Asphalt Binders Blended with a High Percentage of

Biobinders: Aging Mechanism Using FTIR and Rheology

Xu Yang 1; Zhanping You, Ph.D., P.E., M.ASCE 2; and Julian Mills-Beale 3

Abstract: The objective of this study is to characterize the rheological properties and aging mechanism of asphalt binders blended with high
percentages of biobinders using Fourier transform infrared spectroscopy (FTIR). The petroleum asphalt was partially replaced by the bio-
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binders at fractions of 30 and 70% by weight. Rotational viscometer (RV) and dynamic shear rheometer (DSR) tests were conducted for the
rheological properties, and the rolling thin film oven (RTFO) test was conducted for the aging simulation. Loss of volatiles was obtained from
the RTFO test, whereas the oxidation characterization was investigated through the FTIR test. The rheology results showed that the bio-
blended asphalt binder exhibit different rheological properties as compared with the control asphalt binder before and after the RTFO-aging.
The mass loss test showed that the loss of volatiles of biobinders were much higher than the control asphalt binder. FTIR spectra analysis
showed that additional C═C, C─O, C═O and OH bonds were generated during the aging. Further chemical analysis revealed that the aging of
biobinder originates from three aspects: the loss of volatiles, the dehydrogenation which formulates higher molecular weight compounds such
as asphaltene, and the oxidation which resulted in chemicals such as acids, alcohol, and ester. DOI: 10.1061/(ASCE)MT.1943-5533
.0001117. © 2014 American Society of Civil Engineers.
Author keywords: Biobinder; Rheological property; Aging mechanism; Loss of volatiles; Oxidation; Fourier transform infrared
spectroscopy (FTIR).

Introduction Biobinder is normally generated from a thermal-chemical

More than 90% of the pavements in the United States are made of
asphalt and more than 550 million tons of asphalt mixtures are pro-
duced to satisfy the construction needs of the industry. The limited
storage of petroleum asphalt motivates pavement researchers to
seek approaches to reduce the use of fresh petroleum asphalt, such
as using recycled asphalt materials and exploring alternative bind-
ers from other resources. The widely used recycled asphalt materi-
als include recycled asphalt pavement (RAP), recycled asphalt
shingles (RAS) and recycled concrete pavement (RCP). Biobinders
from biomass resources are candidates for alternative binders. The
resources of biobinders include animal waste, switchgrass, con-
rnstover, cedar, coffee or tea residue, and rapeseed. Some of these
biomass resources have great reserves. It is reported that more than
335 million tons of animal wastes are produced annually in the
United States (Fini et al. 2011). The biological potential of the for-
estlands of the United States is 29.1–34.6 billion cubic feet per year
(Spurr and Vaux 1976). Thus, it is a paramount potential to use
biobinders in the pavement industry, as long as the technology
is mature and the biobinder performance is satisfactory.
1
Ph.D. Candidate and Research Assistant, Dept. of Civil and Environ-
mental Engineering, Michigan Technological Univ., Houghton, MI 49931-
1295. E-mail: xyang2@mtu.edu
2
Professor, Dept. of Civil and Environmental Engineering, Michigan
Technological Univ., 1400 Townsend Drive, Houghton, MI 49931-1295
(corresponding author). E-mail: zyou@mtu.edu
3
Assistant Professor, Civil Engineering Dept., College of Engineering,
California Baptist Univ., 8432 Magnolia Ave., Riverside, CA 92504.
E-mail: jmillsbe@calbaptist.edu
Note. This manuscript was submitted on November 4, 2013; approved
on April 29, 2014; published online on July 30, 2014. Discussion period
open until December 30, 2014; separate discussions must be submitted for
individual papers. This paper is part of the Journal of Materials in Civil
Engineering, © ASCE, ISSN 0899-1561/04014157(11)/$25.00.
processing named pyrolysis. There are several types of pyrolysis
for the biomass materials according to the temperature and resi-
dence time, including fast pyrolysis, slow pyrolysis, carbonization,
and gasification. Three main components are generated during the
process, including chars, gases, and liquids. It is found that fast
pyrolysis can yield higher liquids out from the biomass with high
capacity compared with others (Nan et al. 1994). In the fast pyroly-
sis, the biomass materials are heated rapidly to 450–600°C in the
absence of air, then the vapors are cooled sharply (<2 s). The chars
and gases can be reused as the energy resources. The pyrolysis
temperature can also affect the biobinder yield and properties
(Westerhof et al. 2009). The formation of biobinder involves the
depolymerisation and fragmentation of cellulose, hemicelluloses,
and lignin, resulting in a large amount of different compounds in-
cluding carboxylic acids, ketones, phenols, aldehydes, alcohols,
and esters. Beaumont (1985) described the chemical components
of biobinder generated by pyrolysis and found that biobinder
contains more than 50 compounds. Original biobinders generated
through the pyrolysis process normally contain some water (as high
as 15–30% by weight) which originates from the water present
in the biomass feedback and the chemical reactions during the
pyrolysis process. In terms of this, Metwally and Williams (2010)
proposed an approach to reduce the water content of biobinders
from wood resources to as low as 5–8% by weight.
Elemental and Chemical Composition of Biobinder
Biobinders from different biomass resources may have various
elemental compositions, as shown in Table 1. Compared with
petroleum asphalt, the biobinders have much higher oxygen (O)
content and lower carbon (C) content. The content of the nitrogen
varies from the biomass resources. For instance, biobinders derived
from swine waste and soybeans have much higher N contents com-
pared with others primarily because of the high N content in the
swine waste and the soybeans. Because the elemental composition

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 Table 1. Elemental Composition of Biobinder from Different Sources Table 2. Some Properties of Asphalt Binder PG 58-28
Biobinder resource C (%) H (%) N (%) O (%) Specification Test
Physical properties values results
Swine waste (Fini et al. 2011) 72.58 9.76 4.47 13.19
Waste wood (Czernik and 56.4 6.2 0.1 37.3 Specific gravity — 1.03
Bridgwater 2004) Rotational viscosity @135°C (Pa-S) <3 0.320
Switchgrass (Mullen and 47.53 6.81 0.51 45.19 jG
j= sin δ @ 58°C for virgin binder (kPa) >1.0 1.218
Boateng 2008) jG
j= sin δ @ 58°C for RTFO residue (kPa) >2.2 2.916
Alfalfa (Mullen and Boateng 2008) 56.84 7.86 3.73 31.3 Creep stiffness @−18°C (MPa) >300 176
Cornstover (Metwally and 46.5 5.9 — 46.2
Williams 2010)
Oakwood (Metwally and 60.5 6.5 — 34.6
Williams 2010) found that the waste wood resourced biooil can improve the fatigue
Coffee residue (Chaiya 2011) 32.38 10.13 2.08 — performance of asphalt concrete.
Laurel (Ertaş and Hakkı Alma 2010) 49.65 8.1 5.0 41.63 In addition to the modification of asphalt, biobinders are also
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Tea waste (Uzun et al. 2010) 69.26 8.97 6.19 15.58
Rapeseed (Onay and Koçkar 2006) 72.8 10.8 3.3 13.1
Soybean (Şensöz and Kaynar 2005) 67.89 7.77 10.84 —
of biobinders may have influence on the physical and chemical
properties, the properties of biobinders may be very different from
one another.
Some chemical compositions of biobinders have also been in-
vestigated in previous studies. In general, the chemical composi-
tions of biobinders from different resources may be different.
Acid, alcohol, alkene, ester, and ketone are found in the biobinders
from switchgrass and alfalfa (Mullen and Boateng 2008). Levoglu-
cosaan, hydroxyacetaldechyde, acetic acid, glyoxal, and pyrolytic
lignin were detected in biobinders from woods (Scott et al. 2001).
In addition, it is also found that the percentages of these chemicals
are dependent on the pyrolysis condition (Mohan et al. 2006). The
components of biobinders can also fall into saturates, aromatics,
polars, and asphaltenes, which are the common components of
petroleum asphalt (Miao and Wu 2004). The main characteristics
of biobinders include suspended char, low PH, high-temperature
sensitivity, water content, and inhomogeneity (Bridgwater 1999).
Application of Biobinders in Asphalt Industry
According to Raouf and Williams (2010), the application of bio-
binders in asphalt industry can fall into three categories, as asphalt
modifier (<10% asphalt replacement), as asphalt extender (25–75%
asphalt replacement), and as direct alternative binder (100% asphalt
replacement). Most of the previous studies explored the feasibility
of using biobinder as asphalt modifiers. It was found that bio-
binders from different resources may have different effects on
the petroleum asphalt. Williams et al. (2008) studied the properties
of asphalt binders modified by biobinders from oak wood, switch
grass, and corn stover and found that the addition of oak wood bio-
binder can improve the rutting resistance while the switchgrass bio-
binder performed an opposite effect. The biobinder derived from
swine waste was able to reduce the asphalt stiffness in a wide range
of temperatures and improve the low temperature performance
(Fini et al. 2010, 2011; Mills-Beale et al. 2014). Kim et al.
(2012) studied the effect of the biobinder from biofuel coproduct
on the subgrade of flexible pavement performance using the
mechanistic-empirical pavement design guide. The study indicated
that such biobinder can improve the stability of subgrade soil and
enhance the pavement sustainability. Wen et al. (2013) have found
that biobinder from waste cooking oil would decrease the rutting
and fatigue resistance but improve the thermal cracking resistance.
Waste cooking oil was also found to be a good rejuvenator of aged
asphalt binders (Asli et al. 2012). Yang et al. (2014) evaluated the
mechanical performance of biooil modified asphalt mixtures and
used to modify the asphalt materials containing crumb rubber,
nanomaterial, and reclaimed asphalt pavement (Fini et al. 2012;
Peralta et al. 2012; Hill et al. 2013; Onochie et al. 2013). Some
components such as lignin in the biobinders can exhibit antioxidant
effects when added into the petroleum asphalt (Tang and Williams
2009). Nevertheless, some other studies indicated that the petro-
leum asphalt containing biobinders age quicker when subjected
to high temperature and abundant fresh air (Metwally and Williams
2010; Onochie et al. 2013; Yang et al. 2013). The aging of bio-
binder can be attributed to polymerization, oxidation, and potential
loss of volatiles (Naske et al. 2009; Hilten and Das 2010). It is
found that the there is a concentration of carbonyl, ester, and ether
groups during the aging of biobinder as an effect of oxidation
(Czernik et al. 1994; Diebold 2000).
Research Objective
The objective of this study is to characterize the rheological proper-
ties and analyze the aging mechanism of asphalt binders partially
replaced by high percentages of biobinder generated from waste
wood resources. Most of the past related studies focused on asphalt
modified by low percentage of biobinders. Because biobinder is a
renewable material which can be a potential alternative pavement
material in the future, it is necessary to study the chemical and
physical properties of asphalt binders blended with a high percent-
age of biobinders. In addition, the aging mechanism of biooil
blended asphalt will be studied using the FTIR. The chemical com-
ponent changes and the chemical reactions during the aging should
also be researched because it is not widely known for such new
materials.
Materials and Sample Preparation
Asphalt Binder
The asphalt binder used in this study is the performance grade as-
phalt PG 58-28. Some properties of the asphalt binder are shown in
Table 2. The properties were obtained according to the Superpave
specification, and all of the test results met the requirements.
Biobinders
The biobinders were derived from the waste wood feedstock col-
lected in the upper Michigan area which was then processed
through a fast pyrolysis. Two types of biobinders are used in this
study, the untreated biobinder (UTB) and treated biobinder (TB).
The untreated biobinder is the biobinder directly obtained as the
ultimate product from the production source while the treated
biobinder is the untreated biobinder product that has undergone

© ASCE 04014157-2 J. Mater. Civ. Eng.

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 Table 3. Chemical Compositions of Biobinders gain a comprehensive picture of the dynamic shear modulus, the
Chemicals Test values (wt%) DSR test was conducted at different temperatures and frequencies.
The test temperature range was 40–70°C with an increment of 6°C.
Carbon 59.5
The loading frequencies conducted for each temperature were 0.01,
Hydrogen 6.6
Nitrogen 0.37
0.1, 1, 5, 10, and 25 Hz.
Insoluble 42.94
Solids 2.20 Short-Term Aging Simulation
Furfural 0.054 The short-term aging occurs during the construction of asphalt
3-methyl-1,2-cyclopentandione 0.245 materials associated with the stiffness and viscosity increment of
Phenol 0.027 asphalt binders. It can be simulated using the rolling thin film oven
2-methoxyphenol 0.144 (RTFO) test in laboratory. Previous studies stated that the biobinder
o-cresol 0.065 cannot be used at temperature higher than 120°C because of the
m-cresol 0.077 significant aging (Metwally and Williams 2010). Therefore, the
2-methoxy-4-methylphenol 0.176 RTFO test in this study was adjusted from the stand test. The bind-
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p-cresol 0.034
2-methoxy-4-vinylphenol 0.444
Eugenol 0.093
2,6-dimethoxyphenol 0.409
Isoeugenol 0.444
Levoglucosan 3.721
4-allyl-2,6-dimethoxyphenol 0.309
a dewatering process. The treatment process involves mildly heat-
ing the original biobinder at 110°C (Metwally and Williams 2010).
Some chemical compositions of biobinders were determined
through the gas chromatography-mass spectrometry (GC-MS).
Table 3 shows the chemical compositions of biobinders used in this
study.
Preparation of Bioblended Asphalt Binders
The asphalt binder is replaced with 30 and 70% biobinders by
weight to prepare the bioblended asphalt binders. A total of five
different binders are investigated in this study, the PG 58-28 as
the control binder, the PG58-28 partially replaced by 30 and
70% untreated biobinder (i.e., 30 and 70% UTB), and the
PG58-28 partially replaced by 30 and 70% treated biobinder
(i.e., 30 and 70% TB). The blending of control binder and bio-
binder was conducted by a high shear mixer. The asphalt binder
and biobinder were firstly preheated to 130 and 110°C, respec-
tively. Then, the blending was conducted by the high shear mixer
at 120°C and 5,000 rounds per minute (RPM) for 20 min.
Experimental Program
Binder Property Characterization and Aging Simulation
Rotational Viscosity
The rotational viscosity (RV) of the asphalt binder can be used to
determine the asphalt binder workability and the construction tem-
perature of asphalt mixtures. The standard procedure for the RV test
follows ASTM D 4402 (ASTM 2012). In this study, the RV test for
both virgin and RTFO aged binders were conducted to obtain the
viscosity property and the aging effect. The test temperature range
was 100–140°C with 10°C increments.
Dynamic Shear Modulus
The dynamic shear modulus can reflect the mechanical responses
of asphalt binders under traffic loading. It can be determined
through the dynamic shear rheometer (DSR) test according to
AASHTO T 315 (AASHTO 2009). In this study, the dynamic shear
moduli of both virgin and RTFO aged binders were investigated to
obtain the stiffness property and the aging effect. In addition, to
ers were conditioned at 120°C for 20 min. The residues of the
RTFO test provide samples for the property characterization and
aging analysis.
Aging Mechanism Analysis
The aging of the asphalt binder during the construction stage is
primarily from two dimensions: the loss of volatiles and the oxi-
dation effect. The loss of volatiles was determined by the mass loss
in the RTFO test although the oxidation was determined by the
chemical bond changes such as carbonyl (C═O) and sulfoxide
(S═O) in the spectra of Fourier transform infrared spectroscopy
(FTIR) test.
Mass Loss
Mass loss of asphalt binders is determined by the percent weight
reduction because of the loss of volatiles at high temperatures. It is
calculated using the following equation:
weight before aging − weight after aging
Mass loss ¼ × 100
weight before aging
Chemical Bond Changes
The FTIR test has been applied to qualitatively and quantitatively
analyze the oxidation of asphalt binders (Lamontagnea et al. 2001;
Ouyang et al. 2006; Petersen 2009; Yut and Zofka 2011). The FTIR
spectra and the functional groups of petroleum asphalt and bio-
binders are shown in Fig. 1. It was observed the spectra of asphalt
binder and biobinders were very different, which was primarily
because of the different chemical compounds in the asphalt and
biobinders.
Peak height and band area in a FTIR spectrum are widely used
to indicate the concentration of a certain bond. For asphalt oxida-
tion quantitative analysis band area rather than the peak height is
used for two reasons: (1) band areas provide less variations
(Yut and Zofka 2011), and (2) several vibrations may occur in
the same band so that it’s difficult to obtain the single peak height
(Lamontagnea et al. 2001). Previous studies provide the quantita-
tive calculation for the oxidation analysis. The carbonyl (C═O) and
sulfoxide (S═O) indexes are normally used to characterize the
oxidation of asphalt binders. In this study, more bonds were inves-
tigated to study the effect of aging on the bond changes. The bond
indexes are calculated by the following equations:
X
Carbonyl index∶I C═O ¼ AR1,600 = AR
X
Sulfoxide index∶I S═O ¼ AR1,030 = AR

© ASCE 04014157-3 J. Mater. Civ. Eng.

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 0.6
2.0 10000

CH2 & CH3 bend

0.5 CH2 bend (Alkanes)

Rotational viscosity (cP)

(Alkanes) 1.5

0.4 1000
Absorbance

Absorbance
0.3 CH3 bend 1.0
(Alkanes) C=C & C=O stretch 30% UTB
0.2 C-H bend (Aromatic) 70% UTB
(Aromatics) 100
0.5 100% UTB
S=O stretch C=O stretch
Control
0.1 (Sulfoxides) (Aldehydes,
Ketones) 30% TB
70% TB
0.0 0.0 100% TB
400 600 800 1000 1200 1400 1600 1800 2000 2700 2800 2900 3000 3100 10
Wave number (cm )
-1
Wavenumber (cm )
-1
90 110 130 150
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(a) Temperature (°°C)

2.0 Fig. 2. RV test results for control asphalt binder, UTB, TB, and asphalt
C-C, C-O & C=O O-H stretch binders containing 30% UTB, 70% UTB, 30% TB, and 70% TB
Acids, Ether & Ester (Alcohol, Acids)
C-O-C CH2 bend
(Ether) CH3 bend (Alkanes)
1.5
(Alkanes)
C=C & C=O stretch Experimental Results and Discussions
(Aromatics)
Absorbance

CH2 & CH3 bend

(Alkanes)
1.0 Rotational Viscosity
C-O C=O stretch
(Alcohol) (Aldehydes, Fig. 2 displays the RV test results for the control asphalt binder and
Ketones) bioblended asphalt binders. The viscosities of pure UTB and TB
0.5 are also included in the figure, represented as 100% UTB and
100% TB. Overall, with the increase of the biobinder fraction in
the control asphalt, the rotational viscosity decreased except for
the 30% UTB. The viscosities of 70 and 100% UTB were 33.6
0.0
600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 and 71.1% lower than that of the control asphalt binder on average,
-1
Wavenumber (cm ) respectively. The viscosities of 30, 70, and 100% TB were 20.7,
(b) 42.3, and 64.0% lower than that of the control binder on average,
respectively. The test results indicate that the biobinder was softer
Fig. 1. Spectra and functional groups: (a) Spectra and functional than the asphalt binder in the temperature range 100–140°C. The
groups for the asphalt binder; (b) spectra and functional groups for comparison between the untreated and treated biobinders shows
the biobinder that the treated biobinder has a slightly higher viscosity than the
untreated biobinder. This phenomenon may be because of the
higher moisture content in the untreated biobinder. When the binder
X is heated at a temperature higher than 100°C, the free water foams
Aromaticity index∶I AR ¼ AR1,600 = AR
and reduces the viscosity. As the test continues the free moisture in
the biobinder escapes and the viscosity increases again. This is the
X reason why the curve slopes of 70 and 100% UTB altered at tem-
C─O bond index∶I C─O ¼ ðAR1,035 þ AR1,120 þ AR1,214 Þ= AR peratures higher than 130°C. Because the mixing temperature is
determined by the rotational viscosities of the asphalt binder, it
is expected that the addition of high percent biobinder into the as-
X
CH2 bond index∶I CH2 ¼ ðAR1,465 þ AR2,850 þ AR2,920 Þ= AR phalt binder can reduce the mixing temperature and thus save the
energy needed to heat the binder and aggregate.
Fig. 3 plots the RV test results of control binder and bioblended
X asphalt binders after the RTFO aging. It is observed that with the
CH3 bond index∶I CH3 ¼ ðAR1,375 þ AR2,960 Þ= AR increase of the biobinder fraction, the rotational viscosity increased.
The rotational viscosities of 30 and 70% UTB were 40.6 and
where AR1,600 = the band area around 1,600 cm−1 ; AR1,030 = the 290.8% higher than that of the control asphalt binder on average,
band area around 1,030 cm−1 ; AR1,035 , AR1,120 , and AR1P ,214 = the respectively. The rotational viscosities of 30 and 70% TB were 64.2
band areas around 1,035, 1,120, and , respectively; AR = and 86.9% higher than those of the control asphalt binder on aver-
the total area of all bands. age, respectively. This trend is contrary to the observed results of
In this study, the FTIR test was conducted using a Jasco-FT-IR- the pre-RTFO aging condition. This could be attributed to the ac-
4200 spectrometer, with a scan number of 32 and a resolution of celerated aging of the biobinder compared with the control asphalt
4 cm−1 . The binder specimens were spread on silicon slides with a binder.
thickness of around 0.1 mm. The test was conducted for both virgin The aging factors of the control asphalt binder and bioblended
and RTFO aged binders. The rationale for testing both unaged and binders were calculated, as shown in Fig. 4. The aging factor was
short-term aged binder was to understand the morphological determined as the ratio of the viscosity after RTFO aging to the
changes or evolution of bonding structure when high percent viscosity before RTFO aging. For the asphalt binder partially re-
biobinder is utilized in traditional asphalt binders. placed by TB, with the increase of biobinder fraction, the aging

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 100000 1.0E+06

1.0E+05
Rotational viscosity (cP)

10000

predicted G* (Pa)
1.0E+04

1000
1.0E+03
30% UTB
70% UTB
100 1.0E+02
Control Control
30% TB 30% UTB
70% TB 1.0E+01 70% UTB
High temperature
10 30% TB
90 110 130 150
70% TB
Temperature (°°C) 1.0E+00
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1.0E-03 1.0E-02 1.0E-01 1.0E+00 1.0E+01 1.0E+02 1.0E+03 1.0E+04

Fig. 3. RV test results for control asphalt binder and asphalt binders Reduced frequency (Hz)
containing 30% UTB, 70% UTB, 30% TB, and 70% TB after RTFO
aging Fig. 5. Master curve plot for jG
j of virgin control binder and binder
blending containing biobinders (temperature range 40–70°C, reference
temperature 58°C)

factor increased. However, it was found that the aging factor of

30% UTB was even a little lower than those of the control asphalt
binder. Considering the fact that the 30% UTB before RTFO aging
had a higher rotational viscosity than the control asphalt binder,
which was out of trend, it is thought that the 30% UTB had already
been overaged before the RTFO aging. The overaging may occur
during the mixing of the asphalt binder and biobinder or during the
heating to take out the biobinder from the tank. Thus, it is safe to
conclude that with the increase in the biobinder content, the aging
factor of the bioblended asphalt binders also increases.
Dynamic Shear Modulus
Fig. 5 illustrates the master curve for the dynamic shear modulus
(jG
j) of the control binder and bioblended asphalt binder before
RTFO aging. The reference temperature to shift the data points is
58°C. In general, with the increase of the biobinder fraction, the
jG
j decreased except for the 30% UTB. This trend is consistent
with the RV test result, in which the bioblended binder containing
30% UTB was thought to be over aged before the test. The jG
js of
the bioblended binders containing 30 and 70% TB were averagely
15.9 and 27.7% lower than those of the control asphalt binder, re-
spectively. The jG
j of the asphalt binder containing 70% UTB was
averagely 31.6% lower than that of the control asphalt binder on
average. This indicates that the virgin biobinder is also softer than
the control asphalt binder PG 58-28. In addition, it is observed that
the master curve slopes of bioblended asphalt binder were lower
than the control binder. Specifically, with the increase in the bio-
binder fraction, the slope also decreased. Because a lower slope
indicates a lower sensitivity to temperature change, which is desir-
able, the high partial replacement of traditional asphalt with bio-
binder can benefit from lower sensitivity to temperature change.
It was also found that in the low reduced frequency (high temper-
ature and low frequency) area, the jG
j difference between the
bioblended binders and the control asphalt binder was lower as
compared with that in the high reduced frequency area (low temper-
ature and high frequency). Because rutting occurs more easily at
high temperature and low frequencies and that a higher jG
j is nor-
mally preferable for the high temperature performance, the results
indicate that the addition of biobinder is beneficial for the high
temperature performance of asphalt binders.
Fig. 6 displays the master curve plot for the jG
js of the control
binder and bioblended asphalt binders after RTFO aging. With the
increase of biobinder fraction in the bioblended binders, the jG
j
also increased. The jG
js of the binders containing 30 and 70%
UTB were averageing 23.2 and 437.5% higher than the control as-
phalt binder, respectively. The jG
js of the binder blending containing
1.0E+07
1.0E+06

1.0E+05
Predicted G* (Pa)

8
Blending containing UTB 1.0E+04
6
Aging Factor

Blending containing TB
1.0E+03
Control
4 30% UTB
1.0E+02
70% UTB
30% TB
2 1.0E+01 70% TB

0 1.0E+00
0 20 40 60 80 1.0E-03 1.0E-02 1.0E-01 1.0E+00 1.0E+01 1.0E+02 1.0E+03 1.0E+04
bio-binder percent in the blending (%) Reduced frequency (Hz)

Fig. 4. Aging factors of the binder blending containing biobinders sub- Fig. 6. Master curve plot for jG
j of control asphalt binder and binder
jected to RTFO aging blending containing biobinders after RTFO aging

© ASCE 04014157-5 J. Mater. Civ. Eng.

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 6
that there were a considerable amount of light weight volatiles in
5 the biobinders. In fact, because the biobinders are cooled sharply
from vapors to a very low temperature in the fast pyrolysis, there
may be some lightweight compounds with boiling points lower
Mass loss (%)

4
than the conditioning temperature in the RTFO test. For instance,
3 alcohol and hydroxyacetaldechyde, whose boiling points are lower
than 120°C, were detected from biobinders generated from switch-
2
grass and woods (Scott et al. 2001; Mullen and Boateng 2008).
1 These lightweight compounds would escape when the temperature
is higher than the boiling points. The high mass loss also indicated a
0 high emission if the construction temperature is higher than 120°C.
Control 30% UTB 30% TB 70% UTB 70% TB 100% UTB 100% TB Therefore, some more detailed information of these chemicals
should be revealed to evaluate the influence on the environment
Fig. 7. Mass loss of control asphalt binder and bind blending contain-
and field construction technicians. If such effect is considerable,
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ing biobinders during the RTFO aging

30 and 70% TB were averagely 40.1 and 223.2% higher than the
control asphalt binder, respectively. This indicates that after the
RTFO aging, the biobinders were stiffer than the control asphalt
binder. Considering that the jG
js of bioblended asphalt binders
were lower than the control asphalt binder, the results indicate
the aging of biobinders was much more significant than that of
the control asphalt binder.
Aging Mechanism Analysis
Mass Loss
As previously discussed, the short-term aging of the asphalt binder
is primarily because of the loss of volatiles and oxidization. The
loss of light weight compounds would increase the average
molecular weight and increase the asphalt viscosity. In addition,
the mass loss is an indication of potential asphalt binder emission
during construction. In this study, the mass loss test was conducted
using the RTFO test. Fig. 7 shows the loss of volatiles for the con-
trol binder and bioblended asphalt binder. With the increase of bio-
binder fractions, the mass loss increased significantly. The mass
loss of the control asphalt binder was almost zero whereas the pure
untreated biobinder had mass loss as high as 5.37%. This indicates
further approaches to reduce the effect should also be considered
for the practical application.
Comparing the results between the two types of biobinders, it is
found that the untreated biobinder had slightly higher mass loss
than the treated biobinder. This is probably because of the higher
moisture content in the untreated biobinder. The temperature of
the RTFO test in this study was 120°C, which was higher than
the boiling point of water. The Superpave specification requires
that the mass loss during the RTFO test should be lower than 1%.
Based on this, the bioblended asphalt binders cannot meet this
requirement. In contrast, because of the loss of the lightweight
components, the average molecular weight of the binders would
increase and the binder stiffness should also go up. Considering
the results from the RV and DSR tests, it can be concluded that
the high mass loss contributed to the stiffness increase of bio-
blended binders during the RTFO aging.
FTIR Analysis
As previously discussed, the FTIR test can provide the chemical
bond information of the bioblended binders before and after the
RTFO aging. Fig. 8 displays the FTIR spectra for the control as-
phalt binder and bioblended binders before and after the RTFO
aging. The spectra were normalized for easier comparison. In
the normalization, an absorbance height of one was adapted for
the peak at 1,465 cm−1 without changing the relative height ratios
of the peaks. It is observed the main peaks for the control asphalt

4 7

3
5
70% TB RTFO
70% TB Virgin
Absorbance

Absorbance

4
2 30% TB RTFO
30% TB Virgin
3
70% UT Virgin
70% UT RTFO
30% UT Virgin 2
1 30% UT RTFO

Control Virgin 1
Control RTFO

0 0
800 1000 1200 1400 1600 1800 2800 3000 320034003600
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig. 8. Normalized FTIR spectra for control asphalt binder and bioblended asphalt binders before and after RTFO aging

© ASCE 04014157-6 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2015, 27(4): 04014157

 binder were located at 2,960 (CH3 stretch), 2,925 and 2,855 cm−1
(CH2 stretch), 1,375 cm−1 (CH3 bend), 1,465 cm−1 (CH2 bend),
1,030 cm−1 (S═O), 1,600 cm−1 (C═C stretch), 700 to
900 cm−1 (C─H bend), and 1,650 to 1,740 cm−1 (C═O stretch).
The corresponding functional groups are as seen in Fig. 1. For
the bioblended asphalt binders, there are additional peaks at
3,500 cm−1 (O─H stretch), and 1,120 cm−1 and 1,214 cm−1
(C─O stretch). From Fig. 1, the peaks at 3,500, 1,120, and
1,214 cm−1 are representative for alcohols, acids, ethers, and
esters.
Literature review showed that a trace of sulfur (S) element exists
in wood resourced biobinders (Mohan et al. 2006), so the peak
around 1,035 cm−1 for bioblended asphalt binder is representative
for both C─O stretch from the biobinders and the S═O from the
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From the chemical composition and the atomic weight of carbon
and hydrogen, it was calculated that the atom number ratios be-
tween C and H in the control asphalt binder and biobinder are
1∶1.58 and 1∶1.33, respectively. Considering that the carbon and
hydrogen ratio in benzene is 1∶1, whereas in alkane it is approx-
imately 1∶2. Higher carbon and hydrogen ratios indicate that some
hydrogen atoms are replaced by other atoms. Therefore, either
more C═O bond or C═C bonds exist in the biobinder compared
with that in the control asphalt binder. Fig. 9 shows the bond in-
dexes of various bonds. It was found that the C═O bond concen-
tration in the biobinder was much higher than that in the control
asphalt binder, whereas the C═C bond from aromatics did not show
much difference. This indicates that the percentage of aromatic
compounds in the biobinder is close to that in the asphalt binder,

control asphalt binder. This is the reason that the peak around
1,030 cm−1 was rightly shifted to approximately 1,035 cm−1 after
the biobinders were blended into the control asphalt binder, as seen
in Fig. 8. Moreover, no additional peaks other than the peaks dis-
played in Fig. 1 were observed after blending the biobinder into
the control asphalt binder. This is an indication that there were
no chemical reactions between the asphalt binder and biobinders.
but the percentage of compounds containing C═O bond such as
alcohol and acids should be much higher in the biobinder. In ad-
dition, some OH bonds may also exist in the bioblended binders as
it does not change the atom number ratio between carbon and hy-
drogen if the hydrogen atom is replaced by an OH radical. Previous
studies have revealed that waste wood resourced biobinders contain
a number of compounds such as acid, alcohols, alkenes, esters, and

0.04 0.25
Control Virgin 30% UT Virgin
0.2
0.03 Control RTFO 30% UT RTFO
Bond index
Bond Index

0.15
0.02
0.1

0.01
0.05

0 0
C-H of S=O C=C of C=O CH3 OH C-H of C-O C=C of C=O CH3 OH
Aromatic Aromatic Aromatic Aromatic
(a) (b)

0.14 0.4
0.12 70% UT Virgin 0.35 30% TB Virgin
70% UT RTFO 0.3 30% TB RTFO
0.1
Bond Index

Bond Index

0.25
0.08
0.2
0.06
0.15
0.04
0.1
0.02 0.05
0 0
C-H of C-O C=C of C=O CH3 OH C-H of C-O C=C of C=O CH3 OH
Aromatic Aromatic Aromatic Aromatic
(c) (d)
0.14 1
Virgin RTFO aged
0.12 70% TB Virgin
0.8
Bond index of CH 2

0.1 70% TB RTFO

Bond Index

0.08 0.6

0.06
0.4
0.04
0.2
0.02

0 0
C-H of C-O C=C of C=O CH3 OH Control 30% UTB 70% UTB 30% TB 70% TB
Aromatic Aromatic
(f)
(e)

Fig. 9. Bond indexes of control asphalt binder and bioblended binders before and after RTFO aging: (a) control asphalt binder; (b) 30% UT blended
binder; (c) 70% UT blended binder; (d) 30% TB blended binder; (e) 70% TB blended binder; (f) bond index of CH2

© ASCE 04014157-7 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2015, 27(4): 04014157


ketones (Mullen and Boateng 2008). So the FTIR spectra for the
tested bioblended asphalt binders are in good agreement with pre-
vious studies.
Previous studies show that the oxidation of asphalt binders has
great influence on the evolution of the carbonyl (C═O stretch
around 1,700 cm−1 ) and sulfoxide bonds (S═O stretch located
at 1,030 cm−1 ) (Ouyang et al. 2006; Petersen 2009; Xu and Huang
2010). However, because little sulfur is contained in the biobinder
from wood resources, sulfoxide is not considered in the oxidation
of the pure biobinder. Literature review shows that the oxidation of
biobinder is associated with the increase of ketones (C═O around
1,715 cm−1 ), carbonyl (C═O around 1,700 cm−1 ), ester (C─O
stretch at 1,214 cm−1 ), ether groups (C─O stretch at 1,120 cm−1 ),
and aromatic groups (Czernik et al. 1994; Diebold 2000; Scholze and
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Meier 2001; Hilten and Das 2010; Yao et al. 2013). Thus, the
oxidation analysis for bioblended asphalt binder would take account
into the C═O bond around 1,700 cm−1 stretch, S═O bond around
1,030 cm−1 , C─O bonds at 1,035, 1,120, and 1,214 cm−1 , and
C═C bond in aromatics. In addition, the bond change on the CH2
and CH3 will also be investigated for deep understanding of the
aging effect.
With the spectra displayed in Fig. 8, the bond indexes for the
control binder and the bioblended asphalt binders were obtained
and displayed in Fig. 9. Seven bond indexes were displayed: the
C─H bend of aromatics, the C─O stretch of acid, alcohol, ester,
and ethers, the C═C stretch of aromatic skeletons, the C═O bond,
the S═O bond, the CH2 and CH3 bond of alkanes, and the OH
stretch. Because the bond index of CH2 is much higher than others,
the bond index of CH2 was plotted separately in Fig. 9(f) to clearly
display other bond indexes. It is found that the OH index signifi-
cantly increased after the blending of the biobinder into the control
asphalt binder, which is primarily because of the various chemicals
in the biobinders such as alcohol, acid, ester, and ethers. Similarly,
the C─O and C═O bond of bioblended binders were also much
higher than that in the control asphalt binder. This is as expected
because of the relative higher percentage of oxygen in the bio-
binders. In addition, the bond indexes of the C─H stretch and
C═C stretch of aromatics from the control asphalt binder and bio-
blended binders were close. This indicates that the fractions of the
compounds containing aromatic structure in the control asphalt
binder and biobinders are also close.
The effect of RTFO aging on the chemical components can be
evaluated through the changes of the bond indexes, which reflect
the concentration of the bonds. For the control asphalt binder, the
bond index changes were very limited, as shown in Fig. 9(a). There
were almost no changes of the indices of S═O and C═O bond,
which were normally found associated with the asphalt aging. This
is consistent with the rheological test results discussed previously.
For the bioblended binders, significant increase of bond indexes
were observed for the C─H and C═C of aromatics, C─O stretch,
C═O, and O─H stretch. The increase of C─H and C═C of aro-
matics indicates the formulation of chemical compounds contain-
ing aromatic structures during the aging. Literature review shows
that resins or lightweight molecular compounds react with the oxy-
gen and formulate aromatics or aromatic hydrocarbons (Yao et al.
2013). The formulation of chemical compounds containing aro-
matic structures also indicates the increase of C∶H ratio resulted
from the dehydrogenation process. Because there were no signifi-
cant bond index changes for the control asphalt binder, the aromatic
skeletons here were primarily formulated from the compounds in
the biobinders. In other words, the lightweight compounds in the
biobinders are easier to transfer to bigger-sized compounds con-
taining aromatic skeletons compared with the petroleum asphalt
binder. The C─O stretch, C═O stretch, and O─H stretch can be
© ASCE 04014157-8
J. Mater. Civ. Eng., 2015, 27(4): 04014157
R H R OH O
R
R R O
R R OH
H H
Most reduced Most oxidized
Fig. 10. Typical oxidation process of organic compounds
indication for the oxidation as oxygen element intrudes into the
system. Literature review shows that an increased concentration
of carbonyl (C═O around 1,700 cm−1 ), ester (C─O stretch at
1,214 cm−1 ), and ether (C─O stretch at 1,120 cm−1 ) is a character-
istic for the oxidation in biobinders (Czernik et al. 1994; Diebold
2000). In fact, it is thought that the oxidation occurs as long as the
ratio of carbon content to oxygen content decreases (Scholze and
Meier 2001). It was observed that most of the bond indexes of
C─O, C═O, and O─H stretches in the bioblended binders in-
creased after the RTFO aging. Because the C═O, C─O, and
O─H bond normally exists in alcohols, acids, and ester, it is an
indication that the concentration of these chemical components in-
creased during the aging. Considering that the oxidation of control
binder was not significant, the oxidation primarily occurred on
the biobinders.
On the contrary to the increase of bond indices discussed pre-
viously, it is observed that the CH2 bond of all bioblended binders
decreased significantly during the aging, as shown in Fig. 9(f). This
phenomenon can be interpreted by the oxidation process of organic
compounds. The typical oxidation process of an organic compound
is illustrated in Fig. 10 (Larsen 2013), in which R represents a ran-
dom radical whereas H and O represent the hydrogen and oxygen
atoms, respectively. The original compound contains a CH2 radical
and two other random radicals. During the aging, one of the two
hydrogen atoms was replaced by the OH stretch and an alcohol was
formulated. After further oxidation, a carbonyl bond replaces the
hydrogen atom and the OH radical, and a ketone was formulated.
The preceding oxidation step broke the bond between R radical and
the centered carbon atom and an OH radical was implanted. Here,
an acid was formulated. During this process, the CH2 bond disap-
peared whereas C─O, O─H, and C═O bonds were formulated.
Moreover, if the lost R represents a CH2 radical, a CH3 radical
would be formulated after the break of the bond between R radical
and the centered C atom. This can explain why the CH3 bond index
slightly increased after the aging, as shown in Fig. 9. This oxidation
process perfectly explains the bond concentration changes during
the RTFO aging in this study. In addition, no significant CH2 bond
change was observed for the control asphalt binder, so this oxida-
tion process primarily occurred on the biobinders.
Comparing the four bioblended binders (30% UTB, 70% UTB,
30% TB, and 70% TB), it was found that the increase in indices of
C─O, C═O, and O─H bonds of 30% UTB were lower than others.
This is also in agreement with the previous findings in the rheo-
logical test that the 30% UTB was preaged before the RTFO test.
In addition, in terms of the bond index change, no significant differ-
ences between the UTB-blended and TB-blended asphalt binders
were observed.
The formulation of aromatic compounds is normally associated
with the molecular increase in chemical compounds. The largest-
size molecular fraction in the binders is asphaltene, whose molecu-
lar structure contains large amount of aromatic skeletons (Groenzin
and Mullins 2000; Sedghi et al. 2013). In addition, considering the
C∶H ratio of asphaltene (around 1∶1.2) is higher than the average
values in the asphalt binder (around 1∶1.5) and biobinder (1∶1.33),
this is in agreement with the dehydrogenation process during the
aging. This is also an indication of the formulation of chemical
J. Mater. Civ. Eng.

Fig. 11. Aging of biobinder
components such as asphaltene and other relatively heavy weight
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compounds. The increase of the molecular size can also contribute
to the higher stiffness of biobinders. The increase of aromatic skel-
etons in the bioblended binders also indicates the compounds in
the biobinders are not stable when subjected to high temperature
and oxygen. The increase of C─O, C═O, and O─H bond indicates
that the oxidation easily occurs in biobinders. The CH2 bonds in
the compounds of the biobinders are easily to be attacked by
oxygen. Then, ketone, acid, and esters are generated during the
oxidation step.
Based on the previous analysis, during the aging of bioblended
asphalt binders, three phenomena occurred: the loss of light weight
compounds, the molecular size increase resulting from dehydro-
genation, and the increase in C─O, C═O, and OH bonds resulted
from the oxidation, as illustrated in Fig. 11. All of the changes have
significant influence on the rheological properties of biobinders and
hence the mechanical performance of asphalt mixtures. Because
aging is a big concern for asphalt binders during the construction
and service life, the aging of biobinders should be well addressed if
it is used in the asphalt industry with a high fraction. In addition,
some chemicals are generated and lost during the aging process, so
the effect of these chemicals on the environment and the field pav-
ing crew should also be evaluated to ensure the safe construction of
pavements incorporating biobinder modifiers. Furthermore, at-
tempts at refining the biobinder end product directly at the source
before its usage are highly encouraged. This can be attained by
reevaluating the fast pyrolysis approach and including other proc-
esses that will yield bioasphalt fractions with fewer propensities for
future aging.
Findings and Conclusions
This research studied the rheological properties and conducted the
aging analysis of asphalt binders blended with high percentage of
biobinders. The rotational viscometer (RV) and dynamic shear
rheometer (DSR) were conducted for the rheological property
characterization. The rolling thin film oven (RTFO) test was
conducted for the aging simulation. The mass loss of lightweight
compounds were obtained from the RTFO test, and the chemical
analysis were conducted from the Fourier transform infrared
spectroscopy (FTIR) test. The main findings and conclusions are
summarized as follows:
1. The bioblended asphalt binders overall showed lower rota-
tional viscosity compared with the petroleum asphalt before
RTFO aging. The UTB-blended binder had a lower viscosity
than the TB-blended binder, which is thought to be because of
the higher water content of untreated biobinders.
2. The bioblended asphalt binders are more prone to aging com-
pared with the control asphalt binder according to the RV and
DSR test results for RTFO aged binders.
© ASCE 04014157-9
J. Mater. Civ. Eng., 2015, 27(4): 04014157
3. Significant mass loss was observed for the bioblended asphalt
binders during the aging, indicating some light weight com-
pounds exist in the biobinders. Furthermore, the mass loss
of UTB-blended binders was higher than the TB-blended
asphalt binders.
4. The C═C and C─H of aromatics increased during the RTFO
aging, indicating the dehydrogenation process, which resulted
in the formulation of bigger molecular compounds such as
asphaltene.
5. The significant increase of C─O, C═O, OH bonds during the
RTFO aging indicates the oxidation effect which increased the
fractions of acids, ketones, and esters. The further analysis
showed that the chemical bonds in the biobinders are easier
to be attacked by oxygen for more progressive aging to occur.
6. The high mass loss of bioblended asphalt binders may indicate
a high emission during the practical construction. Further
study on such volatile compounds should be further investi-
gated to evaluate the environmental effects. In addition, the
effect of the new generated chemicals during the aging should
also be assessed.
Current Challenges and Future Effort
In this study, the research team studied the rheological properties
and aging performances of bioblended asphalt binders. It is found
that the fast aging resulted from the loss of volatiles and oxidation
is a significant concern. Although the biobinders investigated were
generated from waste wood resources, the characters revealed in
this study may also apply on biobinders derived from other resour-
ces using similar techniques. In the future study, some efforts
should be made to solve this problem.
To reduce the loss of volatiles, the cooling temperature in the
fast pyrolysis can be increased above the asphalt construction
temperature so that the low-boiling point compounds would be
excluded in the biobinders. Research can also be conducted on
the use of catalysts or inhibitors to achieve this goal. As a result,
the mass loss would decrease and the environmental effect concern
can be eliminated. In addition, some approaches need to be found to
stabilize the chemical components in the biobinders so that the
aging resistance could be improved.
Acknowledgments
The research work was partially sponsored by the Federal Highway
Administration through Michigan Department of Transportation
(MDOT). The authors also appreciate the guidance and involve-
ment of Nathan Maack, Andre Clover, Benjamin Krom, and John
Barak of MDOT. This research could not have been completed
without the contributions of Dr. R. Christopher Williams. The
authors appreciate Christopher DeDene, James Vivian, Morgan
Hensen for the assistance on materials and data collection. MDOT
assumes no liability for its content or use thereof. The content of
this report reflect the views of the authors, which is responsible for
the accuracy of the information presented in this paper. The con-
tents may not necessarily reflect the views of MDOT and do not
constitute standards, specifications, or regulations.
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