Construction and Building Materials 25 (2011) 129–137

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Construction and Building Materials

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Effects of thermal oxidative ageing on dynamic viscosity, TG/DTG, DTA and FTIR
of SBS- and SBS/sulfur-modified asphalts
Feng Zhang *, Jianying Yu, Jun Han
Key Laboratory of Silicate Materials Science and Engineering of Education Ministry, Wuhan University of Technology, Wuhan 430070, PR China

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

Article history: Thermal oxidative ageing as an inevitable process in the practical application of road asphalt has a great
Received 19 March 2010 effect on the properties of polymer-modified asphalts (PMAs). In this article, the influences of short-term
Received in revised form 11 May 2010 and long-term thermal oxidative ageing on the dynamic viscosity, thermal stabilities, and infrared spec-
Accepted 19 June 2010
tra of styrene–butadiene–styrene (SBS)- and storage-stable SBS/sulfur-modified asphalts were studied
respectively. Although the addition of sulfur improved the dynamic viscosity and the thermal stability
of SBS-modified asphalt significantly due to the formation of a chemically crosslinked polymer network
Keywords:
structure, the improved properties declined evidently after ageing and the losses of properties became
Asphalt
SBS
very severe with the ageing aggravated and the binder with sulfur showed a visible viscous behaviour
Sulfur compare with the corresponding binder without sulfur after ageing due to the severe degradation of vul-
Ageing canized SBS, therefore SBS/sulfur-modified asphalt was more susceptible to ageing. Besides, the SBS
Dynamic viscosity structure also had a great effect on the properties of binders before and after ageing. In infrared spectra
Thermal stability analysis, the structural evolutions of binder under different ageing modes were characterized by using
FTIR right ageing index and the conclusions of thermal analysis and dynamic viscosity tests were confirmed
further by the changes of butadiene and carbonyl indexes.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Asphalt have been widely used in road pavement as the binder
of aggregate. Unfortunately, high-temperature rutting and low
temperature cracking of asphalt cement or coating layer, due to se-
vere temperature susceptibility, limit its further application [1].
Therefore, it is necessary to modify asphalt. Styrene–butadiene–
styrene triblock copolymer (SBS) as one of the modifiers of asphalt
is a synthetic thermoplastic elastomer. The styrene, referred as the
hard block, is usually the dispersed phase, and provides the
strength of the material, while the butadiene, the soft block, con-
tributes to the elasticity of SBS. The hard block dispersed in the soft
one forms physical crosslinks, a three-dimensional network. At
temperatures above the glass transition temperature of the styrene
block, the physical crosslinks disappear. Upon cooling, the cross-
links reform, and the strength and elasticity of the SBS are restored.
At a given temperature in the range of the glass transition temper-
atures of both soft block and hard block (90 °C to.+90 °C) [2], the
SBS behaves like an elastomer. SBS can contribute to asphalt
strength and elastic properties in a wide range of temperature by
blending SBS with asphalt [3,4]. So SBS is one of the most promis-
ing modifiers for asphalt. Unfortunately, SBS is destined to separate
* Corresponding author. Tel.: +86 27 59735058; fax: +86 27 87863591.
E-mail address: wucifanying@163.com (F. Zhang).
from the asphalt when stored at high temperature, which is the
major obstacle to the application of SBS-modified asphalts in pav-
ing [5]. To resolve the problem, many measures have been taken,
such as using kaolinite clay or organobentonite or adding carbon
black and so on [6–10], however one of the most effective and
practical ways is to add sulfur in SBS-modified asphalt. It is com-
monly believed that sulfur chemically crosslinks the polymer mol-
ecules and chemically couples polymer and asphalt through sulfide
and/or polysulfide bonds [11].
Some publications to date concern the studies on SBS/sulfur-
modified asphalt. Wen Guian has studied the rheological proper-
ties of SBS/sulfur-modified asphalt systematically and pointed
out the influences of some important factors such as sulfur level,
SBS structures or contents on the rheological behaviours of modi-
fied binders, and studied the morphological changes of storage-sta-
ble SBS/sulfur-modified asphalt at elevated temperature [11–13].
The similar studies were also reported in other publications
[14,15]. However, the studies on other important properties of
storage-stable SBS/sulfur-modified asphalt including dynamic vis-
cosity, thermal stability, infrared spectra have not been reported in
many publications. Moreover, thermal oxidative ageing as an inev-
itable process in practical road paving has a great effect on the
properties of asphalt. The performances of asphalt pavement actu-
ally depend on the properties of aged asphalt. The high-tempera-
ture properties of SBS-modified asphalt can be improved

0950-0618/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2010.06.048
130 F. Zhang et al. / Construction and Building Materials 25 (2011) 129–137
significantly with the addition of sulfur as reported earlier, how-
ever if the improved properties also can be retained after ageing
is not reported in many publications. Besides the relationship be-
tween the property and the structure of storage-stable SBS/sul-
fur-modified asphalt after ageing is still not reported in many
publications.
The present work seeks to identify the changes in dynamic vis-
cosity and thermal stabilities of SBS- and storage-stable SBS/sulfur-
modified asphalts through short-term ageing test (thin film oven
test, TFOT) and long-term ageing test (pressurized ageing vessel,
PAV), to compare SBS-modified asphalt with storage-stable SBS/
sulfur-modified asphalt by ageing, to investigate the structural
characteristics of binders by using infrared spectrography.
2. Experimental
2.1. Materials
Asphalt, SK-90 paving asphalt, was obtained from the SK Petro-
leum Asphalt Factory, Southern Korea. The physical properties of
the asphalt are as follows: softening point: 46.3 °C (ASTM D36);
penetration: 87 dmm (25 °C, ASTM D5); viscosity: 0.32 Pa.s
(135 °C, ASTM D 4402).
SBS1301 and SBS4303 were produced by the Yueyang Petro-
chemical Co., Ltd., China. SBS4303 is a star-like polymer, containing
30 wt.% styrene, the average molecule weight is 350,000 g/mol.
SBS1301 is linear polymer, containing 30 wt.% styrene, the average
molecule weight is 110,000 g/mol. Elemental sulfur is a commer-
cial product (industrial grade) of yili Chemical Co., Ltd., China.
2.2. Preparation of samples
The modified asphalts were prepared using a high shear mixer
(made by Weiyu Machine Co. Ltd., China). Firstly, asphalt (400 g)
was heated until it became fluid in an iron container, then upon
reaching about 180 °C, the SBS and sulfur powder (the amounts
were based on 100 parts asphalt) were added to the asphalt under
high-speed shear mixing for 40 min, the shear speed is 4000 r/min.
Subsequently the mixture was stirred by a mechanical stirrer at
180 °C for 2 h, the rotation speed was 3000 r/min.
2.3. Thin-layer chromatography with flame ionization detection (TLC-
FID)
In the TLC-FID, 2% (w/v) solutions of the unaged and aged base
asphalts were prepared in dichloromethane, and 1 ll sample solu-
tion spotted on chromarods using a spotter. The separation of bitu-
men into four generic fractions (saturates, aromatics, resins and
asphaltenes) was performed by a three-stage development using
n-heptane, toluene and dichloromethane/methanol (95/5 by vol-
ume), respectively. The fractions were determined by means of
Iatroscan MK-5 analyzer (Iatron Laboratories Inc., Tokyo, Japan).
2.4. Storage stability test
The storage stability of modified asphalts was measured as fol-
lows. The sample was poured into an aluminum toothpaste tube
(32 mm in diameter and 160 mm in height). The tube was sealed
and stored vertically in an oven at 163 °C for 48 h, then taken
out, cooled to room temperature, and cut horizontally into three
equal sections. The samples taken from the top and bottom sec-
tions were used to evaluate the storage stability of the SBS-modi-
fied asphalts by measuring their softening points. If the
difference of the softening points between the top and the bottom
sections was less than 2.5 °C, the sample was considered to has
good high-temperature storage stability. If the softening points dif-
fered by more than 2.5 °C, the SBS-modified asphalt was consid-
ered to be unstable.
2.5. Standard ageing procedure
Two conventional tests were used to simulate the thermal oxi-
dative ageing for PMAs: thin film oven test (TFOT, standard ASTM
D1754) and the pressure ageing vessel (PAV, standard ASTM
D6521).
Short-term ageing was addressed by the thin film oven test
(TFOT). Binders were aged during 5 h at 163 °C in air as described
in the standard ASTM D1754. This technique has been validated for
some time for unmodified asphalts for which it is considered to be
more severe than actual jobsite conditions; in the case of modified
asphalts, its validity is still open to doubt [16]. However, in the ab-
sence of anything better, it has been used with considerable suc-
cess to compare different PMAs during laboratory studies [16,17].
Long-term ageing was addressed by the pressure ageing vessel
(PAV). Binders were aged during 20 h at 100 °C under 2.1 MPa of
air as described in the standard ASTM D6521. In the case of
unmodified asphalts, the simulated ageing provided is recognized
to be equivalent to several years of service in a road, but how long
this equivalence is depends on the asphalt recently, a study of sev-
eral experimental pavements [16,17] found this simulated ageing
to be equivalent to 4 years.
2.6. Dynamic viscosity test
The dynamic viscosity of binder under different temperatures
was determined using a strain-controlled rheometer (RDA II, Rheo-
metrics) with parallel plate geometry (25 mm in diameter), was
used to determine the dynamic viscosity of the asphalts before
and after ageing. Temperature sweeps (from 30 to 138 °C) with
2 °C increments were applied at a fixed frequency of 10 rad/s and
variable strains. In each test, about 1.0 g of sample placed on the
bottom plate, covering the entire surface, and the plate was then
mounted in the rheometer. After the sample was heated to become
a melt, the top plate was brought into contact with the sample, and
the sample was trimmed. The final gap was adjusted to 1 mm. The
actual strain and torque were measured to calculate the viscoelas-
tic parameters such as complex viscosity (g), phase angle (d). All of
the tests were conducted within the linear viscoelastic range.
2.7. Thermal analysis
Thermal analysis was performed using a TA Instrument, model
SDT 2960, under nitrogen atmosphere, sample mass around 7 mg,
with a constant heating rate of 10 °C/min, heated from room tem-
perature to 750 °C. The nitrogen flow during the experiments was
120 ml/min. The TG, DTG, and DTA versus temperature curves
were used to evaluate the thermal stabilities of binders respec-
tively. All experiments were performed three times for
reproducibility.
2.8. Fourier transform infrared (FTIR) spectroscopy
A FTIR spectrometer, infinity 60 AR (Mattson, resolution
0.125 cm1), was used to determine the functional characteristics
of modified binders before and after ageing in wavenumbers rang-
ing from 4000 to 400 cm1. Binders were dissolved in carbon disul-
fide with 5 wt.% concentration, then dropped onto KBr table and
dried for the FTIR analysis.
 F. Zhang et al. / Construction and Building Materials 25 (2011) 129–137
3. Results and discussion
3.1. Storage stability
A good compatibility between the polymer and the asphalt is
necessary to avoid separation during storage, pumping and apply-
ing the asphalt and to achieve the expected properties in the pave-
ment [18]. Stability tests can determine whether the interactions
created between the polymers and the asphalts during mixing
are strong enough to resist a separation of the polymer in the con-
ditions in which it is stored. The softening point variation has been
accepted to find out if phase separation occurred during the high-
temperature storage stability test.
The high-temperature storage stabilities of the SBS- and the
SBS/sulfur-modified asphalts with different SBS structures were
presented in Table 1. Obviously, for the SBS-modified asphalt in
the absence of sulfur, the differences in softening points were
large. As shown in Table 1, the differences in softening points were
14 °C for the SBS1301-modified asphalt and 35.8 °C for the
SBS4303-modified asphalt. Due to the more higher molecule
weight of SBS4303, the phase separation of the SBS4303-modified
asphalt was more severe. Storage-stable SBS-modified asphalts can
be prepared by reaction with sulfur at high temperature under
high shear mixing. The sulfur level was based on the asphalt. It
can be seen that the storage stability of the SBS-modified asphalt
was improved evidently with the addition of sulfur. When
0.1 wt.% sulfur was added to the SBS-modified asphalts, the differ-
ence in softening point was not more than 2.5 °C for the asphalts
modified by two structures of SBS, which meant the compatibility
of SBS-modified asphalt was improved significantly with the addi-
tion of sulfur. The SBS/sulfur-modified asphalt with 0.1 wt.% sulfur
had a good storage stability.
3.2. Dynamic viscosity
For the base asphalt, to clarify the effect of ageing on the chem-
ical components, the chemical components before and after ageing
were studied using TLC-FID, the four generic fractions, namely sat-
urates, aromatics, resins and asphaltenes, were determined, as
shown in Table 2. In short-term ageing, the content of the hard as-
phalt components such as asphaltenes and resins increased, while
the content of aromatics decreased, the varying trend became very
apparent with ageing aggravated, as shown by the changes in the
contents of the asphaltenes and aromatics after PAV ageing, the
saturates content remained comparatively constant in the process.
Obviously, the further ageing increased the asphaltenes content, by
which the rheological and thermodynamic properties of the as-
phalt binder were influenced.
In the dynamic viscosity test for asphalt, complex viscosity as a
fundamental rheological parameter is often used to express the
contribution of the asphalt binder to permanent deformation. With
increasing complex viscosity, the high-temperature performance
of the asphalt will be improved [19]. For PMAs, this improvement
can be attributed to the certain entanglements and interactions
among polymer molecules and between polymer and asphalt com-
ponents. Nowadays complex viscosity as an important rheological
parameter to evaluate the high-temperature performances of
Table 1
Effect of sulfur on storage stabilities of SBS-modified asphalts (SBS content: 3.5 wt.%).
Sulfur content (wt.%) DS°C1
SBS1301
0 14
0.1 0.2
131
Table 2
The chemical components of the base asphalt before and after ageing.
Unaged After TFOT After PAV
Saturates (%) 16.3 15.66 15.76
Aromatics (%) 49.19 46.06 38.36
Resins (%) 24.55 26.69 28.1
Asphaltenes (%) 9.96 11.99 17.78
PMAs is used widely. As one of the two significant effects of sulfur
on the properties of the SBS-modified asphalt, the improvement on
high-temperature complex viscosity was pronounced with the
addition of sulfur. The complex viscosity versus temperature plots
for all binders before and after ageing were shown in Fig. 1a–f. The
improved high-temperature performance of the storage-stable
SBS1301/sulfur-modified asphalt compare with the SBS1301-mod-
ified asphalt was shown in the increasing complex viscosity after
the transition temperature: 83.1 °C as shown in Fig. 1a, this can
be attributed to the formation of a polymer network structure in
asphalt matrix by chemically crosslinking and there were more
entanglements among polymer molecules at elevated temperature.
However, after TFOT ageing, as shown in Fig. 1b, the magnitude of
the increase in complex viscosity disappeared completely at ele-
vated temperature and the difference of complex viscosity be-
tween the two binders was slight in the whole temperature
domain, which indicated the crosslinking polymer network was
destroyed after ageing. After PAV ageing, as shown in Fig. 1c, the
complex viscosity of the binder with sulfur was lower than that
of the one without sulfur over the whole temperature range. Obvi-
ously, thermal oxidative ageing declined the improved complex
viscosity of the storage-stable SBS1301/sulfur-modified asphalt
and this loss of complex viscosity became more severe with the
ageing aggravated.
Compare with the SBS1301-modified asphalt, the SBS4303-
modified asphalt endured a similar change by the addition of sulfur
before and after ageing, however, due to the structural characteris-
tics of SBS4303, the SBS4303-modified binder series also showed
somewhat different behaviour. In Fig. 1d, the improved complex
viscosity of the vulcanized binder was shown in the increasing
complex viscosity after 63.5 °C, this transition temperature was
much lower than that of the storage-stable SBS1301/sulfur-modi-
fied asphalt. Because there were more polybutadiene structures
in SBS4303 compare with SBS1301, so SBS4303 was more reactive
with sulfur, the pronounced complex viscosity can be seen at the
lower transition temperature. Thermal oxidative ageing had a sim-
ilar effect on the complex viscosity of the SBS4303-modified as-
phalt. After TFOT ageing, the reduction in the magnitude of the
increase in complex viscosity can be observed after 100 °C and
the further reduction can be seen after PAV ageing, as shown in
Fig. 1e and f respectively. Due to the structural characteristics of
SBS4303, the loss of the complex viscosity of the SBS4303/sulfur-
modified asphalt was not like that of the SBS1301/sulfur-modified
asphalt.
Usually, there are two main changes that occur in PMAs during
thermal oxidative ageing process. On one hand, the increase of
hard asphalt components such as asphaltene, resins after ageing
led to the improvement on the elasticity of binder, on the other
hand, ageing prompted the decomposition of polymer dispersed
in asphalt matrix and resulted in an increase in the viscous behav-
iour of binder. Measurements of d are generally considered to be
more sensitive to the chemical structure and therefore the modifi-
cation of asphalt than complex viscosity [20]. To investigate the ef-
fects of thermal oxidative ageing on the structures of modified
SBS4303
binders further, the complex viscosity versus phase angle plots
35.8
for the SBS- and the SBS/sulfur-modified asphalts before and after
0.1
ageing were shown from Fig. 2a to d. For the SBS1301-modified as-
132 F. Zhang et al. / Construction and Building Materials 25 (2011) 129–137

Fig. 1. The complex viscosity versus temperature plots: (a) SBS1301- and SBS1301/sulfur-modified asphalts. (b) SBS1301- and SBS1301/sulfur-modified asphalts after TFOT
ageing. (c) SBS1301- and SBS1301/sulfur-modified asphalts after PAV ageing. (d) SBS4303- and SBS4303/sulfur-modified asphalts. (e) SBS4303- and SBS4303/sulfur-modified
asphalts after TFOT ageing. (f) SBS4303- and SBS4303/sulfur-modified asphalts after PAV ageing.

phalt, it can be seen from Fig. 2a that the shift of the curve towards
lower phase angles after TFOT ageing was observed for the com-
plex viscosity value greater than 87.1 Pa s, however, for the com-
plex viscosity value below 87.1 Pa s, the curve showed more
higher phase angle, which implied that the polymer dispersed in
asphalt decomposed under the influences of heat and oxygen and
rearranged in smaller fragments, therefore the viscous behaviour
of the binder increased. After PAV ageing, a continuous shift of
the curve towards lower phase angles can be seen over the whole
complex viscosity range. The elasticity of binder increased signifi-
cantly due to the obviously increased asphaltene content in the
prolonged ageing process of PAV ageing [21]. Though the polymer
 F. Zhang et al. / Construction and Building Materials 25 (2011) 129–137
Fig. 2. The complex viscosity versus phase angle plots before and after ageing: (a) SBS1301-modified asphalt. (b) SBS1301/sulfur-modified asphalt. (c) SBS4303-modified
asphalt. (d) SBS4303/sulfur-modified asphalt.
dispersed in asphalt also decomposed severely, the change of as-
phalt components still played a predominant role in the effect of
this ageing process on the rheological behaviour of the binder.
For the SBS1301/sulfur-modified asphalt, as shown in Fig. 2b, the
rheological behaviour of the binder differed completely from that
seen for the SBS1301-modified asphalt after ageing. It can be di-
vided up into two sections. The first section occured above a com-
plex modulus value of 1472.4 Pa s and showed a shift of the curve
towards lower phase angles indicating the hardening (ageing) of
the PMA. The second section occured below the complex modulus
value of 1472.4 Pa s and showed an opposite shift of the curve to-
wards higher phase angles after ageing and the shift became more
obvious with the ageing aggravated, thereby indicating a change
towards a more viscous rather than more elastic behaviour after
ageing [21]. The change towards a more viscous behaviour after
ageing and the increase in d after ageing, agreed with the assump-
tion that there was a more evident breakdown of the polymer sub-
structure during ageing into smaller copolymer structures
compare with the SBS1301-modified asphalt.
For the SBS4303-modified asphalt, as shown in Fig. 2c, a contin-
uous shift of the curve towards more higher phase angles in almost
the whole complex viscosity range after TFOT ageing showed an
obvious viscous behaviour of the aged binder, this can be attrib-
uted to the structural characteristics of SBS4303. Compared with
SBS1301, there are more polybutadiene structures containing in
the molecule of SBS4303 by the same weight. The unsaturated car-
bon–carbon double bond of butadiene was easier to be oxidized.
Therefore the SBS4303-modified asphalt was more susceptible to
133
ageing. After PAV ageing, the continuous shift of the curve towards
lower phase angles in the whole complex viscosity range compare
with the unaged binder showed the predominant role of the chan-
ged asphalt components on the rheological behaviour. For the stor-
age-stable SBS4303/sulfur-modified asphalt, the complex viscosity
versus phase angle plot before and after ageing was shown in
Fig. 2d, it can be seen that the shifts of the phase angle curves after
TFOT and PAV ageing were similar to those shown for the SBS1301/
sulfur-modified asphalt series to some extent. When the complex
viscosity value was above 8764.3 Pa s, there was a continuous shift
of the curve towards lower phase angles with the ageing aggra-
vated indicating the hardening (ageing) of asphalt. From
848.6 Pa s to 8764.3 Pa s, the opposite shift of curve towards higher
phase angle after ageing showed the increase in the viscous behav-
iour of the aged binders. When the complex viscosity was below
848.6 Pa.s, the viscous behaviour of aged binder became more
apparent with the ageing aggravated due to the severe degradation
of the vulcanized SBS.
From the complex viscosity versus phase angle plots depicted
above, we can see that the rheological behaviour of the SBS/sul-
fur-modified asphalt depended strongly on the effect of polymer
decomposition compare with the SBS-modified asphalt after
ageing.
3.3. Thermal analysis
The thermal stability of modified asphalt is an important prop-
erty to be considered in the analysis for the structural characteris-
134 F. Zhang et al. / Construction and Building Materials 25 (2011) 129–137
tics of asphalt binder [22]. In this paper, the thermal stabilities of
all binders were studied by thermogravimetry, the thermodynamic
behaviours of all samples are similar, which only can be illustrated
by that of the SBS1301-modified asphalt as shown in Fig. 3. The TG
thermogram showed that all binders have undergone the two ma-
jor mass loss stages. The first stage degradation occured in the
temperature range, 300–550 °C, and the mass loss of binder was
mainly due to the volatilization of light asphalt components such
as saturates and aromatics and the decompositions of asphaltene
and SBS [23,24]. This was the main mass loss stage as demon-
strated by the dramatic event in the DTG curve for each binder.
For most binders, there was an inexplicit multiplet peak on the
top of DTG curve, this is because the mass loss in the stage was
achieved by different steps and the DTG peak value was very sen-
sitive to the characteristic of each component. The DTA curve re-
vealed one obvious endothermic event before 550 °C and there
was an little endothermic peak on the top of the curve, which cor-
responded to the appearance of the multiplet peak of the DTG
curve exactly. The second-step mass loss started at 550 °C and
ended at 760 °C, the mass loss was mainly attributed to the further
volatilization of the decayed residues of asphaltene and rubber.
From 550 °C to 650 °C, the mass loss rate increased slowly with
increasing the temperature, after 650 °C, the DTG curve became
flat and the DTA curve showed one obvious exothermal event,
which showed the carbonization of residues.
Because the shape of the multiple peak of DTG curve was very
irregular for most binders and the differences among peak values
in each multiple peak were very small, so it was unreasonable
for us to evaluate the thermal stabilities of different binders by
using the maximum decomposition temperature of DTG curve.
Fortunately, there was an small endothermic peak on the top of
DTA curve, which corresponded to the appearance of the multiple
peak of DTG curve for each binder exactly. The maximum endo-
thermic temperature of the DTA curve, TDTA max, in this measure
also can be used in the evaluations for the thermal stability of bin-
der, as demonstrated by others [25]. To investigate the thermal sta-
bility of modified binder before and after ageing, TDTA max and the
onset temperature of the mass loss effects (T0) and the residue con-
tent at 760 °C for all binders were shown in Table 3. Besides, in this
text, to confirm the drawn conclusions further by evaluating TDTA
max, T0 and residue content, we used the integral procedural
decomposition temperature (IPDT) method to investigate thermal
stabilities of binders. Integral procedural decomposition tempera-
ture (IPDT) as proposed by Doyle provided a semi-quantitative
means for comparison of relative thermal stabilities [26,27]. The
integral procedural decomposition temperature is derived as a
Fig. 3. Thermodynamic behaviour of SBS1301-modified asphalt.
means of summing up the whole shape of the normalized data
curve. IPDT accounts the whole shape of the curve and it sum up
all of its dips and meanderings in a single number by measuring
the area under the curve. Thus thermal stabilities of binders have
also been determined by calculating IPDT values. To place all bind-
ers on an equal procedural footing, the curve is integrated on the
basis of the total experimentally accessible temperature ranges.
The area under the curve divided by the total area is the total curve
area, A, is normalized with respect to both residual mass and tem-
perature, A is converted to a temperature, T A , by
T A ¼ ðT end  T ini ÞA þ T ini ð1Þ
T A represents a characteristic end of volatilization temperature
rather than an IPDT having practical significance. The second curve
area K can be derived by drawing rectangle bearing X-axis up to
T A and the Y-axis mass fraction remaining at Tend. K is the ratio be-
tween the area under the curve (inside the rectangle) and total rect-
angle area. The IPDT determined by substituting AK for A in Eq. (1).
This index, the integral procedural decomposition temperature is a
reproducible datum having practical significance as an integrated
half-volatilization temperature [27]. The calculated IPDT value for
all binders were also presented in Table 3. Before ageing, the IPDT,
TDTA max and T0 of the SBS/sulfur-modified asphalt were higher than
those of the corresponding SBS-modified asphalt, it meant that the
thermal stability of the SBS/sulfur-modified asphalt was improved
due to the formation of a crosslinked polymer network structure in
asphalt matrix as mentioned earlier. After TFOT ageing, there was
an increase on T0, IPDT and TDTA max for each modified binder, as
shown in Table 3. There were two opposite effects of ageing on the
thermal stability of binder. On one hand, ageing prompted the poly-
condensation of light components in asphalt, led to the increase of
asphaltene content as shown in Table 2, which contributed to the im-
proved thermal stability of binder, on the other, ageing also
prompted the degradation of polymer dispersed in asphalt. The poly-
mer substructure was broken down by the effect of heat and oxygen
and rearranged in smaller fragments, this resulted in the decline in
the thermal stability of the modified binder. The final thermal stabil-
ity of binder depended on the combined effect. For each modified
binder, in the process of short-term ageing (TFOT), the increase of
asphaltene content played a predominant role in the effect of ageing
on the thermal stability of binder. For all TFOT aged binders, how-
ever, there was an obvious decline in T0, IPDT and TDTA max after a
long-term ageing (PAV) expect for the TFOT aged SBS4303-modified
binder, which showed a severe polymer degradation occurred in
most TFOT aged binders by the prolong ageing process. Though the
asphaltene content also increased evidently with the ageing aggra-
vated, the severe decomposition of polymer has declined the pre-
dominant effect of increased asphaltene on the thermal stability of
binder to a great extent. For the TFOT aged binder with SBS4303 so-
lely, the decomposition of polymer has been finished mainly during
TFOT ageing due to the susceptibility of SBS4303 to heat and oxygen
as confirmed by the corresponding shift of the phase angle curve,
therefore the further decomposition of polymer in PAV ageing did
not cause an obvious effect on the predominant role of increased
asphaltene. In addition, the T0, IPDT and TDTA max of modified binder
with sulfur were much lower than those of the corresponding binder
without sulfur after PAV ageing indicating the thermal stability of
the SBS-modified asphalt declined with the addition of sulfur in
the long-term ageing process and the degradation of the vulcanized
SBS became more severe with the ageing aggravated. This will re-
duce the service life of the SBS/sulfur-modified asphalt. These con-
clusions also can be confirmed further by the residue content at
760 °C. As shown in Table 3, the binder which owned more better
thermal stability also had more higher residue content at the final
 F. Zhang et al. / Construction and Building Materials 25 (2011) 129–137 135

Table 3
Summary of TG/DTG/DTA properties results for the modified binders before and after short-term and long-term thermal and oxidative ageing.

Sample Onset temp °C1 Maximum temp IPDT Mass loss% Residue at
DTA °C1 °C1 300–500 °C 500–760 °C 760 °C/%
1301 391.98 465.44 453.69 70.67 20.57 3.7
1301T 401.21 475.52 478.06 72.8 16.74 7.99
1301P 394.94 466.02 459.66 68.99 20.94 4.86
130101 398.19 469.75 467.19 69.99 19.17 6.01
130101T 399.95 472.32 468.17 71.77 17.2 6.37
130101P 391.98 460.7 441.6 72.77 22.13 1.51
4303 390.56 456.42 435.67 65.56 27.11 0.91
4303T 391.48 458.75 447.76 63.94 26.7 2.68
4303P 392.41 463.26 451.13 66.99 24.54 2.81
430301 393.17 462.06 462.67 68.05 20.95 5.56
430301T 395.42 464.74 467.65 69.94 18.85 6.26
430301P 382.15 452.92 440.7 69.77 25.51 1.46

Sample notation: 1301: SBS1301-modified asphalt (3.5 wt.% SBS1301). 130101: SBS1301/sulfur-modified asphalt (3.5 wt.% SBS1301; 0.1 wt.% sulfur). 4303: SBS4303-
modified asphalt (3.5 wt.% SBS4303). 430301: SBS4303/sulfur-modified asphalt (3.5 wt.% SBS4303; 0.1 wt.% sulfur). T: After short-term ageing (TFOT). P: After long-term
ageing (PAV).

test temperature and the changes of residue content of all binders
before and after ageing also conformed to the drawn conclusions
by evaluating T0, IPDT and TDTA max.
3.4. Infrared spectroscopy analysis
The FTIR spectrum of the base SK-90 asphalt was given in
Fig. 4a. The strong peaks within 2850–2960 cm1 region were typ-
ical CAH stretching vibrations in aliphatic chains. The peak at
1603.6 cm1 was attributed to C@C stretching vibrations in aro-
matics. The CAH asymmetric deforming in CH2 and CH3, and the
CAH symmetric deforming in CH3 vibrations were observed at
1458.2 cm1 and 1375.2 cm1 respectively. The peak at
1030 cm1 was ascribed to S@O stretching vibrations. The small
peaks within 740–910 cm1 region were typical CAH vibrations
of benzene ring. The FTIR spectra of the SBS- and the SBS/sulfur-
modified asphalts with different SBS structures before and after
ageing were shown in Fig. 4b–e. Compare with the FTIR spectrum
of the base SK-90 asphalt, there was only an new peak appeared at
966.1 cm1 in the spectrum of binder containing SBS and the new
peak at 966.1 cm1 was corresponding to the bending vibration of
CAH in the butadiene double bonds ACH@CHA. The monitoring of
ageing was performed by studying the changes in the spectra ob-
tained, in particular those affecting three characteristic bands:
the carbonyl functions C@O (centred around 1700 cm1), the buta-
diene double bonds (centred around 966.1 cm1) and the sulfoxide
functions S@O (centred around 1030 cm1). The first provided the
monitoring of the oxidation of the whole binder, the second the
monitoring of the deterioration of the SBS copolymer as a result
of modification of the butadiene copolymer by diminution of the
double bond [28] and the third monitoring might provide the mon-
itoring of the change on the structure of the vulcanized SBS copoly-
mer. This monitoring was performed by considering the area of the
functional bands or (in order to avoid the effect of the analyzed
quantities, that is to say the thickness of the film) by calculating
structural indices [28,29] of the following equations:
Area of the carbonyl band centered around 1700 cm1
IC@O ¼ P
Area of the spectral bands between 2000 cm1 and 600 cm1
ð2Þ
Area of the sulfoxide band centered around 1030 cm1
IS@O ¼ P
Area of the spectral bands between 2000 cm1 and 600 cm1
ð3Þ
Area of the ethylene band centered around 966 cm1
ICH@CH ¼ P
Area of the spectral bands between 2000 cm1 and 600 cm1
ð4Þ
The structural indices of all binders were shown in Table 4. Be-
fore ageing, the ethylene index of the SBS4303-modified asphalt
was larger than that of the SBS1301-modified asphalt due to the
higher butadiene content of SBS4303 and this index of modified
binder declined with the addition of sulfur as a consequence of vul-
canization. The ethylene index of modified binder without sulfur
declined evidently with the ageing aggravated, which implied the
polybutadiene structure of SBS underwent a significant degrada-
tion. For the SBS4303/sulfur-modified asphalt, the same conclusion
also can be found, however this trend became unnoticeable for the
SBS1301/sulfur-modified binder because most ethylene bonds
have been exhausted in vulcanization. In the case of the
SBS4303-modified asphalt, the dramatic decrease in the ethylene
index only after short-term ageing confirmed the drawn conclu-
sion by the corresponding thermal analysis and the shift of the
phase angle curve as mentioned earlier. For all binders, the car-
bonyl index increased evidently with the ageing aggravated as
the consequence of an increase in the content of the most polar
components that constituted higher molecular size. Compare with
the SBS-modified asphalt, the corresponding SBS/sulfur-modified
asphalt owned more higher carbonyl index after ageing, which im-
plied the modified binder was more susceptible to thermal oxida-
tive ageing. As for the sulfoxide index, there was only an increase
after TFOT ageing, indicating that the functional sulfoxide in-
creased during short-term ageing and decomposed moderately un-
der the severe ageing condition of long-term ageing (PAV). The
decomposition of sulfoxides (at high temperature) formed through
the oxidation for asphalt has been verified in previous work [28]
and using the sulfoxide as an ageing index always may lead to a
confused conclusion.
4. Conclusion
In this work, the similar conclusions about the effects of ther-
mal oxidative ageing on the properties and the structures of the
SBS- and the SBS/sulfur-modified asphalts were obtained by apply-
ing thermal analysis and dynamic viscosity test. Before ageing, the
addition of sulfur to the SBS-modified asphalt resulted in the for-
mation of a chemically vulcanized SBS network structure in the
modified binder, the complex viscosity and the thermal stability
of modified binder were improved significantly. However, after
ageing, the SBS/sulfur-modified asphalt showed an obvious viscous
behaviour compare with the SBS-modified asphalt due to the more
severe breakdown of a vulcanized polymer substructure into smal-
ler copolymer structures, consequently the improved high-temper-
ature dynamic viscosity has lost and the thermal stability of the
vulcanized binder was influenced to a great extent with the ageing
136 F. Zhang et al. / Construction and Building Materials 25 (2011) 129–137

Fig. 4. FTIR spectra analysis of modified asphalts before and after ageing and base asphalt: (a) Base asphalt (b) SBS1301-modified asphalt. (c) SBS1301/sulfur-modified
asphalt. (d) SBS4303-modified asphalt. (e) SBS4303/sulfur-modified asphalt.

aggravated. In FTIR analysis, the ageing degree of modified binder
was monitored by the changes of the carbonyl and ethylene in-
dexes which indicated the functional characteristics of modified
binder before and after ageing. Before ageing, the addition of sulfur
declined the ethylene index of the SBS-modified asphalt as the re-
sult of the chemically crosslinking reaction occurred among poly-
butadiene molecules. After ageing, the decline in the ethylene
index showed the degradation of polymer and the increase in the
carbonyl index indicated an increase in polar asphalt components
that constituted higher molecular size and these changes became
more obvious with the ageing aggravated. Compare with the
SBS-modified asphalt, the more higher carbonyl index of the SBS/
 F. Zhang et al. / Construction and Building Materials 25 (2011) 129–137 137

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