Construction and Building Materials 101 (2015) 1078–1087

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Construction and Building Materials

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

Fourier Transform Infrared Spectroscopy characterization

of aging-related properties of original and nano-modified
asphalt binders
Hui Yao, Qingli Dai, Zhanping You ⇑
Department of Civil and Environmental Engineering, Michigan Technological University, 1400 Townsend Drive, Houghton, MI 49931, USA

h i g h l i g h t s

 Six functional groups containing the carbonyl group were analyzed.

 The carboxylic acids, amide and ketones are the primary components.
 The mild aging of asphalt enhances the resistance to rutting and moisture damage.

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

Article history: The objective of this study is to analyze the effect of aging on asphalt binders under the conditions of dry
Received 20 March 2015 and sufficient oxygen, and to identify the functional groups related to the fatigue and rutting of asphalt
Received in revised form 28 August 2015 mixtures. During the asphalt aging process, the six functional groups (carboxylic acids, aldehydes,
Accepted 15 October 2015
amides, anhydrides, esters and ketones) containing the carbonyl group can be found in the asphalt bin-
ders based on the Fourier Transform Infrared Spectroscopy (FTIR) test results and references. The func-
tional groups containing the carbonyl group in the asphalt binders can be also used to correlate to the
Keywords:
oxidation extent of asphalt binders. Three nanomaterials were added into the control asphalt binder to
Asphalt
Fourier Transform Infrared Spectroscopy
study the effect of aging. The three materials included polymer modified nanoclay (PMN), non-
(FTIR) modified nanoclay (NMN) and nanosilica (NS). The rolling thin film oven (RTFO) and pressure aging vessel
Aging (PAV) aging effects of the asphalt binders were analyzed to understand the functional polar groups in the
Carbonyl groups asphalt system under short- and long-term aging conditions, respectively. The different asphalt binders
were tested by FTIR to obtain the spectra of chemical groups. The FTIR characterization results indicate
that the carboxylic acids and ketones are the main aging components in the asphalt when exposed to air
and oxygen. The esters and aldehydes in the asphalt are kept to a limited amount. Furthermore, these
functional groups, along with the carbonyl group are closely related to the susceptibility of rutting and
the fatiguing of asphalt mixtures.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction asphalt binders. The modifiers include various polymers, different

Nowadays, asphalt material is widely applied in pavement engi-
neering. The properties of asphalt binders determine the perfor-
mance of the asphalt pavement. The viscosity of asphalt binders
relates to the mixing and compaction temperatures. The modulus
of asphalt binders has a connection with the high- and low-
temperature performance of asphalt mixtures. In order to improve
the performance of pavement, different modifiers are mixed with
⇑ Corresponding author.
E-mail addresses: huiyao@mtu.edu (H. Yao), qingdai@mtu.edu (Q. Dai),
zyou@mtu.edu (Z. You).
fibers, some waste materials and many kinds of nanomaterials
[1,2]. Currently, aging is the main problem with asphalt and anti-
aging research in different fields is still a hot topic. The quality
and life of the pavement also relate to the speed of aging of the
materials used in asphalt mixtures and cement concretes [3–5].
Oxidation causes the degradation of pavement and decreases
the bonding strength between the asphalt and the aggregates. This
will lead to pavement embrittlement and pavement distress, par-
ticularly pavement cracking [6]. The aging of asphalt is caused by
the processes of volatilization, oxidation, and steric hardening.
Volatilization and oxidation of asphalt are produced by chemical
reactions or the changing of the asphalt structure. Steric hardening

http://dx.doi.org/10.1016/j.conbuildmat.2015.10.085
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
 H. Yao et al. / Construction and Building Materials 101 (2015) 1078–1087
of asphalt is produced by intermolecular reconstruction. Asphalt
aging also relates to the physical properties of asphalt, as well as
the compositional changes in the asphalt. Aging is a non-
reversible process caused by ultraviolet (UV) light, oxygen, and
heating when exposed to air [6–8]. The carbonyl groups and sul-
foxide groups increase in molecular structure, as do the polar func-
tional groups (polar asphalt) in asphalt molecules. The carbonyl
groups in the asphalt binder include carboxylic acid, aldehyde,
amide, anhydride, ester and ketone. During the oxidation of
asphalt, the polar and aromatic compositions in the asphalt
agglomerate, and it reduces the mobility and reactivity. This can
be due to the micellar catalysis, which allows the molecules to
be buried in the micelle at reaction sites. For example, ketones
may be highly concentrated in the polar parts and aromatics due
to the reactions from the components bonded to benzylic carbons.
Ketones in asphalt decrease the compatibility at low temperatures.
Researchers showed that the new asphaltene components might
be formed from the maltenes or polar aromatics after asphalt oxi-
dizes. The new asphaltenes had the same impact on viscosity as the
original asphaltenes [8–10].
During oxidation, both polar sulfoxides and ketones are pro-
duced in the asphalt. They contain an electronegative oxygen and
a dipole, which can interact with other dipoles to form new com-
ponents. Generally speaking, the sulfoxide is more polar than the
ketone. From the literature reviews [8–10], the ketones were
formed beyond the oxidation spurt, and the ketones and sulfoxides
might not be the fundamental reason for an increase in viscosity
after oxidation. It is possible that the molecular agglomerations
were the primary reason for the increase in the viscosity. It is
reported that the molecular weight of polymers is connected with
the viscosity. During the formation of ketones, the reaction leads to
the formation of larger agglomerates which have significant effects
on the molecular weight, and also increases the viscosity. In addi-
tion, the mild oxidation in asphalt binders decreases the moisture
damage of asphalt mixtures. The aging process of asphalt is shown
in Fig. 1.
Nanomaterial is a new kind of popular material with many
incredible features. It is possible that nanomaterials could be a
good modifier and may fundamentally change the properties of
asphalt binders and mixtures. Nanomaterials may be utilized to
improve the performance and durability of construction and build-
ing materials. The nano-SiO2 (Silicon dioxide) and styrene–buta
diene-styrene (SBS) were also used together in the modification
of asphalt. The results showed that the asphalt mixture modified
by 5% SBS and 2% nano-SiO2 (by weight of the control asphalt)
improved the mechanical properties of asphalt binders and mix-
tures [11]. Carbon nanofibers (CNFs) were mixed with asphalt
cement, and viscoelastic and fatigue characteristics of CNF-
modified asphalt binders were investigated. The resistance to rut-
ting of modified asphalt cement (AC) was improved and the fatigue
life of CNF-modified AC was increased [12,13]. The performance of
UV Heating Oxygen Weather
Asphalt
Resin asphaltene,
Carbonyl Sulfoxide Nitrogen
and maltene
groups groups oxides
partially produce
Polar groups and aromatic components in
the asphalt
Fig. 1. The aging processes of asphalt exposed to air.
1079
asphalt binders modified by non-modified nanoclay (NMN) and
polymer modified nanoclay (PMN) was examined, and the
microstructures were observed. With the addition of NMN into
the control asphalt binder, the complex shear modulus of the
modified asphalt binder increased, while the addition of PMN into
the control asphalt binder decreased the complex shear modulus of
the modified asphalt [2]. Polysiloxane-modified montmorillonite
and/or carbon microfiber were used to modify the asphalt binders
and mixtures. Relative to the control asphalt mixture, the modified
asphalt mixture improved the tensile strength and fracture energy,
decreased the moisture susceptibility, and reduced the risk of
cracking [14]. In this study, three nanomaterials (polymer modified
nanoclay, non-modified nanoclay and nanosilica) were added to
the asphalt to study the effects of aging. The Fourier Transform
Infrared Spectroscopy (FTIR) was employed to identify the compo-
sition of asphalt.
2. Research motivation
The objective of this research is to analyze the effect of aging on
the asphalt binders when exposed to air and oxygen, and identify
the functional groups correlated to the resistance to rutting and
fatigue life of asphalt mixtures. The six functional groups
(carboxylic acid, aldehyde, amide, anhydride, ester and ketone)
containing the carbonyl group can be found in the asphalt binders
from FTIR results and related references. The functional groups
containing the carbonyl group in the asphalt binders can also be
found to relate to the oxidation degree of asphalt binders. Several
nanomaterials were added to the control asphalt binder to study
the effects of aging using the rolling thin film oven (RTFO) and
pressure aging vessel (PAV), which simulates the short- and
long-term aging in the asphalt binders, respectively.
3. Chemistry of carbonyl groups in an asphalt binder
When the asphalt oxidizes, it is likely that the six functional
groups containing the carbonyl group in the asphalt binder are
present, which include carboxylic acids, aldehydes, amides,
anhydrides, esters and ketones.
3.1. Carboxylic acid
Carboxylic acid in the asphalt binder, referred as R–C (O) OH, a
carboxyl group (C (O) OH) and R (the rest of the molecules) is
composed of an organic compound [15]. Due to both sides of the
hydrogen-bond, acceptor and donor, the carboxylic acids display
a polar activity. Carboxylic acids normally exist as dimeric pairs
in non-polar media for the self-associate effect. The carboxylic
acids only dissociate the H+ cations and RCOO anions [16]. The
alkyl groups on the benzene rings can be oxidized in carboxylic
acid no matter what the chain length of the alkyl groups is [17].
3.2. Aldehyde groups
Aldehyde groups are also organic, and the structure can be
demonstrated as R-CHO. It also features a sp2 hybridized and
planar carbon, and the carbon atom connects to oxygen with a
double bond. A carbonyl group is located in the center, and the
carbon atom bonds to the hydrogen and R group. The bond
between the carbon and hydrogen is not actually acidic, but the
aldehyde group is a polar group [15,18,19]. Due to the high reactiv-
ity of the formyl group, it is hard for the aldehydes to exist in the
natural state, and it is commonly prepared by the oxidation of
alcohol [20,21]. The formyl group can be reduced and oxidized to
alcohol (–CH2OH) and carboxylic acid (–COOH), respectively [21].
1080 H. Yao et al. / Construction and Building Materials 101 (2015) 1078–1087
3.3. Amides
Acid amides are an organic group that normally have three
kinds of structures, an organic amide (RCONR0 2), a sulfonamide
(RSO2NR0 2) and a phosphoramide (R2PONR0 2). The common
formula of functional groups containing the amide is RnEOxNR0 2,
and E represents different elements with n and x representing
the number of atoms [15]. The simple amide is the RCONH2 and
can be derivate from ammonia. Due to the carbonyl bond in the
amide, the amide is a hydrogen bond acceptor. The existence of
the hydrogen and nitrogen bond makes the amide a hydrogen bond
donor [22].
3.4. Anhydrides
Anhydrides are organic, acidic compounds, and have two acyl
groups (RCO-, carbonyl and alkyl groups), which are bonded by the
oxygen atom [15]. The preparation of acetic anhydrides can be
derived from the carbonylation of methyl acetate. It has a pleasant
smell, and it is a cheap and readily way to produce acetic anhydrides
[16,23]. Acid anhydrides normally have the same reactions as the
acid chlorides, and the speed of the reactions is a little slow [16].
3.5. Esters
Esters can be derived from an inorganic/organic acid and they
are commonly obtained from carboxylic acids and alcohol. The
hydroxyl group (–OH group) in the esters is replaced by the –O-
alkyl group [15]. R and R0 are the hydrocarbon parts in the organic
esters (RCO2R0 ) [15,24]. Esters can be the hydrogen bond acceptors
in the reactions, however, esters are normally not the hydrogen
bond donors [24].
3.6. Ketones
Ketones are organic compounds containing the carbonyl groups
(carbon and oxygen atoms with a double bond), and its structure is
RC (=O) R0 , where the R and R0 are the hydrocarbon groups. The
symmetrical and asymmetrical ketone groups depend on the con-
nected alkyl groups. The carbonyl group is a polar group due to the
higher electronegativity of oxygen. Typically, the ketones are
acceptors of hydrogen bonds, not the donors. The ketone itself will
not show the tendency to self-associate together [16].
Sometimes, the peaks of bonds are shifted by a few wavenum-
bers (around 5–10 cm 1 wavenumbers) due to the infrared
detection and some chemical reactions in the material. The peak
of bonds should be adjusted by the actual detection results. The
carbonyl groups in the asphalt binder are displayed in Fig. 2, based
on the references [15,25].
O
O O
C R'
C C R N
R H
R OH R'
1) Carboxylic Acid 2) Aldehyde 3) Amide
R O R' O O
C C
C C
O O H OR' R R'
4) Anhydride 5) Ester 6) Ketone
Fig. 2. Six functional groups containing the carbonyl group.
4. Fourier Transform Infrared Spectroscopy characterization
method
Infrared spectrometry (IR) is playing an important role in the
industry and in research. For instance, U.S. pharmaceutical compa-
nies must submit the IR spectra of products when the product
application is being processed by the Food and Drug Administra-
tion to show the molecular structures. IR provides more valuable
chemical information about the molecular bonds or vibrations than
other methods. FTIR is a technical method used to detect the infra-
red absorption of samples [26,27]. Spectral data is collected in wide
range wavelengths. The carbon and hydrogen content in the
organic asphalt is over 90% [28]. Normally, in organic compounds,
six movements are involved in the CH2 groups:symmetrical
stretching, anti-symmetrical stretching, scissoring, rocking, wag-
ging, and twisting [29]. The movements of molecules are smaller
than those of lighter H atoms. The symmetrical stretching and
anti-symmetrical stretching are commonly detected in asphalt.
The Jasco IRT 3000 FTIR spectrometer was used to detect the
samples in the study. The solid samples were placed on the silicon
substrates and the calculation of the ratio of specific bonds
(wavelength range) in the asphalt was carried out. Two methods,
‘two points’ and ‘no base point’, are generally used in the IR ratio
calculation (Fig. 3). When the specific range is determined for the
bond ratio calculation and the overlap and shift phenomena of
bond peaks cannot be avoided due to the complexity of the asphalt
material, the method of ‘two points’ may cause the ratio computing
line to cross the peak area. It can affect the accuracy of the ratio
calculation. However, the calculation method of ‘no base point’
can avoid the error, and the difference between the saturated
and unsaturated bonds can be differentiated.
5. Materials preparation
The PG58-34 control asphalt was obtained from Gladstone,
Michigan and pre-modified by acrylonitrile butadiene styrene
(ABS) to improve the performance at low temperatures. The
compatibility between the asphalt and the polymer is enhanced
[2]. Nanoclay (a kind of montmorillonite), has a 2-to-1 layered
and plate structure, and it is commonly used to enhance various
properties of polymers. Sodium ions construct the layer, and it
causes a high expansion pressure in the system. The structure
can easily be intercalated and exfoliated. PMN was treated by the
polysiloxane with organic cation exchanges. After the modification,
Control asphalt
0.4
Control asphalt
0.3
Absorbance(a.u.)
0.2
No base point
Two points
0.1
Two points
0
1900 1850 1800 1750 1700 1650 1600
-1
Wavenumber(cm )
Fig. 3. Ratio calculation methods commonly used in the FTIR spectra.
 H. Yao et al. / Construction and Building Materials 101 (2015) 1078–1087 1081

the strength of PMN improved. The density of NMN and PMN is Control asphalt
0.678 and 0.251 g/cm3, respectively [30,31]. The nanosilica (NS) 1.5
Control asphalt
was from MTI Corporation, United States of America. The density 1.4

and the maximum size of nanosilica are around 0.063 g/cm3 and 1.3
1.2
30 nm, respectively [1,31]. The performance tests of these modified
1.1
asphalt binders were accomplished in previous studies done by

Absorbance(a.u.)
1.0
authors [1,2]. Carbon-Oxygen (C-O)
0.9 single bond stretching area
Nitrogen-Hydrogen
0.8 (N-H) bending
6. Experimental design and procedures 0.7 area Sulfoxide (S=O) area
0.6
The modifiers and their content in the asphalt are 2% and 4% NMN, 2% and 4%
0.5
PMN, and 4% and 6% NS. The nanomaterials were slowly added to the control
asphalt and the modified asphalt binders were blended for two hours in the high 0.4
shear machine under the conditions of 4000 rpm and 135 °C. NMN, PMN and NS 0.3
modified asphalt binders were processed by RTFO and PAV aging in order to analyze 0.2
the effect of aging. The asphalt samples were tested under the original, RTFO and 0.1
PAV conditions using FTIR. The samples were placed on the silicon substrate
0
(100 X cm) with a 350 lm thickness. The FTIR results were recorded with an 1700 1600 1500 1400 1300 1200 1100 1000 900
accumulation of at least 128 scans with a resolution of 4 cm 1. The two duplicates
Wavenumber(cm-1)
for each sample were prepared and tested with FTIR.

Fig. 5. Nitrogen–hydrogen and carbon–oxygen bonds in the asphalt binder (solid

7. FTIR characterization of functional group components state).

The six functional groups (carboxylic acid, aldehyde, amide,

anhydride, ester and ketone) contain the carbonyl group in the Control asphalt
asphalt binder. The evidence of these groups can be found in the 2.4
Control asphalt
spectra and references. In addition, the overlapping phenomena 2.2
of the bonds in the spectra are common in complex materials, as 2.0
detected by FTIR. This indicates that some bands are not clearly
1.8
shown in the spectra. The peaks in the spectra show the infrared
1.6
Absorbance(a.u.)

absorbance in the materials and it also reflects the extent of bonds

in the materials. If the amount of bonds in the asphalt is too small, 1.4
Carbon-Hydrogen stretching
the difficulty of detection increases. The control asphalt was exam- 1.2 bond area (C-H bond, two peaks)
ined by FTIR, and the FTIR spectra are shown in Figs. 4 through 6. 1.0
Nitrogen-Hydrogen stretching
0.8 area (N-H bond)
7.1. Functional group acid amides 0.6 Oxygen-Hydrogen
0.4 stretching area (O-H bond)
Based on the literature review [32,33], the nitrogen and hydro-
gen (N–H) stretching bond and N–H bending bond are observed 0.2

around the region of 3100–3500 cm 1 (including a shoulder band) 0

4000 3500 3000 2500
and 1550–1640 cm 1 in the spectra from Table 1, respectively. The
Wavenumber(cm-1)
N–H stretch bond is also located in the region of 3250–3400 cm 1
and the N–H bend bond is located in the region of 1580–1650 cm 1 Fig. 6. Oxygen–hydrogen and nitrogen–hydrogen bonds in the asphalt binder (solid
from the references [34,35] (Primary amine: two N––H bands from state).
3300 to 3400 cm 1 and 3250 to 3330 cm 1, Secondary amine: one

N–H band from 3310 to 3350 cm 1 in the spectra of representa-

Control asphalt tives). N–H wag is located in the region from 665 to 910 cm 1 in
0.4
Control asphalt the spectra. Normally, the shoulder band of the N–H stretching
Amide bond is the overtone of the N–H bending bond. This indicates that
Ketone the N–H stretching and bending bonds can be observed at the same
0.3 Acid time and in the same material, such as the aniline (primary amine)
and diethylamine (secondary amine) [34,35]. Fig. 4 displays that
Absorbance(a.u.)

the carbonyl groups (C@O) in the amide (located in the region

Aldehyde
1640–1690 cm 1) can be observed in the spectrum of the control
0.2 Ester asphalt binder. This bond (C@O) is the aging index in the asphalt
Anhydride materials and it is formed by the complex oxidation reaction in
Anhydride
the asphalt. The aging of asphalt relates to the performance of
0.1 asphalt binders and asphalt mixtures [3]. From Figs. 5 and 6, the
N–H stretching and bending bonds can be seen in the control
asphalt binder. The content of the nitrogen element in the asphalt
binder is around 1% according to the Superpave report [28]. Due to
0 the small amount of the nitrogen element in the asphalt binder and
1900 1850 1800 1750 1700 1650 1600
the overlapping case of spectra, the peak of the nitrogen and
Wavenumber(cm-1)
hydrogen bond in the asphalt binder may not be so strong in the
Fig. 4. Functional groups containing the carbonyl group in the asphalt binder (solid spectra, but it is still detectable. The N–H stretching and bending
state). bond areas are close to the C–H and C–C areas in the spectra of
1082 H. Yao et al. / Construction and Building Materials 101 (2015) 1078–1087

Table 1 limited amount of anhydrides present in the oxidized asphalt.

Functional groups containing a carbonyl in the asphalt binder [32,33]. However, the larger amounts of anhydrides are observed in the
Absorption Assignations- Details older pavement, as well as ketones [6]. Therefore, the evidence of
wavenumber area functional anhydrides in the asphalt is presented, and one peak area ratio is
(cm 1, possible peak groups calculated in this study for the data analysis.
areas)
1670–1820 Carbonyl: Stretching vibration, conjugation
7.3. Functional group esters
C@O moves absorptions to lower wave
numbers, strong intensity
Based on the references [32,33], the two main stretching bonds,
Functional groups: carboxylic acid
1700–1725 C@O Stretching vibration the carbon–oxygen (C@O) double stretching bond and the carbon–
2500–3300 O–H Stretching vibration, strong oxygen single stretching bond (C–O) are observed in the ester
intensity, very board areas group. Fig. 4 shows that the peak of the carbonyl group in the ester
1210–1320 C–O Stretching vibration, strong
is observed at a range of 1735–1750 cm 1. And Fig. 5 shows that
intensity
the more peaks of carbon–oxygen single bond (C–O) are detected
Functional groups: aldehyde
at a range of 1000–1300 cm 1 in the solid samples. It is coincided
1720–1740 C@O Stretching vibration, strong
intensity with Table 1. Due to the trace amount of ester in the asphalt, the
2820–2850 & 2720– =C–H Stretching vibration, medium ester has a limited contribution to the asphalt aging products [9].
2750 intensity, two peaks Therefore, the ester group is one of the products produced during
Functional groups: amide the oxidation of asphalt.
1640–1690 C@O Stretching vibration, strong
intensity
7.4. Functional group carboxylic acids
3100–3500 N–H Stretching vibration,
unsubstituted, have two bands
1550–1640 N–H Bending vibration The references [32,33] mention that the functional carboxylic
Functional groups: anhydride acid group has three bonds connected: the carbon–oxygen double
1800–1830 and 1740– C@O Stretching vibration, two bands stretching bond (C@O), the carbon–oxygen single stretching bond
1775 (C–O), and the oxygen–hydrogen bond (O–H). In Fig. 4, the peak
Functional groups: ester of the carbonyl group [3] in the carboxylic acids can be found in
1735–1750 C@O Stretching vibration, strong the range of 1700–1725 cm 1; the peak of the carbon–oxygen sin-
intensity
gle stretching bond (C–O) [9] can be observed in Fig. 5 in the range
1000–1300 C–O Stretching vibration, two bands or
more
of 1210–1320 cm 1. The evidence of the hydroxyl group is shown
from the raised and broad area [36] in Fig. 6 in the range of 2500–
Functional groups: ketone
1705–1725 Acyclic Stretching vibration, strong
3300 cm 1 in the solid samples. In addition, from the reference of
intensity Campbell’s results [9], the evidence of carboxylic acids in the
3-Membered-1850 Cyclic Stretching vibration, strong asphalt was demonstrated and further conclusions were brought
intensity forward. Therefore, the carboxylic acids exist in the control asphalt.
4-Membered-1780 Stretching vibration, strong
intensity
5-Membered-1745 Stretching vibration, strong 7.5. Functional group aldehydes
intensity
6-Membered-1715 Stretching vibration, strong In accordance with the references [32,33], there are two bonds,
intensity
7-Membered-1705 Stretching vibration, strong
carbonyl group (C@O) and carbon–hydrogen bond (C–H), that exist
intensity in the aldehyde. Fig. 4 shows that the peaks of the carbonyl group
1665–1685 a,b- Stretching vibration, strong in the aldehyde are observed in the range of 1720–1740 cm 1. Two
Unsaturated intensity peaks of the carbon–hydrogen bond can be found in the range of
1680–1700 Aryl ketone Stretching vibration, strong
2820–2850 and 2720–2750 cm 1 in Fig. 6. These ranges in the
intensity
spectra normally represent the C–H bonds in the organic materials.
In 1964, Campbell also commented that the aldehyde had a
contribution to the carbonyl group in the asphalt [9]. Therefore,
asphalt, definitely increasing the difficulty of detection and obser-
the aldehydes are detected in the asphalt samples.
vation. The N–H bending bond in the asphalt is shown in Fig. 5. The
shoulder band in the asphalt at a solid state is demonstrated in
Fig. 6. Therefore, the functional group acid amide can be detected 7.6. Functional group ketones
in the control asphalt binder.
Based on the references [32,33], the carbonyl group in the
ketones can be found at a broad range of 1665–1850 cm 1 in
7.2. Functional group anhydrides Fig. 4, and different kinds of ketones may include acyclic, cyclic,
a,b-unsaturated and aryl ketone. Campbell [9] also demonstrated
The references [32,33] show that two bands around 1800–1830 that the ketones in the asphalt reinforced the absorbance of the
and 1740–1775 cm 1 are observed in the anhydride, a functional carbonyl group at around 1700 cm 1. The ketones are the main
carbonyl group. Two peaks in the range of 1800–1830 and 1740– aging products in the asphalt and it also relates to the performance
1775 cm 1 are observed in Fig. 4. However, in Fig. 4, the peak of the binders and mixtures according to the references [37–40].
between 1800 and 1830 cm 1 is not strong compared to the peak Therefore, ketones can be found in the asphalt.
between the 1740 and 1775 cm 1. Dicarboxylic anhydrides are
produced during the oxidation of asphalt, and the absorption 8. FTIR characterization results and discussions
bands of dicarboxylic anhydrides are around 1725 and
1765 cm 1. Due to the coverage of strong ketone bands, the peaks After the identification of functional groups in the control
around these two bands are not easily observed [6,7], as well as a asphalt, the control and modified asphalt binders were tested by
 H. Yao et al. / Construction and Building Materials 101 (2015) 1078–1087 1083

Control asphalt 2% NMN modified asphalt

0.6 0.5
Control asphalt - Original 2% NMN modified asphalt - Original
Control asphalt - RTFO 2% NMN modified asphalt - RTFO
0.5 Control asphalt - PAV 2% NMN modified aspahlt - PAV
0.4
Absorbance(a.u.)

Absorbance(a.u.)
0.4
0.3

0.3

0.2
0.2

0.1
0.1

0 0
2000 1900 1800 1700 1600 1500 2000 1900 1800 1700 1600 1500
Wavenumber(cm )-1 Wavenumber(cm-1)

1 1
Fig. 7. FTIR spectra of the control asphalt in the range of 1500–2000 cm . Fig. 10. FTIR spectra of 2% NMN modified asphalt in the range of 1500–2000 cm .

2% PMN modified asphalt 4% NMN modified asphalt

0.6 0.8
2% PMN modified asphalt - Original 4% NMN modified asphalt - Original
2% PMN modified asphalt - RTFO 4% NMN modified asphalt - RTFO
0.7
2% PMN modified aspahlt - PAV 4% NMN modified aspahlt - PAV
0.5
0.6
Absorbance(a.u.)
Absorbance(a.u.)

0.4 0.5

0.4
0.3

0.3
0.2
0.2

0.1 0.1

0
0 2000 1900 1800 1700 1600 1500
2000 1900 1800 1700 1600 1500
-1 Wavenumber(cm-1)
Wavenumber(cm )
1
1 Fig. 11. FTIR spectra of 4% NMN modified asphalt in the range of 1500–2000 cm .
Fig. 8. FTIR spectra of 2% PMN modified asphalt in the range of 1500–2000 cm .

4% NS modified asphalt
4% PMN modified asphalt 0.7
0.5 4% Nanosilica modified asphalt - Original
4% PMN modified asphalt - Original
4% Nanosilica modified asphalt - RTFO
4% PMN modified asphalt - RTFO
0.6 4% Nanosilica modified asphalt - PAV
4% PMN modified aspahlt - PAV
0.4
0.5
Absorbance(a.u.)
Absorbance(a.u.)

0.3 0.4

0.3
0.2

0.2

0.1
0.1

0 0
2000 1900 1800 1700 1600 1500 2000 1900 1800 1700 1600 1500

Wavenumber(cm-1) Wavenumber(cm-1)

1
Fig. 9. FTIR spectra of 4% PMN modified asphalt in the range of 1500–2000 cm 1
. Fig. 12. FTIR spectra of 4% NS modified asphalt in the range of 1500–2000 cm .
1084 H. Yao et al. / Construction and Building Materials 101 (2015) 1078–1087
FTIR. The control, NMN, PMN, and NS modified asphalt binders
were tested under the RTFO and PAV aging conditions. The spectra
of the control asphalt and nano-modified asphalt are shown in
Figs. 7 through 13. The peak range of functional polar carbonyl
groups in the asphalt is demonstrated in Table 1.
From the spectra of the control, NMN, PMN and NS modified
asphalt binders, the trends under the unaged, RTFO- and PAV-
aged are almost similar. The extent and amounts of bonds under
different aging conditions are changed. The peak ranges of different
functional carbonyl groups were utilized to represent the ratio of
corresponding functional groups in the asphalt binders. The equa-
tions of ratio calculations of carbonyl groups in the asphalt binders
are shown in Eqs. (1) through (7). The large portion of C–H bonds
mainly focuses on the wavenumber between 4000 and 2000 cm 1,
and the aging components in the asphalt binders primarily concen-
trate on the wavenumbers between 2000 and 600 cm 1. Therefore,
the denominator of the equations is the area of the wavenumbers
between 2000 and 600 cm 1.The results of the ratio calculations in
the control and nano-modified asphalt are shown in Figs. 14
through 16.
Area of the carboxylic acid bands between 1720 and 1700 cm
Iacids ¼ P Fig. 15 displays the results of the ratio calculations of the control
Area of the spectral bands between 2000 and 600 cm 1
Area of the aldehyde bands between 1735 and 1720 cm
Ialdehydes ¼ P
Area of the spectral bands between 2000 and 600 cm
Area of the amide bands between 1660 and 1645 cm 1
Iamides ¼ P
Area of the spectral bands between 2000 and 600 cm 1
Area of the anhydride bands between 1775 and 1750 cm 1
Ianhydrides ¼ P
Area of the spectral bands between 2000 and 600 cm 1
Area of the ester bands between 1750 and 1735 cm 1
Iesters ¼ P 1
Area of the spectral bands between 2000 and 600 cm
Area of the aryl ketone bands between 1700 and 1685 cm 1
Iarylketones ¼ P
Area of the spectral bands between 2000 and 600 cm 1
ð6Þ
Area of the a;b unsaturated ketone bands between 1680 and 1665 cm
Ia;bunsaturated ketones ¼ X ð7Þ
Area of the spectral bands between 2000 and 600 cm 1
Fig. 14 shows the results of the ratio calculations of the unaged
control and nano-modified asphalt. The amides make up the lar-
gest amount present in the asphalt binders compared to the other
functional carbonyl groups. A large amount of carboxylic acids and
ketones also make up in the asphalt binders. It can be seen that the
quantities of aryl ketones are less than those of a,b-unsaturated
ketones. There are small amounts of esters in the asphalt, consis-
tent with the reference [9]. Meanwhile, the anhydrides and aldehy-
des are also found in limited amounts in the asphalt. After
modifying the asphalt, the functional carbonyl groups in the
nano-modified asphalt are more than those of the control asphalt.
This indicates that this modification brings more oxygen into the
modified asphalt during the mixing process.
6% NS modified asphalt
0.5
6% Nanosilica modified asphalt - Original
6% Nanosilica modified asphalt - RTFO
6% Nanosilica modified aspahlt - PAV
0.4
Absorbance(a.u.)
0.3
0.2
0.1
0
2000 1900 1800 1700 1600 1500
Wavenumber(cm-1)
1
Fig. 13. FTIR spectra of 6% NS modified asphalt in the range of 1500–2000 cm .
1
and nano-modified asphalt after RTFO aging, and the amides remain
ð1Þ
as the largest amount present in the asphalt binders relative to the
1 other carbonyl groups. But the carboxylic acids, ketones, and anhy-
1 drides in the asphalt significantly increase. The amount of aryl
ketones is also less than that of a,b-unsaturated ketones. Esters
ð2Þ
and aldehydes do not increase much in the RTFO-aged asphalt.
Fig. 16 displays the results of the ratio calculations of the
ð3Þ control and nano-modified asphalt after PAV aging. The carboxylic
acids in the asphalt continue to increase during PAV aging, and the
amount of carboxylic acids is the largest of the functional carbonyl
groups in asphalt after PAV aging. The amount of ketones in the
asphalt after PAV aging also increases. It is noticed that the quan-
ð4Þ tities of aryl ketones are more than those of a,b-unsaturated
ketones. But the amount of a,b-unsaturated ketones is larger than
that of aryl ketones in the asphalt at the original state and after
ð5Þ
RTFO aging. If the amounts of a,b-unsaturated ketones and aryl
ketones are added together, the ketones are considered the
primary oxidation products of the asphalt. Simultaneously, there
is still a large amount of amides in the asphalt; esters, aldehydes,
and anhydrides increase slightly compared to the amounts at the
1
unaged and RTFO-aged states. Esters remain as the smallest
amount present in the asphalt after PAV aging.
From Figs. 14 through 16, it is implied that the oxidation of
asphalt causes the increase in the functional carbonyl groups,
especially carboxylic acids and ketones, and they are the main
oxidation products. During the aging of the asphalt, the resins
and asphaltenes have some reactions with oxygen and produce
more aromatic hydrocarbons and polar functional groups. This
can be an explanation as to why aryl ketones and carboxylic
acids in the asphalt increase after PAV aging. Aged asphalt at
an earlier stage is good for pavement, in regard to the perfor-
mance. In addition, the data in Figs. 14–16 reveals that the
amount of aging components in the RTFO- and PAV-aged modi-
 H. Yao et al. / Construction and Building Materials 101 (2015) 1078–1087 1085

0.012

0.01

0.008

Ratio of Bonds
0.006

0.004

Carboxylic Acid Aldehyde

0.002 Amide Anhydride
Ester Aryl Ketone
αβ-unsaturated ketone
0
Control 2%NMN 4%NMN 2%PMN 4%PMN 4%NS 6%NS

Fig. 14. Ratio calculations of different bonds in the unaged control and nano-modified asphalt (solid state).

0.01
0.009
0.008
0.007
Ratio of Bonds

0.006
0.005
0.004
0.003
0.002 Carboxylic Acid Aldehyde
Amide Anhydride
0.001 Ester Aryl Ketone
0 αβ-unsaturated ketone
Control 2%NMN 4%NMN 2%PMN 4%PMN 4%NS 6%NS

Fig. 15. Ratio calculations of different bonds in the control and nano-modified asphalt after RTFO aging (solid state).

0.012

0.01

0.008
Ratio of Bonds

0.006

0.004

Carboxylic Acid Aldehyde

0.002 Amide Anhydride
Ester Aryl Ketone
αβ-unsaturated ketone
0
Control 2%NMN 4%NMN 2%PMN 4%PMN 4%NS 6%NS

Fig. 16. Ratio calculations of different bonds in the control and nano-modified asphalt after PAV aging (solid state). Note: Control: control asphalt; NMN: NMN modified
asphalt; PMN: PMN modified asphalt; NS: NS modified asphalt.

fied asphalt is commonly lower than that of the control asphalt,
as well as the aging speeds of the modified asphalt. However,
the amount of the control asphalt at the unaged state is ordinar-
ily lower than that of the modified asphalt. This indicates that
the nanomaterials have a resistance to aging in the asphalt.
These results are consistent with the reference [3].
Based on the literature review, the aging components relate to
the properties of the asphalt. (1) The carboxylic acid in the crumb
rubber asphalt AAB-1 improves the high-temperature properties,
especially rutting resistance [41]. The dry aggregates can be strongly
adhered to by the carboxylic acids (polar group) in the asphalt [42].
The polar groups in the asphalt tends to associate, and less polar or
1086 H. Yao et al. / Construction and Building Materials 101 (2015) 1078–1087
more nonpolar groups result in disassociation [43]; (2) the furan ring
with the aldehyde group improves the resistance to rutting and
water stripping of the asphalt, as well as the fatigue cracking [44];
(3) the amide group helps enhance the toughening and adhesion
in the asphalt [45]. The amide-type agents were also used for
strengthening the coating with aggregates in the asphalt and the
mechanical properties of the asphalt improved [46–48]; (4) the
aging groups, ketones, dicarboxylic anhydrides and carboxylic acids,
are strongly absorbed into the aggregates [49,50]; (5) the phosphate
and amino esters were used as an antistripping additive in the
asphalt. It is designed to improve the adhesion between the asphalt
and the aggregates [51,52]; (6) the ketones and sulfoxides are also
the main factors for the increase in viscosity of the oxidized asphalt
[8]. Therefore, there is a close correlation between the aging compo-
sition and the performance of the asphalt.
The ketones and carboxylic acids increase more after the oxida-
tion of asphalt, and the anhydrides and amides also increase in this
case. Therefore, these functional groups determine the perfor-
mance of these modified asphalt binders in this case. Based on
the performance test results [1–3,5], the mild asphalt aging can
improve the resistance to permanent deformation in asphalt pave-
ment when it is exposed to air and oxygen at an early stage. How-
ever, in long-term service years, the asphalt aging brings the
distress to pavement, and degrades the bonding between the
asphalt and the aggregates.
9. Discussions and conclusions
In this study, three nanomaterials were added to the control
asphalt binder to study the effect of aging; the materials include
polymer modified nanoclay, non-modified nanoclay and nanosil-
ica. The control and the nano-modified asphalt were tested by FTIR
to analyze the different carbonyl groups in the asphalt binders
under RTFO and PAV aging conditions. Based on the FTIR data anal-
ysis of the control and nano-modified asphalt, the following find-
ings can be summarized.
(1) The asphalt aging process was demonstrated and concluded
in this study. The asphalt can be oxidized through heating,
weathering, ultraviolet light, etc. The resins and maltenes
in the asphalt produce polar groups and aromatic compo-
nents, including carbonyl groups, sulfoxide groups and
nitrogen oxides.
(2) The six functional groups (amides, anhydrides, aldehydes,
carboxylic acids, ketones and esters) containing the carbonyl
group were tested in the asphalt oxidation products based
on the FTIR test results and references. The carboxylic acids
and ketones are the primary components in the oxidized
asphalt. There is a limited amount of esters and aldehydes
in the products of oxidized asphalt. The carboxylic acids
and ketones are the key components that correlate with rut-
ting and fatigue resistance in asphalt. In addition, the amides
and anhydrides are also the aging products of the asphalt
when exposed to air. Likewise, there is a close relationship
between the aging components and the improvement of
the rutting resistance and moisture susceptibility.
(3) Based on the test results by our research group [1–3,5] and
the references [49,50], the mild aging of asphalt enhances
the resistance to rutting and the moisture damage of asphalt
mixtures in dry conditions in the early stage. However, dur-
ing the long-term services, the aging of asphalt causes the
degradation of bonding between the asphalt and the aggre-
gates, and the distress of the asphalt pavement appears.
The six carbonyl groups in the control and the nanomaterials
modified asphalt were investigated through the FTIR characteriza-
tion analysis. The amounts of six carbonyl groups in the RTFO- and
PAV-aged asphalt increased. The carboxylic acids and ketones are
the main components of the asphalt, which relate to the perfor-
mance of binders and mixtures. The nanomaterials also have an
anti-aging effect on the asphalt. In addition, the aging components
in the asphalt under different environments will be studied in the
near future.
Acknowledgments
The authors would like to thank Dr. Yoke Khin Yap and
Mingxiao Ye for the help on FTIR testing. The experimental work
was completed at the Transportation Materials Research Center
of Michigan Technological University. Any opinion, finding, and
conclusion or recommendation expressed in this material are those
of the authors and do not necessarily reflect the views of any
organization.
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