
Materials 2016, 9, 859 9 of 20

oxygen, where the higher amounts of oxygen atoms are bound to aliphatic carbon. Therefore, as is
evident from these analyses, the higher oxygen content and aliphatic structure have resulted in higher
Materials 2016, 9, 859 9 of 19
disorder in the structure of NA as compared to PA.
There
There arearevarious
variousbands
bandsthat
thathave
haveemerged
emerged in in the
the second-order
second-order Raman Ramanspectra
spectraofofasphaltic
asphaltic
materials at ~2450, ~2695, ~2735, ~2950, and ~3248 cm −1 . Such bands are allocated to both overtone
materials at ~2450, ~2695, ~2735, ~2950, and ~3248 cm−1. Such bands are allocated to both overtone
scattering
scattering andandcombination
combinationscattering.
scattering.Figure
Figure 44 shows
shows thethe same,
same,wherewhereall allofofthe
theasphaltic
asphaltic materials
materials
display a weak Raman band within the range of 2500~2800 cm − 1 ; this attribute agrees to the overtone
display a weak Raman band within the range of 2500~2800 cm ; this attribute agrees to the overtone
−1

of the D band.
of the D band. DD band
bandisisoriginally
originallyreferred
referredtoto as
as the
the G' band
band asasititisissymmetric
symmetricand andisisapparent
apparentin in
thethe
second-order
second-order Raman
Raman spectra
spectraof crystalline graphite.
of crystalline graphite.It isItalso referred
is also as the
referred as 2D
theor D*orband
2D by several
D* band by
several researchers
researchers [11]. The
[11]. The subtle subtle
band band
of 383 cmof−383
1 reveals
cm−1 reveals the amorphous
the amorphous sp3 -bonded
sp3-bonded carbon.
carbon.

Figure
Figure 4. 4. Ramanspectra
Raman spectraofofPA
PAand
andNA,
NA,showing
showing the
the main
main Raman
Ramanfeatures;
features;the
theDDand
andGGbands.
bands.

3.6. Nuclear Magnetic Resonance Spectroscopy (1H-NMR)

3.6. Nuclear Magnetic Resonance Spectroscopy (1 H-NMR)
Figure 5 gives the proton NMR spectra of varied asphalts. Also, Table 4 and Figure 6 present the
Figure 5 gives the proton NMR spectra of varied asphalts. Also, Table 4 and Figure 6 present the
positions of the chemical shifts [12]. The distinct types of protons in the asphalt samples are analyzed
positions of the chemical shifts [12]. The distinct types of protons in the asphalt samples are analyzed
in terms of their relative proportions through the integration of the spectra. The same are presented
in terms of their relative proportions through the integration of the spectra. The same are presented in
in Table 3.
Table 3.
Table 3. Peak areas as a percentage of total protons for the 1H-NMR spectra of PA and NA.
Table 3. Peak areas as a percentage of total protons for the 1 H-NMR spectra of PA and NA.
Hydrogen Distribution, %
Asphalt
Hα Hβ Hγ
Hydrogen Distribution, %
Har
Asphalt
PA 15.72 66.13 18.15 10.81
H H Hγ Har
NA 13.75 α 56.97β 29.28 8.21
PA 15.72 66.13 18.15 10.81
NA 13.75 56.97 29.28 8.21
Materials 2016, 9, 859 10 of 20
Materials 2016, 9, 859 10 of 19

CDCl3

Absorbance (%)

NA
PA

12 10 8 6 4 2 0

Chemical shift (ppm)

Figure 5. 11H-NMR
Figure 5. H-NMR spectra
spectra of
of NA
NA and
and PA.
PA.

PA and NA are found to exhibit similar spectra, as is evident in the studies of 11H-NMR (Figure 5).
PA and NA are found to exhibit similar spectra, as is evident in the studies of H-NMR (Figure 5).
However, the 11H-NMR data in Table 3 shows the highly complex and rich nature of NA as compared
However, the H-NMR data in Table 3 shows the highly complex and rich nature of NA as compared
to PA.
to PA.
The deuterated chloroform (CDCl3) is presented by the peak of 1H-NMR spectra at 7.3 ppm. To
The deuterated chloroform (CDCl3 ) is presented by the peak of 1 H-NMR spectra at 7.3 ppm.
obtain this result, each of the asphaltic samples was dissolved for the NMR measurements.
To obtain this result, each of the asphaltic samples was dissolved for the NMR measurements.
When considering the1 1H-NMR spectra, which is donated by protons, the aromatic peaks are
When considering the H-NMR spectra, which is donated by protons, the aromatic peaks are easily
easily determined (Har; δ = 6.5~9.5 ppm) from the aliphatic ones (Hal; δ = 0.5~4.5 ppm). Also, the
determined (Har ; δ = 6.5~9.5 ppm) from the aliphatic ones (Hal ; δ = 0.5~4.5 ppm). Also, the spectra
spectra were rendered more dependable and consistent. Furthermore, the aliphatic peaks were
were rendered more dependable and consistent. Furthermore, the aliphatic peaks were segregated
segregated into three types of protons (α, β, and γ) as per their respective positions in the aromatic
into three types of protons (α, β, and γ) as per their respective positions in the aromatic core: Hα ,
core: Hα, δ = 2.0~4.5 ppm; Hβ, δ = 1.0~2.0 ppm; and Hγ, δ = 0.5~1.0 ppm. However, the borders
δ = 2.0~4.5 ppm; Hβ , δ = 1.0~2.0 ppm; and Hγ , δ = 0.5~1.0 ppm. However, the borders defined here
defined here are approximate as the impact of heteroatoms and metals on peak shifting is ignored.
are approximate as the impact of heteroatoms and metals on peak shifting is ignored. Irrespective of
Irrespective of this, the domains described in Table 4 are often utilized.
this, the domains described in Table 4 are often utilized.
Table
Table 4.
4. Proton
Proton NMR
NMR chemical
chemical shifts
shifts (ppm)
(ppm) relative to Tetramethylsilane
relative to Tetramethylsilane (TMS)
(TMS) [12].
[12].

Chemical Shift
Chemical Shift Symbol Description
Range (ppm) Symbol Description
Range (ppm)
Aliphatic hydrogens in sterically hindered positions, highly
Aliphatic hydrogens in sterically hindered positions, highly
9.5‒8.36 Har2 pericondensed polycyclic aromatic compounds (PACs), next to
9.5–8.36 Har2 pericondensed polycyclic aromatic compounds (PACs), next to
heteroatoms andand
heteroatoms some hydrogens
some hydrogens joined
joinedto
tonitrogen
nitrogen
8.36‒6.3
8.36–6.3 Har1Har1 All other aromatic hydrocarbons
All other aromatic hydrocarbons
4.5–3.69
4.5‒3.69 HF HF Aliphatic
Aliphatic hydrogens
hydrogens in methylene
in methylene groupsααto
groups to two
two aromatic
aromaticrings
rings
Aliphatic hydrogens in methylene groups α to an
Aliphatic hydrogens in methylene groups α to an aromatic aromatic ring and
ring
3.69–3.0 HA
3.69‒3.0 HA β to another
and βAliphatic
to another
hydrogens in methyl or methylene groups α to an
3.0–2.0 Hα1 Aliphatic hydrogens
aromatic in methyl
ring which can also or
be methylene
attached in γgroups
positionαor
tofurther
an to
3.0‒2.0 Hα1 aromatic ringorwhich
another canaromatic
the same also be ring
attached in γ position or further to
2.0–1.6 Hβ2 Alicyclic
another or thehydrogens in β position
same aromatic ring to an aromatic ring
Aliphatic hydrogens in methyl or methylene groups β to an
2.0‒1.6
1.6–1.0 Hβ2 Hβ1 Alicyclic hydrogens in β position to an aromatic ring
aromatic ring
Aliphatic hydrogens
Aliphatic in methyl
hydrogens oror
in methyl methylene
methylenegroups
groups γβ to
toan
an
1.6‒1.0
1.0–0.5 Hβ1 Hγ
aromatic ring ring
aromatic
Aliphatic hydrogens in methyl or methylene groups γ to an
1.0‒0.5 Hγ
aromatic ring
Materials 2016, 9, 859 11 of 20

Materials 2016, 9, 859 11 of 19

Table
Materials32016,
gives the data about the aliphatic hydrogen concentration, which is found to11be
9, 859 higher
of 19

in NA than PA. Table

This 3 gives the data about
revelation shows thethat
aliphatic
NA hydrogen concentration,
is composed which is that
of molecules foundare
to be higher branched.
highly
TableNA3than
gives PA.the data about shows
the aliphatic
that NAhydrogen concentration, whichhighly
is found to be higher
It is worthinmentioning This
thatrevelation
aromatic conjugated is composed
compounds of molecules that
not bearingare hydrogen branched.
atomsIt cannot be
in NAisthanworthPA.
1 H-NMR. This
mentioningrevelation
that shows
aromatic that NA
conjugated is composed
compounds of
not molecules
bearing that
hydrogenare highly
atoms branched.
cannot be It
detected bydetected
is worth by 1H-NMR.
mentioning that aromatic conjugated compounds not bearing hydrogen atoms cannot be
An illustration
detected An1H-NMR.
by of the of
illustration types of hydrogen
the types of hydrogenisisdisplayed
displayed inin Figure
Figure 6 below:
6 below:
An illustration of the types of hydrogen is displayed in Figure 6 below:

Figure 6. Illustration of types of hydrogen.

Figure 6. Illustration of types of hydrogen.
Description and chemical shift ranges in 1H-NMR is given above (Table 4).
DescriptionHar2:and
1; Har1 : 2; HF: 3, H
chemical A:Figure
4; H
shift α1:6.
ranges 1 H-NMR
5a,Illustration
b,in
c; H β2: 6;of
Htypes
β1: 7; and Hγ: 8.above (Table 4).
isofgiven
hydrogen.
Hydrogen in α-methyl group: 5a; Hydrogen in α-methylene in alkyl side chain: 5b; and
Har2 : 1; Har1 : 2; HF : 3, HA : 4; Hα1 : 5a, b, c; Hβ2 : 6; Hβ1 : 7; and Hγ : 8.
Hydrogen
Description andinchemical
α-methylene in ranges
shift hydroaromatic
in 1H-NMR ring (5c).
is given above (Table 4).
Hydrogen in α-methyl group: 5a; Hydrogen in α-methylene in alkyl side chain: 5b; and
Har2: 1; Har1: 2; HF: 3, HA: 4; Hα1: 5a, b, c; Hβ2: 6; Hβ1: 7; and Hγ: 8.
3.7. Ultraviolet
Hydrogen and Visible Spectroscopy
in α-methylene (UV-VIS) ring (5c).
in hydroaromatic
Hydrogen in α-methyl group: 5a; Hydrogen in α-methylene in alkyl side chain: 5b; and
Ultraviolet
Hydrogen and visible in
in α-methylene spectroscopy is utilized
hydroaromatic to examine the structure of the aromatic
ring (5c).
3.7. Ultraviolet and Visible
component in the Spectroscopy
asphalts. Figure(UV-VIS)
7 illustrates the UV signal data (absorptivity vs. wavelength)
within the range of 240~600 nm by utilizing the UV instrument. The motive behind selecting this UV
3.7. Ultraviolet
Ultraviolet and Visiblespectroscopy
Spectroscopy (UV-VIS)
range isand that visible
it has a specific sensitivity istoutilized
fractionsto examine
with the structure
high contents of aromatic ofmolecules.
the aromaticAs percomponent
in the asphalts.
UltravioletFigure
the literature and 7 illustrates
[13], visible thethat
UVthe
spectroscopy
it was observed signal data
is utilized
onset (absorptivity
to examine
wavelength vs.peak
the
of absorption wavelength)
structure within
of the
at 270, 320, 380, the range
aromatic
470,
of 240~600 and
componentnm580 innm
by were
utilizing
the of benzene,
the UV
asphalts. naphthalene,
instrument.
Figure anthracene,
7 illustratesThethemotive
UV tetracene,
behind
signal andselecting
data pentacene, respectively.
this
(absorptivity UVvs.range Near
is that it has
wavelength)
260thenm of the
withinsensitivity
a specific range toregion,
of 240~600 an nm
fractions absorption
with band with
by utilizing
high the UV
contentsan extended
instrument.
of aromaticwavelength
The tail isbehind
motive
molecules. highly significant,
As per selecting as UV
this
the literature [13],
presented in Figure 7. This signifies that the components equipped with benzene rings are dominant
range
it was is that that
observed it hasthea specific
onset sensitivity to fractions
wavelength of with high
absorption peak contents
at 270,of320,
aromatic
380, molecules.
470, and 580Asnmper were
for all asphaltic materials. While comparing the spectrum of PA with NA, it was observed that the
the literature
of benzene, [13], it wasanthracene,
observed thattetracene,
the onset wavelength of absorption peak at 270, 320, 380, 470,
PAnaphthalene,
spectrum exhibits weaker absorption band atand 261.5pentacene,
nm. The samerespectively.
is depicted in FigureNear 7.260
Thenm of the
and 580 nm were of benzene, naphthalene, anthracene, tetracene, and pentacene, respectively. Near
region, anfindings
absorption suggest that NA
band with is an
equipped
extendedwith awavelength
higher concentration of conjugated
tail is highly systems as
significant, and/or
presented in
260 nm of the region, an absorption band with an extended wavelength tail
larger chromophores as compared to PA. To conclude, the UV-Vis spectra have indicated a similar is highly significant, as
Figure 7. This signifies that the components equipped with benzene rings are dominant for all asphaltic
presented in Figure 7. This signifies that the components equipped
composition of aromatic rings in the aromatic nuclei of both the asphalts. with benzene rings are dominant
materials.
for allWhile
asphalticcomparing
materials.the spectrum
While of PAthe
comparing with NA, it was
spectrum of PAobserved
with NA,that it wastheobserved
PA spectrum exhibits
that the
weaker
PA absorption
spectrum exhibits band weaker
at 261.5absorption
nm. The band sameatis261.5
depicted
nm. The in Figure
same is 7. The findings
depicted in Figuresuggest
7. The that
NA isfindings
equipped suggest that NA is equipped with a higher concentration of conjugated systems and/or as
with a higher concentration of conjugated systems and/or larger chromophores
compared to PA. To conclude,
larger chromophores the UV-Vis
as compared to PA. spectra havethe
To conclude, indicated a similar
UV-Vis spectra havecomposition
indicated a of aromatic
similar
ringscomposition
in the aromatic of aromatic
nucleiringsof bothin the
thearomatic
asphalts. nuclei of both the asphalts.

Figure 7. Cont.
Materials 2016, 9, 859 12 of 19
Materials 2016, 9, 859 12 of 20
Materials 2016, 9, 859 12 of 19

Figure
Figure7.7.UV-Vis
UV-Vis
UV-Visspectra PAand
of PA
spectra of PA andNA.
and NA.
NA.

3.8. X-ray
3.8. X-ray Diffraction
Diffraction (XRD)
(XRD)
Figures 8 and 9 demonstratethe theX-ray
X-ray diffraction
diffraction patterns ofofPA and NA, respectively. The The
Figures 88and and 99demonstrate
demonstrate the X-ray patterns
diffraction patterns of PA PA
and and
NA, NA, respectively.
respectively. The wide
wide peaks at 18°~26° and 42° in Figure 8 represent the X-ray diffractogram of PA. The γ-peak
peaks at 18◦ ~26
wide peaks ◦ and 42and
at 18°~26° ◦ in Figure
42° in 8Figure
represent8 represent
the X-raythe X-ray diffractogram
diffractogram of PA. Theofγ-peakPA. The γ-peak
appears at
appears at around
◦
2θ = 18.90° because of the aliphatic chains or condensed saturated rings. The peak
appears2θ
around at around
= 18.90 2θ = 18.90°ofbecause
because the of the chains
aliphatic aliphaticorchains or condensed
condensed saturated saturated
rings. Therings.
peak The peak
settled
settled at approximately 2θ = 23.20° is known as the graphene band or (002)-band. The formation of
settled
at theatgraphene
approximately
approximately 2θ = 23.20
band =◦ 23.20°
is2θemerged
is known is known
by as theas
staging the graphene
graphene
the aromaticband band orexisting
(002)-band.
or (002)-band.
molecules theThe
The
in formation
formation
asphaltenic of
of the
the graphene
graphene
structure. band
bandAtisthe is
emerged emerged
2θ valueby by
staging
(42.39°), staging the
the aromatic
a weak aromatic
molecules
band is formed, molecules
whichexisting existing
is due to in
thethe in the
asphaltenic
influence asphaltenic
of first structure.
(100)
structure.
At thenearestAtneighbors
2θ valuethe(42.39
2θ value◦ ),the
in a(42.39°),
weak a weak
band
ring structure band iswhich
is[14,15].
formed, formed, is which
due to isthe
due to the influence
influence of first
of first (100) (100)
nearest
nearest neighbors
neighbors in the
in the ring ring structure
structure [14,15]. [14,15].
14000
PA
14000
12000 PA
12000
10000
Intensity (a.u.)

100008000
Intensity (a.u.)

-band (100)-band
80006000

-band(002)-band (100)-band
60004000

2000
4000 (002)-band
10 20 30 40 50 60 70
2000 Diffraction angle 2


10 Figure
20 8. X-ray30diffractogram
40 of PA.
50 60 70

Diffraction angle 2
The NA material is rendered sticky due to the presence of organic mineral substances. The
features of resilience and toughness Figure of asphalts
8. X-ray is obtained with the help of organic substances
Figure 8. X-ray diffractogram
diffractogram of of PA.
PA.
present in it, as it provides the characteristics of binding. H2O2 digestion was deployed to evaluate
the organic
The fraction of
NA material is NA. It was observed
rendered sticky due to be
to91.17 wt %. Figure
the presence of 9organic
demonstrates the XRD
mineral pattern The
substances.
The NAThismaterial iselucidates
renderedthe sticky due to the presence of organic mineral substances. The features
features of resilience and toughness of asphalts is obtained with the help of organic of
of NA. figure major crystalline components composing the bulk sample NA.
substances
of resilience
After and toughness
kaolinite ofquartz
and illite,the asphalts is obtained
is found with
toofbebinding.
the thematerial
clay help ofthat
organic
is wassubstances
present in the present
greatest in it,
present in it, as it provides characteristics H2O2 digestion deployed to evaluate
as it provides
abundance. the characteristics
Lower amounts of of binding.
smectite, H2 Omontmorillonite,
calcite, 2 digestion was deployed
fluorapatite, to
andevaluate the
schertelite organic
were
the organic fraction of NA. It was observed to be 91.17 wt %. Figure 9 demonstrates the XRD pattern
alsoofdetected.
fraction NA. It was As per this analysis,
observed the mineral
to be 91.17 composition
wt %. Figure of the NA isthe
9 demonstrates assessed to be over
XRD pattern 95% This
of NA.
of NA. This figure elucidates the major crystalline components composing the bulk sample of NA.
quartz (SiO 2) and a few percent Feldspars (K-component; KAlSi3O8). On the other hand, the XRD
figure elucidates the major crystalline components composing the bulk sample of NA. After kaolinite
Afterpattern
kaolinite
of PAanddid illite,
not showquartz
peaksis found to be the clay material that is present in the greatest
and illite, quartz is found to be the symbolizing
clay material thethat
crystalline structure.
is present in the greatest abundance. Lower
abundance. Lower amounts of smectite, calcite, montmorillonite, fluorapatite, and schertelite were
amounts of smectite, calcite, montmorillonite, fluorapatite, and schertelite were also detected. As per
also detected. As per this analysis, the mineral composition of the NA is assessed to be over 95%
this analysis, the mineral composition of the NA is assessed to be over 95% quartz (SiO2 ) and a few
quartz (SiO2) and a few percent Feldspars (K-component; KAlSi3O8). On the other hand, the XRD
percent Feldspars (K-component; KAlSi3 O8 ). On the other hand, the XRD pattern of PA did not show
pattern of PA did not show peaks symbolizing the crystalline structure.
peaks symbolizing the crystalline structure.
Materials 2016, 9, 859 13 of 20
Materials 2016, 9, 859 13 of 19

Materials
Compared2016, 9, 859
to
the 13 of 19
Compared to theFT-IR
FT-IRtechnique,
technique,X-ray
X-ray diffraction
diffraction isis aa powerful
powerfultool toolininthe
theidentification
identification andand
characterization
characterization of minerals in NA. The bulk of the clay fraction of many natural asphalts is crystalline,
Compared toofthe minerals in NA. The
FT-IR technique, X-raybulk of the clay
diffraction fraction of
is a powerful toolmany
in thenatural asphalts
identification andis
butcrystalline,
clay particles
but are tooparticles
clay small forare optical
too crystallographic
small for optical methods to be applied.
crystallographic methods Therefore,
to be XRD has
applied.
characterization of minerals in NA. The bulk of the clay fraction of many natural asphalts is
long been a mainstay
Therefore, XRD hasinlong
the identification
beenarea mainstayof clay-sized minerals in of natural asphalts. It is interesting
natural to
crystalline, but clay particles too smallinfor theoptical
identification clay-sized
crystallographic minerals
methods to beinapplied.
note that fine mineral
asphalts. It XRD
Therefore, matter
is interesting is
has longtobeen expected
note that to strengthen
fine mineral
a mainstay in the the
matter bitumen
is expected
identification in the NA and
oftoclay-sized
strengthen impart hardiness
the bitumen
minerals and
in the
in natural
enhance
NA and pavement
asphalts. Itimpart surface
hardiness
is interesting properties
to andthat
note (better
enhance tire–road
pavement
fine mineral mattersurface
surface interaction),
properties
is expected if is added
(better
to strengthen as a modifier
tire−road
the bitumen in the in
surface
interaction),
paving-grade if is
asphaltadded as
cements.a modifier in paving-grade asphalt cements.
NA and impart hardiness and enhance pavement surface properties (better tire−road surface
interaction), if is added as a modifier in paving-grade asphalt cements.
14000
NA
14000 Q
12000
I-S NA
Q
12000
I-S
10000
Q
I-S K
(a.u)(a.u)

10000
Q
8000 I-S K K
Intensity

8000 K
Intensity

6000
C
F Sch Fl K
M I-S
6000 Ch
KI C C I I I I
4000 F Sch Fl K K I-S
M I-S KI-S
Ch
KI C I I I I Fl K
4000 K I-S
2000 I-S K
Fl K

2000
10 20 30 40 50 60 70

10 20 Diffraction
30 angle
40 2(50
) 60 70

Figure Diffraction angle 2K: () kaolinite; Q: quartz; F: feldspar

Figure 9. 9.X-ray
X-raydiffractogram
diffractogram ofof NA.
NA. I-S:
I-S: illite-smectite;
illite-smectite; K: kaolinite; Q: quartz; F: feldspar
(K-component);
(K-component);
Figure Sch:
Sch:
9. X-ray schertelite;M:
schertelite;
diffractogram M: montmorillonite;
ofmontmorillonite; I:I: illite;
NA. I-S: illite-smectite;illite; C:
C:K:calcite;
calcite; Fl:
Fl:fluorapatite.
kaolinite; fluorapatite.
Q: quartz; F: feldspar
(K-component); Sch: schertelite; M: montmorillonite; I: illite; C: calcite; Fl: fluorapatite.
3.9. Scanning Electron Microscopy (SEM)
3.9. Scanning Electron Microscopy (SEM)
3.9. Scanning
A scanningElectron Microscopy
electron (SEM) (SEM) uses a focused beam of high-energy electrons to
microscope
A scanning electron microscope (SEM) uses a focused beam of high-energy electrons to generate
generate
A of a varietyelectron
scanning of signalsmicroscope
at the surface of solid
usesspecimens. The signals that derive from electron–
a variety
sample signals at reveal
interactions the surface of solid(SEM)
information specimens.
about the
a The
sample
focused beam
signals
including thatof high-energy
derive
external
electrons
from electron–sample
morphology
to
(texture),
generate a variety of signals at the surface of solid specimens. The signals that derive from electron–
interactions
chemical reveal information
composition, about
crystalline the sample
structure, including external morphology (texture), chemical
sample interactions reveal information about and orientation
the sample of materials
including externalmaking up the(texture),
morphology sample.
composition, crystalline
Figure 10composition,
presents the structure, and orientation
SEM inspections of materials making up the sample. Figure
minor10
chemical crystalline structure, ofandasphalt microstructures,
orientation of materials indicating
making up some
the sample.
presents the
differences.SEM inspections
The figure of asphalt microstructures, indicating some minor differences. The figure
Figure 10 presents theshows
SEM the broad sizes
inspections of ofasphalt
unevenly distributed clay
microstructures, particles some
indicating on a smooth
minor
shows the broad
surface as The sizes of unevenly
representing NA.the distributed
The other clay particles
image, which on is ahomogeneous
smooth surface as representing
and uniform, is NA.
a
differences. figure shows broad sizes of unevenly distributed clay particles on a smooth
Thesurface
other image,
as representing NA. The other image, which is homogeneous and uniform, is a in
representation which
of the is
PA homogeneous
sample. As and
seen inuniform,
the is
figure, a representation
the PA sample of
has the
no PA sample.
clay As seen
contamination.
therepresentation
figure,
This the PAofsample
observation isthe
in PA has
good no clayAscontamination.
agreement
sample. withinthe
seen thedata This
of
figure,FT-IR
theobservation
X-rayisdiffraction.
andsample
PA in good
has agreement
no clay with the
contamination.
data of observation
This FT-IR and X-ray diffraction.
is in good agreement with the data of FT-IR and X-ray diffraction.

Figure 10. SEM images of PA and NA (showing very fine (clay) particles dispersed into the asphaltic
phase),10.
Figure magnification
SEM images×500.
Figure 10. SEM images ofofPA
PA and NA (showing very fine (clay) particles dispersed into the asphaltic
and NA (showing very fine (clay) particles dispersed into the asphaltic
phase), magnification ×500.
phase), magnification ×500.
Materials 2016, 9, 859 14 of 20
Materials
Materials 2016,
2016, 9,
9, 859
859 14
14 of
of 19
19

3.10.
3.10. Thermogravimetric
3.10. Thermogravimetric Analysis
Thermogravimetric (TGA)
Analysis (TGA)
Analysis (TGA)
To
To acquire
Toacquire and
acquireand select
andselect the
selectthe best
thebest attributes
bestattributes and
attributesand measurements
andmeasurements
measurements for
forfor asphalt
asphalt
asphalt products,
products,
products, itit imperative
it is is
is imperative
imperative
to
to gauge
to gauge
gauge the thermal
the thermal
the thermal stability
stability
stability of the asphalt
of the materials
of the asphalt materials
asphalt materials pertaining
pertainingpertaining to
to their weight their
to their weight
weight
loss due loss
loss due
due to
to volatilization. to
volatilization.
volatilization. This
This is
is an
an essential
essential property
property that
that needs
needs consideration
consideration when
when generating
generating
This is an essential property that needs consideration when generating high-performing asphalts for high-performing
high-performing
asphalts
asphalts for
particularfor particular
particular applications.
applications. applications.
Thermogravimetric
Thermogravimetricanalysis
Thermogravimetric analysis
analysiswaswas
was performed
performed
performed to
to comprehend
comprehend
to comprehend the
the thermal
the thermal behaviorbehavior
thermal behavior of
of the
of the asphalticthe
asphaltic materials.
asphaltic materials.
materials. Figures
Figures 11Figures 11 and 12
11 and 12the
and 12 represent represent
represent the TGA (Thermogravimetric
the TGA (Thermogravimetric
TGA (Thermogravimetric analysis)
analysis) andanalysis) and DTA
and DTA
DTA (Differential
(Differential
(Differential thermogravimetric)
thermogravimetric)
thermogravimetric) curves acquired curves
curves acquired
heatingat
acquired
at the the
atrate heating
theof rate
rate of
10 ◦ C/min,
heating 10
10 °C/min,
°C/min, respectively.
ofrespectively. respectively.

Region (i) Region (ii) Region (iii)

Region (i) Region (ii) Region (iii)
100
100

80
PA
PA
80
%)
(wt.%)
loss(wt.

60
60 NA
NA
Weightloss

40
40
Weight

20
20
RESIDUE 8.83 %
RESIDUE 8.83 %
RESIDUE 0.99 %
0 RESIDUE 0.99 %
0

100 200 300 400 500 600 700

100 200 300 400 500 600 700
Temperature
Temperature ((C)
C)
Figure
Figure 11.
11. TGA
TGA curves
curves of
of PA
PA and
and NA.
NA.

1.0
1.0 Region (i) Region (iii)
Region (i) Region (ii) Region (iii)
Region (ii)
C)
%/oC)
o

0.8
0.8
(wt.%/
change(wt.

0.6
0.6
weightchange

0.4
Derivativeweight

0.4

Exo NA
Derivative

0.2 Exo NA
0.2
Endo
Endo PA
PA
0.0
0.0

100 200 300 400 500 600 700

100 200 300 400 500 600 700
Temperature
Temperature ((C)
C)

Figure
Figure 12.
12. DTA
DTA curves
curves of
of PA and
PA and NA.
andNA.
NA.
curves of PA

Table
Table555presents
presents the
presentsthe onset
theonset and
onsetand the
andthe offset
theoffset temperature
temperatureofof
offsettemperature thermal
ofthermal
thermal degradation
degradation (Tonset , Toffset), yield
Table degradation (T(T onset, Toffset), yield
onset , Toffset ), yield
of carbonaceous
of carbonaceous residue,
carbonaceous residue, and
residue, and the
and the maximum
the maximum decomposition
maximumdecomposition temperature
decompositiontemperature
temperature(T (T max) at 700 °C.
(Tmax)) at 700 °C.
◦ C.
of max at 700
When the
When the temperature
thetemperature is subjected
temperatureisissubjected to
subjectedtoto an increase, the tendencies of thermal decomposition of
When anan increase,
increase, thethe tendencies
tendencies of thermal
of thermal decomposition
decomposition of
of the
the
the two
two asphaltic
asphaltic materials
materials are
are observed
observed to
to be
be similar.
similar. Up
Up to
to at
at least
least 180
180
◦
°C
°C (TGA
(TGA curve),
curve), the
the samples
samples
two
are asphaltic materialsafter
are observed to be similar. UpThe
to at least 180findings
C (TGAreveal
curve), theboth
samples are
are found
found
found to be
to be
be stable,
tostable,
stable,
afterafter
which
which
which
mass
mass
mass
loss
loss
loss occurs.
occurs.
occurs. The The analytical
analytical
analytical findings
findings reveal
reveal that
that
that
both both
PA
PA
PA and
and and
NA
NA
NA exhibit
exhibit different
different weight
weight loss
loss behavior
behavior within aa temperature range of 25 °C°C◦to 700
7001°C for
for 1113
hh and
exhibit
13 min. different weight loss behavior withinwithin temperature
a temperature range of range
25 ◦ Cofto25700 to
C for °Ch and and
min.
13 min.
Materials 2016, 9, 859 15 of 20

After subjecting the samples to high temperatures, it was observed that NA lost large amounts
of weight as compared to PA. This indicates that NA has low thermal stability among its molecules.
This is in accordance with the elemental analysis and TLC-FID data (Tables 1 and 2). Also, when
considering that H2 and CH4 evolution is the reason behind higher weight loss during heating [16],
the asphalt with the higher hydrogen content (i.e., NA) has a larger weight loss.
As can be seen in Figure 11, the linear superposition of the component reactions in asphalt
corresponds to the TGA curves with significant peaks and shoulders. As mentioned before, the asphalt
components are segregated into four categories of SARA composition: saturates, aromatics, resins, and
asphaltenes [17]. Each of these components has different combustion activity (S + A > R > A) [18], thus
each component reaction may correspond to a single mass loss peak.
For PA and NA, at temperatures of 333.3 ◦ C, 441.62 ◦ C, and 546.62 ◦ C; and 286.63 ◦ C, 433.30 ◦ C,
and 489.96 ◦ C, respectively, the three major exothermic events are easily differentiated. The existence of
these three events is due to the susceptibility of present organic material to igniting in the atmosphere.
After the completion of the thermal treatment process, the NA sample had a charred residue of
8.83 wt %, while PA had 0.99 wt % of residue. Such a revelation indicates that NA is constituted of
mineral materials that are transformed into ash during combustion.
The three pronounced regions of weight loss, i.e., (i), (ii), and (iii), are evident in Figure 11.
Region (i) is formed due to the radical polymerization reaction, whereby the oil content comprising
primarily saturates and aromatics is subjected to distillation and combustion [19]. As the oil content
has low molecular weight and pyrolysis temperature, they are removed at a low temperature.
In region (ii), the peripheral functional groups and heteroatom bonds are fragmented, the resins
are oxidized and dehydrogenated, and then asphaltenes and char are generated in the cracking/
polymerization reactions. The weight loss of asphalts in this region is due to these reactions. The
second peak (405~500 ◦ C) is attributed to the release of secondary volatiles and char combustion.
The last region (iii) is reflected in the second mass loss peak in the TGA peak, within the
temperature range of 530~680 ◦ C. In this stage, the aromatic molecules show a steady increment,
asphaltenes decompose [20], and char is formed due to the condensation of free radical molecules.
The char, which is found to be comparatively stable, is eventually burned.

Table 5. TGA and DTG thermogram data of PA and NA loading at a heating rate of 10 ◦ C/min.

Asphaltic Samples Tonset (◦ C) Toffset (◦ C) Tmax (◦ C) Residue at 700 ◦ C (wt %)

PA 286.63 548.28 333.30/441.62/546.62 0.99
NA 189.96 504.99 286.63/433.30/489.96 8.83
Tonset, the onset temperature of thermal degradation (◦ C); Toffset, the offset temperature of thermal degradation
(◦ C); Tmax, the maximum decomposition temperature (◦ C).

3.11. Differential Scanning Calorimetry (DSC)

The asphalts are composed of a combination of distinct hydrocarbons with varied chemical
structures and molecular weights. Therefore, it is crucial to comprehend their compositions and their
impact on determining the complete thermal behavior of asphalts. Figure 13 demonstrates the DSC
scans of both PA and NA.
In the temperature range of −40 ◦ C to 0 ◦ C, asphalts exhibit a broad glass transition. When
asphalts are subjected to the DSC scans, different melting peaks or shifts within the peak positions
due to variant temperatures are observed, which correspond to the varied shapes of asphalts.
There are two distinct glass transition temperatures exposed through the DSC curves, namely,
the upper glass transition (Tg2 ) and the lower glass transition (Tg1 ). Whereas Tg2 is obtained from
the maltene–asphaltene interphase region, Tg1 is obtained from the maltene phase [21]. When NA is
cooled or heated, the crystallites melt and generate a small endothermal peak (T = +44.15 ◦ C) next to
the glass transition (Tg2 = −11.45 ◦ C).
Materials 2016, 9, 859 16 of 20
Materials 2016, 9, 859 16 of 19

PA
23.0
Cp1 = 0.193 J/gC
NA
T = -31.16 C Cp2 = 0.220 J/gC
22.5 g1
T = -13.49 C
g2

Endothermic peak

Heat flow (mW)

22.0
T = -11.45 C
g2 Peak = + 44.15 C
Cp2 = 0.090 J/gC Area = 1.645 mJ
21.5 H = 0.2061 J/g

T = -28.12 C
g1
21.0 Cp1 = 0.409 J/gC

20.5
Endo
Exo
20.0

-40 -20 0 20 40 60 80 100

Temperature (C)

Figure 13. DSC curves of PA

PA and
and NA.
NA.

Both PA and NA have Tg (onset) near −36.5 °C. The low molecular weights of the materials in the
Both PA and NA have Tg (onset) near −36.5 ◦ C. The low molecular weights of the materials in the
asphaltic fractions are the facilitator of the onset of Tg. Nonetheless, the differences between their
asphaltic fractions are the facilitator of the onset of Tg . Nonetheless, the differences between their
major glass transition temperatures are dissimilar. When comparing PA with NA, PA has a lower,
major glass transition temperatures are dissimilar. When comparing PA with NA, PA has a lower,
weaker glass transition (Tg1 = −31.16 °C) than NA, which has a high glass transition (Tg1 = −28.12 °C).
weaker glass transition (Tg1 = −31.16 ◦ C) than NA, which has a high glass transition (Tg1 = −28.12 ◦ C).
The reason behind this characteristic is the differences in their chemical structure, molecular weight,
The reason behind this characteristic is the differences in their chemical structure, molecular weight,
and distribution. NA has a high concentration of saturates (14.17 wt %) and other sulfur-containing
and distribution. NA has a high concentration of saturates (14.17 wt %) and other sulfur-containing
compounds with an average molecular weight of 252 Da, which makes it a black sticky material.
compounds with an average molecular weight of 252 Da, which makes it a black sticky material.
In the case of PA, it has approximately 328 Da of molecular weight along with aromatics in
In the case of PA, it has approximately 328 Da of molecular weight along with aromatics in
multi-ring structures, 4.40 wt % paraffin, and 18.97 wt % naphthene aromatics. The high molecular weight
multi-ring structures, 4.40 wt % paraffin, and 18.97 wt % naphthene aromatics. The high molecular
and inflexible nature of the multi-ring molecular structures in PA result in its greater Tg transition.
weight and inflexible nature of the multi-ring molecular structures in PA result in its greater
Tg is defined as the temperature at which all the molecular translational motion of the asphalt
Tg transition.
freezes, which leads to the rigidness of the material at or below this temperature. The Tg is related to
Tg is defined as the temperature at which all the molecular translational motion of the asphalt
the low-temperature performance of asphalts. PA is found to have a more brittle nature in low
freezes, which leads to the rigidness of the material at or below this temperature. The Tg is related
temperature (approximately between −40 and 0 °C) as compared to NA.
to the low-temperature performance of asphalts. PA is found to have a more brittle nature in low
The endothermic peaks are more evident in PA than NA. Two major melting peaks are detected
temperature (approximately between −40 and 0 ◦ C) as compared to NA.
in the PA’ DSC thermogram that relate to the dissolution of crystallized fractions in the hydrocarbon
The endothermic peaks are more evident in PA than NA. Two major melting peaks are detected
matrix. Also, there is a small peak emerging between these two endothermic peaks.
in the PA’ DSC thermogram that relate to the dissolution of crystallized fractions in the hydrocarbon
When heating the asphalts to the wax dissolution, Lesueur (2009) [22] explained the wide
matrix. Also, there is a small peak emerging between these two endothermic peaks.
endothermic effects occurring between −30 °C and 100 °C in several naturally wax- (or saturate-)
When heating the asphalts to the wax dissolution, Lesueur (2009) [22] explained the wide
encompassing binders. Hence, the highly visible broad endothermic band up to 100 °C in all the
endothermic effects occurring between −30 ◦ C and 100 ◦ C in several naturally wax- (or saturate-)
asphaltic samples relates to the melting of diverse naturally occurring waxes existing in the asphalt
encompassing binders. Hence, the highly visible broad endothermic band up to 100 ◦ C in all
[22,23].
the asphaltic samples relates to the melting of diverse naturally occurring waxes existing in the
asphalt [22,23].
3.12. Physical and Rheological Analysis
3.12. Table
Physical and Rheological
6 gives Analysis to different physical and rheological properties, comprising
the data pertaining
penetration, softening
Table 6 gives point,pertaining
the data ductility, and viscosity.
to different physical and rheological properties, comprising
penetration, softening point, ductility,
Table 6. and viscosity.
Conventional rheological properties for PA and NA.

Asphalt
Property
PA NA
Penetration at 25 °C, 1/10 mm (dmm) 63.33 147.00
Softening point, (°C) 49.00 40.00
Ductility at 25 °C, (cm) >140 >140
Viscosity at 135 °C, (Pa·s) 0.50 0.35
Viscosity at 180 °C, (Pa·s) 0.10 0.08
Materials 2016, 9, 859 17 of 20

Table 6. Conventional rheological properties for PA and NA.

Asphalt
Property
PA NA
◦ C,
Penetration at 25 1/10 mm (dmm) 63.33 147.00
Softening point, (◦ C) 49.00 40.00
Ductility at 25 ◦ C, (cm) >140 >140
Viscosity at 135 ◦ C, (Pa·s) 0.50 0.35
Viscosity at 180 ◦ C, (Pa·s) 0.10 0.08

3.12.1. Penetration
The major objective of deploying a penetration test is to categorize asphalt cements for the purpose
of detecting and acquiring the desired materials. However, it can be used for other purposes as well,
such as detecting extended heating of asphalts placed within the storage tanks. It is also useful in
evaluating the properties of asphalts, which defines how the respective material has corresponded to
time and weathering after it is removed from the pavement [24]. As seen in Table 6, NA has a greater
value of penetration, i.e., 147.00 dmm, than PA, which has a value of 63.33 dmm. For avoiding cracks
in pavements, soft NA is utilized in the construction of pavements during colder climates and PA is
utilized in hot climates.

3.12.2. Softening Point

The softening point of road asphalt is defined as the temperature at which the asphalt transforms
from its solid state to a definite liquid state due to the application of some external force and heat.
It can be related to the temperature susceptibility of asphalt at high temperature changes. At high
temperature, asphalt has less resistance to internal share force. Hence, the asphalt is unable to resist
an applied force. As the softening point increases, the deformation of the asphalt decreases due
to its increase in resistivity towards high temperatures [25]. Table 6 depicts the softening point of
both PA and NA. From the table, it can be seen that PA has a higher softening point (49.00 ◦ C) than
NA (40.00 ◦ C). Also, when the softening point is increased, the C/H ratio including the degree of
aromatization also increases. The presence of compounds (saturates) with lower molecular weight
is a major facilitator in increasing the softening point. Also, the rupture in the double bonds and
straight chains, and the polymerization reactions of the radicals formed under the catalytic effect in
the asphalts result in a higher softening point.

3.12.3. Ductility Test

The purpose of conducting a ductility test is to evaluate the resistivity of asphalt towards cracking
and raveling. It is known that high-ductility asphalts have superior flexibility and tenacity. Similarly,
asphalts with lower ductility have a higher tendency to crack under heavy loads or severe temperature
variations. The procedures of refining and consistency have great influence on the ductility of the
asphalts [24]. As seen in Table 6, after performing the ductility test, it was observed that both PA and
NA display high ductility values (>140 cm) (Table 6). Therefore, this revelation suggests that both the
asphalt materials will provide good performance during the service life of pavement.

3.12.4. Viscosity
Viscosity plays a significant role during the manufacturing of asphalt, which comprises distinct
stages such as transportation, laying, mixing, and compaction. Depending on the binder, the ranges of
viscosity are determined at each of the abovementioned stages [26]. Generally, at a high temperature
of 135 ◦ C, the viscosity is applied for evaluating workability, as per the Superpave specification [27].
Also, depending on the grade or viscosity, the asphalts are kept in asphalt plants at temperatures
between 149 ◦ C and 177 ◦ C for convenience of pumping [28]. Hence, the current research selected
Materials 2016, 9, 859 18 of 20

the temperatures of 135 ◦ C and 180 ◦ C for the purposes of viscosity testing. The results revealed in
Table 6 suggest that PA has greater viscosity values as compared to those of NA. On this basis, varied
workability and storage temperatures are anticipated from the tested asphaltic materials.

4. Conclusions
The current research utilized petroleum asphalt (PA) from an anonymous refining company in
South Korea, which was inspected by deploying extensive analytical and rheological techniques to
characterize the asphaltic sample. To further estimate the findings and confirm their placement
in the framework of the enhanced materials, structural comparisons with natural asphalt (NA)
were conducted. The natural asphalt was acquired from Utah, USA. The results obtained from the
examination of the asphalts through the battery of analytical techniques were found to be harmonious
and comprehensible in terms of the known origins of the samples.
The major findings of the study drawn from the analysis of the data are portrayed below:

- The results of this study revealed a clear distinction between the elemental compositions of PA
and NA.
- The SARA composition and the colloidal index stability were highly affected by the chemical
composition of the feedstock and the technology of asphalt production.
- Whereas the average value of the molecular weight of PA was found to be 328 Da, it was
252 Da for NA. Therefore, the compound types existent in the asphalts have diverse molecular
weight distribution.
- UV-Vis spectroscopy indicates the existence of more highly conjugated systems in NA than in PA.
- NA has a lower carbon aromaticity than PA as observed from the analyses of FT-IR, Raman,
and NMR tests. Also, NA has comprehensive alkylated aromatic structures with large amount
of oxygenates.
- Whereas clay minerals are present in NA, they are absent in PA. This result was obtained from
the FT-IR, XRD, and SEM analyses.
- Thermogravimetric analysis performed in air atmosphere indicated that the PA sample was
thermally more stable than the NA sample.
- When performing the differential scanning calorimetry of NA and PA, the former binder
demonstrated a narrow endothermic peak at about 40~50 ◦ C, while the latter displayed two
broad endothermic bands at 14.50 ◦ C and 48.5 ◦ C. This revelation corresponds to the melting of
different crystallizing wax fractions present in the asphalt.
- Due to the different exhibition of chemical composition and structure in both the asphalts, PA and
NA performed differently in the rheological tests.

It is strongly recommended that further work should be undertaken to investigate the mechanical
properties of asphalt cement binders (and their relationship to pavement performance. Future work
may involve the use of different test methods such as forced vibration co-axial shear test (FVAST),
dynamic shear rheometer (DSR), bending beam rheometer (BBR), and pressure aging vessel (PAV), etc.

Acknowledgments: This work was performed as a part of the project of the development of eco-friendly
pavements to minimize greenhouse gas emission. We appreciate the financial support from the “Transportation
Logistics research program (Grant 15TLRP-B079261-02)” of MOLIT (Ministry of Land, Infrastructure & Transport)
and KAIA (Korea Agency for Infrastructure Technology Advancement) of the Republic of Korea.
Author Contributions: Nader Nciri performed the chemical experiments, carried out the data interpretation, and
drafted the paper. Jeonghyun Kim performed the physico-rheological experiments. Namho Kim and Namjun Cho
monitored and led the whole research project. All authors read and approved the final manuscript.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2016, 9, 859 19 of 20

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