Construction and Building Materials 154 (2017) 310322

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Construction and Building Materials

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Characterization of fume composition and rheological properties of

asphalt with crumb rubber activated by microwave and TOR
Ming Liang a,b, Shisong Ren a, Weiyu Fan a,, Hao Wang b, Wenyao Cui a, Pinhui Zhao c
a
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, China
b
Department of Civil and Environmental Engineering, Rutgers University, Piscataway, NJ 08854, USA
c
Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

CR activated by microwave and TOR

reduces PAHs and sulfur compounds
in asphalt fumes.

Microwave treatment on CR enhances
relaxation performance of modified
asphalt.

TOR greatly improves viscoelastic
behavior of CR modified asphalt at
high temperatures.

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

Article history: This paper studied asphalt fume chemical composition, rheological properties and microstructure of
Received 3 May 2017 asphalt with crumb rubber (CR) activated by microwave and trans-polyoctenamer (TOR). To that end,
Received in revised form 10 July 2017 asphalt fume was trapped through laboratory fume generation and capture system, which was subse-
Accepted 29 July 2017
quently analyzed by Gas Chromatography-Mass Spectrometry system (GCMS). Moreover, the rheologi-
cal behavior and microstructure of CR modified asphalt (CRMA) were characterized by dynamic shear
rheometer (DSR) and FTIR. The GCMS results indicated that CR activated by microwave and TOR reduces
Keywords:
the contents of PAHs and sulfur compounds, implying the lower toxicological potential of fume. TOR has
Asphalt fume
CR modified asphalt
the greater effect of reduction in the toxicological species. The rheological results indicated that CR acti-
TOR vated by TOR significantly improves modulus, zero shear viscosity (ZSV), and recovery ability of CRMA at
Microwave high temperatures, which cause asphalt binder having the stronger resistance to rutting. The enhance-
Rheology ment in thermo-mechanics is due to chemical cross-linking among TOR, rubber, and asphalt, which
was verified by FTIR results. On the other hand, microwave treatment on CR affects high temperature per-
formance of CRMA negatively in comparison to the untreated CRMA. However, microwave treatment
leads to the faster stress relaxation response of CRMA, indicating the stronger resistance to thermal
cracking.
2017 Elsevier Ltd. All rights reserved.

Corresponding author.
E-mail addresses: liangmingupc@126.com (M. Liang), fanwyu@upc.edu.cn (W. Fan).

http://dx.doi.org/10.1016/j.conbuildmat.2017.07.199
0950-0618/ 2017 Elsevier Ltd. All rights reserved.
 M. Liang et al. / Construction and Building Materials 154 (2017) 310322
1. Introduction
The recycling and reutilization of waste tires are attracting
increasing attention in recent years, because the disposal of dis-
carded tires (such as stockpile and landfill), poses adverse impacts
on environment (potential fire hazardous, breeding grounds for
rats, mosquitoes) [1]. The recycle of post-consumer tires is the
most popular route to produce crumb rubber (CR) [2]. Generally,
crumb rubber is produced by mechanical grinding at the ambient
or cryogenic condition, resulting in different properties of rubber
powders [3,4]. The relative high surface/volume ratio, irregular
shape can be achieved for CR produced from ambient grinding
while CR particles produced from cryogenic grinding have the flat
and edgy surface [5,6]. One of the most cost-effective applications
for crumb rubber is used as asphalt modifier in paving and roofing
industry, which can improve asphalt rheology and also solve solid
waste problems [7]. Previous studies have developed two general
methods to prepare crumb rubber modified asphalt (CRMA), i.e.
dry process and wet process [811]. In dry process, CR is mixed
with aggregates and asphalt, as the filler of asphalt mixtures. Very
limited interactions between asphalt and rubber exist in dry pro-
cess. On the contrary, asphalt blended with CR at elevated temper-
atures for several hours in wet process has an advantage over dry
process. Viscoelastic properties of asphalt can be improved signif-
icantly by the chemical and physical interactions among asphalt
and rubber particles [12,13]. Therefore, wet process is the pre-
ferred one for producing CR modified asphalt.
However, the extent of enhancement of performance in wet
process is mainly determined by the interfacial properties of rub-
ber particles and the interactions between asphalt component
and particles [14,15]. Since rubber molecules are vulcanized, their
three-dimensional networks are hardly cleaved in asphalt even
Table 1
The traditional test results and chemical compositions for base asphalts.
Items Results
Q K
Penetration (25 C, dmm) 65
Softening point (R&B, C) 47.9
Ductility (10 C, cm) 45.0
Viscosity (135 C, Pas) 0.524
Saturates (%) 22.7
Aromatics (%) 42.1
Resins (%) 26.7
Asphaltenes (%) 8.5
Fig. 1. Laboratory modified asphalt fumes generation and capture system.
311
blending for long time and at elevated temperatures. This leads
to incompatibility problems and the sedimentation of rubber par-
ticles at the bottom of bulk asphalt phase and further affects the
performance of CRMA negatively [16,17]. Many attempts [1822]
have been taken to break the CAS or SAS bonds in rubber chemical
linking networks (devulcanization) and to improve compatibility
of CR with asphalt. Those approaches include high-speed shear dis-
integration, pre-blending process with matrix, microwave treat-
ment and plasticization. It is noted that microwave treatment
[2325] was found being an effective method to break the cross-
linked SAS or CAS bonds among the three-dimensional networks
of rubber molecules. Yu et al. (2011) reported that CR irradiated
by microwave improves conventional properties and storage sta-
bility of modified asphalt [26]. Poyraz (2013) analyzed crumb rub-
ber treated by microwave through FT-IR characterization and
indicated that short-term microwave irradiation (four minutes)
can devulcanize the scrap GTR particles effectively [27]. In addi-
tion, various additives, cross-linking agent [28], polyphosphoric
acid [29], polymeric reactants with conjugated diene [30], etc.,
were also incorporated in the rubber/asphalt blends to retard the
separation process of rubber particle from bulk asphalt phase.
Among the above-mentioned additives, trans-polyoctenamer
(TOR) is a polymeric reactive rubber with double-bond structures
in molecules [30,31]. TOR is prepared by a metathesis polymeriza-
tion of cyclooctene monomer and synthesized from 1, 3-butadiene
and 1, 5-cyclooctadiene. When TOR was mixed with CR/asphalt
blends, it improves workability of blends and allows blends with
lower viscosity owing to its low glass transition temperature. More
importantly, the fairly good compatibility exists with CR/asphalt
blends after adding TOR, which can facilitate the interaction
between CR and asphalt through crosslinking of sulfur components
in rubber and asphaltene [32,33].
Although CRMA shows advantages such as the better resistance
to rutting and cracking, low noise at tire-pavement surface, and so
on, it demands the high processing temperature in plant and the
high mixing temperature with aggregate in construction due to
its higher viscosity as compared to conventional asphalt [10]. This
contributes the higher energy consumption and more hazardous
67 gaseous emissions. It is a fatal disadvantage for CRMA because
48.8 more emphasis is put on environmental protection as well as occu-
68.5
pational health. Several studies [3436] have investigated the
0.609
27.3 composition and quantity of fume released in production plant
32.7 or construction area.
39.1 Some researches [3740] compared gaseous emissions from the
0.9 production, mixing, and paving of CRMA with those generated
from conventional asphalt. The findings revealed that the increased
312 M. Liang et al. / Construction and Building Materials 154 (2017) 310322

concentrations of emissions are found for CRMA and the binder
containing CR potentially releases more hazardous emissions than
conventional binder. Thus, several ways aiming to reduce the gas-
eous emissions in construction of hot-mix asphalt (HMA) have
been tried in the literature. Cui et al. (2015) investigated the vola-
tile organic contents (VOCs) of asphalt by addition of SBS, layered
double hydroxides (LDHs), and activated carbon [41]. They argued
that SBS and activated carbon can suppress the release of aromatic
hydrocarbons and polycyclic aromatic hydrocarbons. Rasoulzadeh
(2011) employed post-consumer latex and vacuum residue to pro-
duce paving-grade asphalt instead of air-blowing process, decreas-
ing polycyclic aromatic hydrocarbons emissions [42]. However,
there are limited studies on assessment and mitigation methods
for gaseous emission of asphalt containing crumb rubber. The
effective methods to reduce gaseous emissions of CRMA need more
extensive investigations. The available literature on asphalt modi-
fied by microwave treated CR and TOR only focused on physical
and mechanical properties.
This study evaluated gaseous emission and rheological proper-
ties of asphalt with CR activated by microwave and TOR, with the
aim of reducing gaseous emissions during the production of CRMA
and improving viscoelastic properties. To achieve this goal, the
capture system of generated asphalt fume was developed in the
laboratory. The trapped fumes were characterized using Gas Chro-
matography coupled with Mass Spectrometers (GCMS system) to
quantify the composition of emissions. Moreover, viscoelastic
properties of modified asphalt were characterized using dynamic
shear rheometer by means of dynamic shear frequency sweep

Fig. 2. The total ion chromatorgraphy of un-condensable gaseous fume (the top) and the condensates (the bottom) for base asphalt.
 M. Liang et al. / Construction and Building Materials 154 (2017) 310322 313

Fig. 3. The total ion chromatorgraphy of un-condensable gaseous fume (the top) and the condensates (the bottom) for CRMA.

tests, temperature sweep tests, flow measurements, relaxation
tests, and multiple stress creep-recovery tests. Moreover, the
microstructure of various CRMA was examined by FTIR.
Crumb rubber with the particle size of 40 meshes was made from post-
consumer vehicle tires by cryogenic grinding. Rubber particles were dried in an
oven before microwave treatment to have the moisture content lower than 0.1%.
TOR additive was supplied by EVONIK Company in form of pellets. The recom-
mended dosage of TOR was 4.5% by weight of CR.

2. Materials and methods 2.2. Asphalt fume generation and capture

2.1. Materials
Two base asphalt materials with the penetration grade of 50/70 (abbreviated as
Q and K) were obtained from PetroChina Co., Ltd in this study. The traditional rhe-
ology test results and chemical compositions were displayed in Table 1, including
penetration, softening point, ductility, viscosity and SARAs fractions. Although
two asphalt materials have the same penetration grade, their chemical composi-
tions are indeed very different, especially for asphaltenes content. Besides, the oil
sources of two asphalts are different.
A special device was developed to capture asphalt fumes in the laboratory, as
displayed in Fig. 1. This system simulated the laboratory preparation process of
CRMA where fumes were trapped by the capture system. The specific amount of
base asphalt Q was poured into the generator. Air in the device should be swept
out by blowing nitrogen for 15 min. Afterwards, CR was mixed into asphalt binder
under agitation when the temperature reached 140 C, followed by controlling the
temperature at 180 C and stirring at the constant speed for 3 h. The capture pro-
cess began at the end of reaction and the generator was connected to syringe by
a rotating three-way valve. Then the syringe was connected with the collecting
314 M. Liang et al. / Construction and Building Materials 154 (2017) 310322

bag and fumes were boosted into collecting bags. Repeating the steps until all
fumes was trapped in bags. The trapped fumes in the collecting bag were separated
in two phases, i.e. gaseous fume and condensate, when they were cooled down to
room temperature.
2.3. Microwave treatment on CR and preparation of CRMA
CR was firstly subjected to microwave irradiation in the microwave oven to
activate rubber particles. As previously mentioned, pre-dried CR was spread out
homogeneously on a porcelain disk, which was placed in microwave oven for
500 W and 5 min. 50 g CR was treated for each time to ensure the uniform and suf-
ficient irradiation. The CR irradiated by microwave (abbreviated as CRIM) was
sealed in an aluminum foil bag for the modification of asphalt. The CRMA for vis-
coelastic characterization was prepared following the similar procedure of prepar-
ing CRMA for fume generation and collection. TOR was added into hot matrix in
combination of CR at the same time. The following abbreviations, CRMA, CRIMMA,
CRTORMA and CRIMTORMA, were used for representing asphalt modified by CR,
CRIM, CR + TOR and CRIM + TOR, respectively.
2.4. Test and evaluation methods
Gaseous fume and condensates were characterized by GCMS system equipped
with positive electron ionization (EI) and quadrupole mass analyzer (Agilent
7890 A-5975 C). For gaseous fume, chemical species in asphalt fume was separated
by HP-5 (30 m  320 lm  0.1 lm) and analysis was carried out for an oven
temperature program from 30 C (held for 1 min) to 230 C (held for 20 min) at
10 C/min. On the other hand, condensates were extracted into hot benzene solvent
and separation was performed using HP-5MS (30 m  250 lm  0.25 lm). Analysis
for condensate was carried out for an oven temperature program from 50 C to
120 C (held for 10 min) at 5 C/min and then to 300 C at 10 C/min. Aiming to
identify chemical species in asphalt fume qualitatively and quantitatively, air and
benzene were referenced as blank sample for gaseous fume and condensates anal-
ysis, respectively. Species of chemicals in fume were determined by the position of
response peaks in the ion chromatorgraphy. The contents of chemical species were
determined by the area of corresponding peaks of fume deducting the peak of blank
sample.
The viscoelastic behavior of CRMA was characterized by a hybrid rheometer
HR-1(TA Company, USA). Oscillation frequency sweep tests were implemented
from 0.1 to 100 rad/s within the linear viscoelastic region at 10, 25, 50 and
75 C. Also, oscillation temperature sweeps, with a continuous heating ramp of
1 C/min and frequency of 10 rad/s, were carried out from 10 to 100 C. Moreover,
high-temperature viscoelastic behavior of modified asphalt was evaluated by mul-
tiple stress creep recovery (MSCR) tests. MSCR tests were performed at two stress
levels with ten cycles and each cycle includes one-second loading followed by
nine-second unloading. Stress relaxation within a wide time range of CRMA was
tested at 10 C. In a large deformation scale, flow behavior in steady state was
measured from shear rate of 103 s to 102 s at 60 C. More importantly, 25 mm
parallel plates in diameter (1 mm gap) were selected for measurements at
medium-high temperature range and 8 mm parallel plates in diameter (2 mm
gap) were used for the rheological tests below room temperature. Moreover, in
order to acquire repeatable rheological results, two replicates of specimen were
performed.
Fourier transforms infrared (FTIR) spectroscopy is a simple analytical technol-
ogy to characterize chemical bonds in different samples. In this study, Thermo Fish-
ers Nicolet 6700 was used to determine the microstructure of various CR modified
asphalt in the range of wave number from 4000 cm1 to 400 cm1.
3. Results and discussions
3.1. Chemical composition of CRMA fume emissions
The asphalt fumes in the collecting bag were separated in two
phase at room temperature, i.e. un-condensable gaseous fume
and the condensate. The total ion chromatorgraphy obtained from
GCMS were shown in Figs. 2and 3 (base asphalt and CRMA as the
examples). The total ion chromatorgraphy showed their percent-
ages by area normalization method. Thus, the composition and
content of two fume phases were obtained, as showed in Tables
2 and 3, respectively. During the process of fume generation,
experimental parameters such as temperature, heating rate, and
stirring rate, were controlled precisely. As can be seen from Table 2,
there were two inorganic compounds (water and carbon dioxide)
and 13 organic compounds in gaseous fume, including alkanes,
alkenes, alcohols, aldehydes, ketones, and aromatic compounds.
The contents of ethylbenzene (RT = 36.031 min) and o-xylene
(RT = 36.486 min) were higher than the other aromatic com-
pounds. The addition of CR to asphalt results in more chemical spe-
cies emitting into fumes, which were mainly sulfur compounds
such as hydrogen sulfide, carbonyl sulfide, methanthiol and carbon
disulfide. These sulfur compounds caused pungent odor during
preparation of CRMA. The content of sulfur compounds of CRIMMA
decreased. Moreover, aromatic compounds decreased in gaseous
fumes of CRIMMA. The contents of sulfur compounds and aromatic
compounds in CRTORMA were the lowest among the studied
asphalt samples.
Table 3 showed the compositions and contents of the conden-
sates for base asphalt and various CRMA. Apparently, the conden-
sates were composed of a very large amount of compounds that
were heavier compounds with larger molecule of alkanes, alkenes,

Table 2
The compositions and contents of gaseous fume for base asphalt and various CRMA.

Number Base asphalt Various modified asphalt

CRMA CRIMMA CRTORMA
Compounds Content/wt% Compounds Content/wt% Content/wt% Content/wt%
1 Carbon Dioxide 1.03 Carbon dioxide 4.11 3.68 4.10
2 Ethane 0.05 Hydrogen sulfide 0.24 0.11 0.08
3 Water 1.92 Water 1.09 1.56 1.89
4 Propylene 0.04 Carbonyl sulfide 0.19 0.08 0.06
5 Propane 0.08 Propylene 0.03 0.02 0.04
6 Methanol 0.23 Propane 0.01 0.03 0.02
7 Acetaldehyde 0.08 Methanol 0.21 0.30 0.48
8 2-butene 0.03 Acetaldehyde 0.03 0.02 0.03
9 Iso-butane 0.12 Methanthiol 0.07 0.02 0.01
10 Acetone 0.04 2-butene 0.30 0.32 0.44
11 Pentane 0.07 Ethanol 0.14 0.21 0.27
12 Cyclopentene 0.03 iso-butane 0.14 0.18 0.21
13 Toluene 0.32 n-butane 0.20 0.27 0.19
14 Ethylbenzene 2.42 Carbon disulfide 0.22 0.14 0.09
15 o-xylene 3.54 2-methyl furan 0.07 0.09 0.07
16 5-methyl indan 0.07 0.06 0.05
17 Benzene 0.04 0.03 0.04
18 Cyclohexene 0.07 0.05 0.08
19 Methyl isobutyl ketone 0.26 0.31 0.32
20 Toluene 0.19 0.22 0.21
21 Phenylethane 0.99 0.81 0.78
22 o-Xylene 1.93 1.24 1.07
 M. Liang et al. / Construction and Building Materials 154 (2017) 310322 315

cycloalkanes, aromatic hydrocarbons, polycyclic aromatic hydro-
carbons (PAHs) as well as a small amount of alcohols and esters.
Thereinto, aromatic hydrocarbons were mainly composed by the
substituted benzenes. PAHs include dihydroindene, naphthalene
and xenene, which is an important indicator of toxicological and
carcinogenic effect. Meanwhile, more chemical species such as
cyclohexanethiol, nitrogenous compounds of 2-ethyl acridine
and isoquinoline, emit to fume of CRMA. The content of PAHs
increases and the absolute amount of PAHs become higher for
the condensates, indicating the increased toxicological potential.
Compared to the untreated CR, microwave treated CR alters the
composition of fume, i.e. reducing the contents of aromatic hydro-
carbons and PAHs. Thus, microwave treatment on CR decreases
the toxicological potential of asphalt fume. The results in Table 3
also showed that adding TOR decreases the contents of PAHs and
sulfur compounds in condensates effectively in comparison to
CRMA.
Consequently, microwave treatment on CR or adding TOR in
combination of CR has the positive effect on the decontamination
of fume, which reduces the concentration of PAHs in fume emis-
sion. Furthermore, some researchers such as Kurek et al. [43]
investigated the PAHs emission of conventional asphalt in labora-
tory. Also Zanetti, M.C.et al. [35] carried out laboratory test on gas-
eous emissions of asphalt rubber bitumen. According to our

Table 3
Chemical compositions and contents of the condensates for base asphalt and various CRMA.

Base asphalt Various modified asphalt

CRMA CRIMMA CRTORMA
Compounds Content/wt% Compounds Content/wt% Content/wt% Content/wt%
1 Ethylcyclohexane 2.64 Cyclohexanethiol 1.13 0.74 0.57
2 iso-propyl benzene 1.46 Ethylcyclohexane 0.30 1.04 1.56
3 Propylcyclohexane 1.32 o-methyl ethyl benzene 0.51 0.43 0.40
4 Propylbenzene 0.88 Propylcyclohexane 0.73 1.55 1.49
5 o-ethyl-toluen 8.58 Propylbenzene 0.91 0.82 0.97
6 Mesitylene 3.17 3-ethyltoluene 5.12 3.98 4.08
7 3-ethyltoluene 1.86 Mesitylene 2.22 2.01 1.74
8 3-ethyltoluene 9.79 o-ethyl-toluen 1.03 1.23 0.87
9 Dihydroindene 1.01 1, 2, 3-trimethyl benzene 7.4 5.12 6.27
10 1, 1-dimethyl benzyl alcohol 0.53 Propyl benzene rings 0.9 1.12 0.84
11 1-methyl-3- propyl benzene 0.91 n-nonane 0.17 0.54 0.36
12 o-diethylenzene 2.54 isoquinoline 4.71 3.08 3.24
13 4-ethyl-1, 2-dimethyl benzene 4.49 Decane 1.98 1.54
14 1-methyl-4-propyl benzene 0.70 1-methyl-3-propyl benzene 2.01 1.82 1.58
15 p-isopropyltoluene 4.97 o-diethylenzene 3.01 2.47 2.10
16 2-ethyl-1, 4-dimethyl benzene 7.62 1-ethyl-2, 4-dimethyl benzene 4.53 4.34 3.42
17 1,2,4,5-tetramethyl-benzene 3.40 1-methyl-4-propyl benzene 1.12 0.85 0.94
18 1, 2, 3, 4 - methyl benzene 7.16 2-ethyl-1, 4-dimethyl benzene 4.63 3.40 3.19
19 1-butenyl benzene 1.07 Adjacent cymene 5.49 4.27 3.89
20 Naphthalene 0.34 2-ethyl-1, 3-dimethyl benzene 9.45 7.91 8.04
21 Alkyl cyclopentane 0.31 1, 2, 3, 4-methyl benzene 4.35 3.17 4.03
22 n-dodecane 0.57 1,2,4,5-tetramethyl-benzene 9.24 7.83 6.58
23 Xenene 1.20 Indan 1.49 1.62 1.82
24 n-tetradecane 1.01 1-vinyl-4-ethyl benzene 0.8 0.51 0.64
25 Octyl cyclohexane 0.61 Naphthalene 0.64 0.41 0.58
26 1, 2-hydroxy-5-methyl tertiary butyl-benzene 3.71 p-methyl isobutyl benzene 0.42 0.30 0.32.
27 Ethyl anthraquinone of nitrogen 0.28 1, 3-diethyl-5-methyl benzene 0.33 0.41 0.22
28 1-hexadecene 0.34 2, 4-dimethyl-1-(1-) methyl ethyl benzene 0.27 0.31
29 n-hexadecane 1.68 p-ethyl isopropyl benzene 0.18 0.22 0.12
30 Hendecyl cyclopentane 0.43 (1-methyl-3-butene)-benzene 1.26 1.08 1.18
31 8-cetene 0.29 52-methyl ethyl-octane 0.19 0.50 0.67
32 n-heptadecane 0.24 n-dodecane 0.29 0.51 0.47
33 3-octadecene 0.32 Cyclohexene benzene 0.12 0.07 0.08
34 n-octadecane 1.58 n-tetradecane 0.61 0.82 0.89
35 9-octadecene 0.46 1-Tetradecene 0.84 0.97
36 2-methyl octadecane 0.33 3, 52 tertiary butyl-4-hydroxy toluene 0.11 0.08
37 1-nonadecene 0.52 Decyl ring pentane 0.15 0.34 0.45
38 2,6,10,14-tetramethyl hexadecane 0.20 2-ethyl acridine 6.81 5.10 4.85
39 n-eicosane 1.97 Hexadecane 0.85 1.29 1.60
40 1-Docosene 0.57 5, 8-diethyl dodecane 0.11 0.28 0.30
41 n-docosane 3.65 1, 10 - (1, 2-ring butyl) diphenyl 0.21 0.20 0.29
42 Dodecanoic acid, hendecylester 0.85 3-cetene 0.17 0.24 0.18
43 n-tetracosane 0.94 1-phenyl-1, 2-dihydro naphthalene 0.64 0.57 0.51
44 1, 4-dimethyl-2-cetyl cyclohexane 1.10 1-phenyl 1, 2, 3, 4-four hydrogen naphthalene 0.31 0.38 0.48
45 1-hexacosanol 0.54 1- Heptadecene 0.06 0.81 0.75
46 n-hexacosane 0.59 n-octadecane 0.12 0.52 0.60
47 1-cerotene 0.32 1-octodecene 0.90 0.20
48 9, 9-hexyl pentadecane 0.32 1-eicosene 0.15 0.39 0.86
49 Hentriacontane 0.63 5-butyl hexadecane 0.52 1.08 0.94
50 n-eicosane 2.67 5.92 4.67
51 n-docosane 0.59 1.82 3.14
52 3-methyl-heneicosane 1.49 1.99
53 n-tetracosane 0.13 0.72 0.94
54 n-hexacosane 0.58 0.64
55 11-amyl-heneicosane 0.15 0.35 0.17
56 9-octyl docosanoic 0.09 0.28 0.18
316 M. Liang et al. / Construction and Building Materials 154 (2017) 310322

Fig. 4. Master curves of various CRMA at the reference temperature of 25 C.

Table 4
Activation energy calculated from the Arrhenius fitting curves. 3.2.1. Viscoelasticity behavior
Viscoelastic parameters (storage modulus G0 , loss modulus G00 ,
Ea
phase angle, et al.) and their variations with time (frequency) or
CRMA CRIMMA CRTORMA CRIMTORMA temperature can detect the changes of internal structure of vis-
Q 174.7 169.3 177.4 176.6 coelastic materials, which also can reflect the relationship
K 170.8 165.9 171.7 167.6 between molecular structure and macro-scale performance
[44,45]. In this work, viscoelastic parameters were obtained from
frequency sweeps and temperature sweeps by DSR. The time-
review, there was no available information on fume composition temperature superposition (TTS) principle was employed to
for asphalt with CR activated by microwave and TOR. investigate viscoelasticity behavior in a wide time (frequency)
scale for various CRMA. The master curves of various modified
3.2. Rheological properties and effects of microwave and TOR asphalt at the reference temperature of 25 C were obtained by
shifting G0 and G00 curves at different tested temperatures hori-
In order to evaluate the effect of CR activated by microwave and zontally using the shift factor aT. As can be seen in Fig. 4, TTS
TOR on the mechanical performance of CRMA, various rheological fitted the results well, although there was a concern regarding
properties were characterized using small-angle oscillation shear its applicability on polymer modified asphalt. Differences in
test, transient test, and flow test. The viscoelastic behavior, flow modulus among various samples can be distinguished in the
behavior, relaxation properties, and creep-recovery performance low frequency range and such difference was more significant
were obtained for various CRMA. Furthermore, effects of micro- for asphalt Q. CRTORMA of asphalt Q showed the greatest value
wave and TOR on CRMA were also evaluated by FTIR. in G0 while CRIMMA displayed the minimum value in storage
 M. Liang et al. / Construction and Building Materials 154 (2017) 310322 317

Fig. 5. Changes of G0 , G00 with temperature for various CR modified asphalt Q and K.

Fig. 6. Temperature dependence of G*/sin(d) for various CR modified asphalt Q and K.

modulus. Meanwhile, CRIMTORMA showed similar values in G0 age modulus, due to addition of TOR into asphalt K, was less
in comparison with that of CRMA. As to asphalt K, the differ- than that of asphalt Q. This may be resulted from the fact that
ences of mechanical characteristics for asphalt samples in low asphalt K had the lower asphaltene content and the interactions
frequency were not obvious. The extent of improvement in stor- were not as strong as that of asphalt Q.
318 M. Liang et al. / Construction and Building Materials 154 (2017) 310322

Moreover, shifting factors aT at tested temperatures were also
inserted in Fig. 4. The Arrhenius relations were fitted to describe
the variation of shifting factor versus temperature. Consequently,
activation energy can be acquired from the slope of Arrhenius fit-
ting curves, as shown in Table 4. Since activation energy was calcu-
lated from the slope of curve of shifting factor with temperature, it
was related to temperature susceptibility of asphalt. CRTORMA
exhibited the greatest value in activation energy; while CRIMMA
showed the minimum value. Therefore, the addition of TOR can
decrease temperature susceptibility of CRMA, but microwave
treatment on CR had negative effect in terms of temperature
susceptibility.
The effects of microwave treatment and TOR on performance of
CRMA were also studied by temperature sweep tests. Temperature
dependence of G0 and G00 as well as G/Sin (d) were presented in
Figs. 5 and 6, respectively. Generally, G0 and G00 dropped signifi-
cantly with the increase of temperature, but the rates of change
were different. It is noteworthy that a shoulder existed in G0
curves for CRTORMA in the medium-high temperature range,
which indicated the less temperature sensitivity. The shoulder
phenomenon means the presence of network structure in
CRTORMA, indicating greater resistance to deformation at high
temperatures. When the network structure was imposed by stress,
it can recover in a short time period after stress unloading. It was
the network structure in asphalt that causes CRTORMA having
the improved G0 at the tested temperature. What more, the shoul-
der was not so obvious for asphalt K due to the lower asphaltene
in asphalt K. However, the shoulder in G0 curve was not found for
the other samples.
A dotted line in Fig. 8 denotes G/sin(d) = 1kPa and G/sin (d)
was defined as a factor to evaluate rutting resistance of binder.
Thus, failure temperature (the temperature corresponding to
G/sin(d) = 1 kPa) can be obtained (Table 5). The addition of TOR
increased failure temperature of CRMA, compared to the negative
effect of microwave treatment. These results obtained from tem-
perature sweeps were in line with previous discussions.
3.2.2. Viscous flow behavior
The nonlinear viscoelastic behavior measured at large deforma-
tion was evaluated by mean of steady state flow, which can give
unique information related to the internal structure of asphalt bin-
der. The flow curves at 60 C represented by the relationship
between steady viscosity and shear rate were depicted in Fig. 7.
In the low shear rate range, all studied samples showed Newtonian
behavior where viscosity kept constant. The Newtonian plateau
mainly showed the behavior of continuous phase of bulk asphalt,
because CR particles were dispersed in the colloidal medium. The
domain involved CR particles moved together with bulk asphalt
phase under the very small shear stress. At this situation, CR phase
shift with bulk asphalt phase in the synchronized step. As the
increase of shear rate, a shear-thinning behavior was noticed and
became more evident in the higher shear rate range. If the shear
rate was too high (exceeds 1 s1), the asphalt sample between
the two plates will be squeezed out and the results were not reli-
able. Thus, Cox-Merz transformation was applied to amend the vis-
cosity in the high shear rate range. Cox-Merz transformation
indicates the inter-relationship between oscillatory data and
steady shear data, as shown in the following equation:
jg xj gc_ 1
where, g x is complex viscosity as a function of angular frequency
from frequency sweep test; gc_ is shear viscosity as a function of
shear rate from steady state data.
Flow curves amended by Cox-Merz transformation for various
CR modified asphalt were fitted by the Carreau model fairly well
[46]:
g 1
  2 s 2
g0 c_
1 c_ c
Table 6
The parameters obtained from the Carreau model.

Parameters CRMA CRIMMA CRTORMA CRIMTORMA

Table 5
Failure temperature (G*/sin d = 1.0 kPa) for various CRMA. Asphalt Q
g0 (Pas) 5933 5024 8085.5 6752.8
Asphalt Failure Temperature c_ c (s1) 0.045 0.02228 0.01094 0.0179
s 0.129 0.10685 0.1164 0.1145
CRMA CRIMMA CRTORMA CRIMTORMA
Asphalt K
Q 91.0 87.8 96.3 90.1 g0 (Pas) 2361.6 2037.2 2702 2596.8
K 83.6 82.4 87.0 84.6 c_ c (s1) 0.11245 0.07441 0.058 0.08317
s 0.10836 0.09724 0.10854 0.10723

Fig. 7. Flow curves combined with Cox-Merz transformation of various CR modified asphalt Q and K at 60 C.
 M. Liang et al. / Construction and Building Materials 154 (2017) 310322
where, s is rate index that is relevant to the gradient of shear-
thinning region; c_ c is critical shear rate that means the susceptibil-
ity to shear, corresponding to flection point of shear-thinning; g0 is
the asymptotic viscosity when shear rate approaches zero, i.e. zero-
shear-rate viscosity (ZSV).
The resulting fitting parameters were shown in Table 6. It was
found that TOR enhances ZSV values of CRMA significantly.
CRTORMA showed the lowest value in c_ c among all samples, which
implies the most sensitivity to shear force and attributes to the
cross-linking network. Whereas for CRIMMA, microwave treat-
ment on CR reduces ZSV of modified asphalt and causes more ther-
moplastic characteristics. As for CRIMTORMA, ZSV values of
modified asphalt was slightly greater than that of the untreated
CR modified asphalt because of combined effects of TOR and micro-
wave treatment. In addition, the differences among various sam-
ples made with asphalt Q were more significant than those of
asphalt K. The ZSV value of the modified asphalt Q was greater than
that of the modified asphalt K and the opposite case was for c_ c ,
which was associated with their differences in asphaltene contents
and oil sources.
3.2.3. Stress relaxation
Stress relaxation is a typical response of viscoelastic materials.
When stress is loaded on materials to keep a constant strain, stress
will decrease gradually with time. Relaxation modulus G(t) is the
ratio of stress and strain during this process and G(t) depends on
time only in a small deformation range. Stress relaxation perfor-
mance can reflect the cracking tendency of asphalt. The faster
decreasing in relaxation modulus indicates the stronger resistance
to thermo-cracking.
In this study, stress relaxation tests at 10 C were carried out on
various CRMA to evaluate the effect of TOR and microwave treat-
ments on the relaxation performance of asphalt. As depicted in
Fig. 8, two relaxation stages were observed for all samples. The first
was rapid relaxation in very short time and the second is slow
relaxation in which relaxation modulus appears to approach an
asymptotic value. At the first stage, CRTORMA displayed the slow-
est rate of decline in G(t) while CRIMMA showed the fastest relax-
ation. In other words, TOR causes CRMA to take longer time to
reach certain relaxation modulus, whereas microwave treatments
shorten the corresponding relaxation time. When subjected to
stress, molecular conformational changes of maltene and rubber
particles response to the load promptly. However, CRTORMA was
not easy to achieve such rapid molecular conformational changes.
On the other hand, the movement of dispersed rubber phase was
Fig. 8. Variations of relaxation modulus with time for different CRMA at 10 C.
319
mainly responsible for the slow relaxation stage. The shifted rub-
ber phase tends to go back to the initial equilibrium position, but
the tendency became weaker as the elongation of time under con-
stant imposed strain. In addition, asphalt K showed the faster
relaxation at the first stage and had the lower asymptotic G(t) at
the end of second stage.
3.2.4. Multiple Stress Creep-recovery (MSCR)
MSCR was proposed by AASHTO TP70 [47] to characterize high
temperature performance of polymer modified asphalt The high
temperature parameters namely the percentage of elastic recovery
(R) and non-recoverable compliance (Jnr) were determined by sep-
arating the recovered and the non-recovered strain.
Fig. 9 exhibited the percentage of elastic recovery and
non-recoverable creep compliance at 60 C at two stress levels
for various CRMA. As can be seen, the stress level had a great influ-
ence on R and Jnr. The elastic recovery decreased drastically and the
non-recoverable creep compliance increased greatly at 3200 Pa
level in comparison to those at 100 Pa level. Usually, the stress of
100 Pa was in linear viscoelastic range of most modified asphalt,
but the stress of 3200 Pa was in the non-linear viscoelastic range.
This indicated that overloading can cause severe rutting damage
at high temperatures.
For the two stress levels, CRTORMA showed the maximum value
in R and the minimum value in Jnr for asphalt Q and K. However,
CRIMMA presented the minimum R value and the maximum Jnr
value. These results implied that TOR improved high temperature
performance of CRMA due to the chemical cross-linking effect;
while CR treated by microwave treatment adversely impact the high
temperature performance of CRMA. There was almost no difference
between CRIMTORMA and CRMA, indicating that the improvement
of TOR was counterbalanced by microwave treatment.
3.2.5. Effects of microwave and TOR on CRMA
From the above rheological performance, it can be concluded
that microwave treatment on CR impaired viscoelastic behavior
of CRMA, which indicated an inferior mechanical performance on
pavement. Contrary to microwave treatment, TOR improved the
viscoelastic behavior significantly. The FTIR spectra shed some
light on the viscoelastic results. FTIR spectra of base asphalt, CRMA
and microwave activated CRMA was shown in Fig. 10. Fig. 10 also
displayed the FTIR result of base asphalt in order to comparison. It
can be seen that typical absorption peaks occur at similar
wavenumbers for base asphalt, modified asphalt with untreated
CR and microwave irradiated CR. These similar absorption bands
320 M. Liang et al. / Construction and Building Materials 154 (2017) 310322
Fig. 9. The percent recovery and non-recoverable creep compliance at 60 C and two stress level for various CRMA.
Fig. 10. FTIR spectra of base asphalt and asphalt modified by untreated CR and
microwave activated CR.
mainly concentrate at 2952.5 cm1, 2923.3 cm1, 2852 cm1,
1616 cm1, 1457 cm1 and 13376 cm1. Compared with base
asphalt and asphalt with untreated CR, the significant difference
in FTIR for asphalt with microwave irradiated CR occurs at the peak
of 1261 cm1, 1094 cm1, 1031 cm1, 804.7 cm1 and 667 cm1.
The absorption peaks at 1261 cm1, 1094 cm1 and 1031 cm1
are identified as the bending vibrations of OAH, stretching vibra-
tions of CAO and stretching vibrations of S@O, respectively. The
difference of peaks at 804.7 cm1 is caused by substituted benzene.
The peak at 667 cm1 is attributed by CAS stretching vibrations.
More importantly, the emphasis was put on the variation of sulfide
in rubber particle after activation. Thus, peaks between 700 cm1
and 400 cm1 enlarged as shown in the inserted graph. Interest-
ingly, the intensity of CAS bond increases after the microwave
treatment on CR. It is reasonable to deduce that microwave broken
the polysulfide bond, which exposes more carbon-sulfur bond.
Based on FTIR analysis, microwave treatment on CR leads to the
formation of oxygen containing groups because of the presence
of air during microwave irradiation. When chemical bond was
broken by microwave, the oxygen atom was linked inevitably.
Therefore, microwave treatment on CR results in the aging of
Fig. 11. FTIR spectra of TOR, CRMA and CRMA with TOR.
rubber particles. In addition, high-powered microwave cleaved
cross-linked sulfide bond in rubber. Literatures also argued that
microwave had the de-vulcanization effect on crumb rubber
[23,24]. Consequently, the cleft of cross-linked structure and aging
of rubber particles to some extent impaired the mechanical prop-
erties of rubber, which decreases mechanical characteristic of
asphalt in comparison with non-treated CR.
The FTIR results of TOR, CRMA and CRMA with TOR were pre-
sented in Fig. 11. The attributions of absorption peaks at
3439 cm1, 2953 cm1, 2923.3 cm1, 2852.5 cm1, 1617 cm1,
1457 cm1, 13376 cm1, et al. can be illustrated similarly as
Fig. 10 that will not be analyzed there again. Therefore, the empha-
sis is placed on the peak at 966 cm1. The strong peak at 966 cm1
means a great amount of double bonds in TOR. However, the
intensity of peak at 966 cm1 for CRMA with TOR decreases signif-
icantly, which indicates that double bonds in TOR participate in
chemical reaction. The chemical reaction among TOR, CR and
asphalt component greatly improves the elastic behavior. Besides,
there is no absorption band at 966 cm1 for CRMA, which indicates
that CR only affects the physical properties of asphalt by means of
physical interactions. In addition, previous research [31] has indi-
cated that TOR chemically cross-linked the sulfur elements in
 M. Liang et al. / Construction and Building Materials 154 (2017) 310322
asphaltene and maltenes with the sulfur exposed on the surface of
CR particles, which converts thermoplastic characteristics of
asphalt to thermosetting behavior.
Therefore, de-vulcanization effect of microwave on CR as well
as chemical reaction of TOR (verified by FTIR) can give the good
explanations on the rheological results. Chemical cross-linking
among TOR, rubber and asphalt results in improved modulus,
enhanced viscosity, increased recovery ability and decreased tem-
perature sensibility of CRMA, which was expect to endow asphalt
pavement with more elastic character and stronger resistance to
permanent deformation. Whereas, de-vulcanization effect of
microwave on CR impairs high temperature performance of modi-
fied asphalt, but CR activated by microwave leads to a faster stress
relaxation response of CRMA, indicating the stronger resistance to
thermal cracking.
5. Conclusions
This paper studied the composition of fume emissions during
preparation of asphalt modified with CR activated by microwave
and TOR, with the goal of decreasing fume emissions and
hazardous species. Moreover, effects of microwave and TOR on vis-
coelastic behavior of CRMA were also studied.
GCMS results indicated that a large amount of species of
hydrocarbons and heteroatomic hydrocarbons were found in
fume of base asphalt, including alkanes, cycloalkanes, alkenes,
aldehydes, ketones, aromatic hydrocarbons, polycyclic aromatic
hydrocarbons (PAHs) as well as a small amount of alcohols and
esters. However, more sulfur compounds (hydrogen sulfide, car-
bonyl sulfide, methanthiol and carbon disulfide) presented in
the emissions of CRMA, which accounts for pungent odour. More-
over, microwave treatment on CR reduced the concentrations of
aromatic hydrocarbons and PAHs, which can lower toxicological
potential of fumes. The greater extent of reduction in aromatic
hydrocarbons, PAHs, and sulfur compounds in fume was also
observed for TOR.
The rheological results obtained from frequency and tempera-
ture sweeps in the linear viscoelastic region indicated that CR
activated by TOR greatly improved viscoelastic functions (G0 , G00 ,
G/Sin (d)) and decreased temperature susceptibility of asphalt,
which is expect to endow asphalt pavement with more elastic
character and stronger resistance to permanent deformation. The
enhancement in thermo-mechanics can attribute to chemical
cross-linking among TOR, rubber and asphalt, which were verified
by FTIR results. On the other hand, CR treated by microwave
impaired high temperature viscoelastic properties of modified
asphalt in comparison with the untreated one. Furthermore, non-
linear viscoelastic functions such as ZSV (steady state flow) and
recovery ability R (MSCR) increased significantly for CRMA with
TOR, implying the stronger resistance to rutting of pavement.
Microwave treatment on CR abated these nonlinear viscoelastic
parameters in comparison to untreated sample. However, CR acti-
vated by microwave led to a faster stress relaxation response of
CRMA, indicating the stronger resistance to thermal cracking.
As a result, microwave treatment and TOR decreased the con-
centrations of aromatic hydrocarbons and PAHs. More importantly,
they improve rheological properties of binder and thus extend
pavement service life, which requires less maintenance and repair
treatments and reduces fume emissions in the construction.
Acknowledgements
Financial support from FRFCU (the Fundamental Research
Funds for the Central Universities, No. 24720156046A) and CUPPIP
321
(China University of Petroleum Postgraduate Innovation Project,
No. 15CX06046A) were acknowledged.
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