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In-field aging process of high content SBS modified asphalt in porous pavement
Raqiqa tur Rasool, Yao Hongru, Adeel Hassan, Shifeng Wang, Haiyan Zhang
PII: S0141-3910(18)30245-3
DOI: 10.1016/j.polymdegradstab.2018.07.023
Reference: PDST 8607
Please cite this article as: Rasool Rt, Hongru Y, Hassan A, Wang S, Zhang H, In-field aging process of
high content SBS modified asphalt in porous pavement, Polymer Degradation and Stability (2018), doi:
10.1016/j.polymdegradstab.2018.07.023.
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pavement
Raqiqa tur Rasool1 , Yao Hongru2, Adeel Hassan1, Shifeng Wang1*, Haiyan Zhang3
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Insulation and Thermo Aging, Shanghai Jiao Tong University, Shanghai, 200240,
PR China.
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2. Shanghai Road & Bridge Group Co. Ltd., Shanghai, 200433, PR China
3. Research Institute of Highway, Beijing, 100088, PR China
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* Corresponding author. Tel.: 86-21-54742671; fax: 86-21-54741297
E-mail address: shfwang@sjtu.edu.cn
ABSTRACT
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Highly modified asphalt (>6.0 wt% styrene butadiene styrene copolymer, SBS) has
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been extensively used for extending the durability of porous asphalt (PA) pavement.
In depth knowledge of the in-field aging of different PA layers is needed because the
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natural aging of PA possessing around 20% voids content severely affects its
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properties. The field core samples were taken from sections of the Shanghai Highway
which had aged 6 years and 9 years outdoors. The recovered modified binders from
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different layers (top, middle and bottom) of the PA were evaluated by chemical and
rheological characterization. After undergoing outdoors aging, chemical
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characterization showed that the carbonyl and sulfoxide content of the modified
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binders had increased for the top layers. The intensities of peaks for bottom layers
were lower, demonstrating that the top part of the PA was more exposure to real
weather aging. Aging in the degradation of SBS, evaporation of lighter components,
oxidation and condensation of the asphalt produces variations in the rheological
properties of the recovered binders. Rheological characterization revealed that the
highly modified binders continue to perform well even after 6 years and 9 years of
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outdoor aging.
1. Introduction
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The higher demands for noise reduction and more stringent safety requirements
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have been the substantial driving forces for long-lasting bituminous substances in the
porous asphalt (PA) pavements; which often contains a high amount of interlocked air
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voids (>20%) [1]. The performance of the PA surfaces is superior to that of dense
graded asphalt surfaces for reducing the noise produced by road-tire contact and the
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amount of spray and splash in wet weather. Normally, when a PA mixture is
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employed, noise is reduced by approximately 3 dB(A) compared with conventional
dense graded asphalt [2]. PA is permeable and the amount of surface water is reduced
under moist conditions, resulting in improved traffic safety and enhanced skid
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resistance at higher speed [3]. However, the open graded surfaces of the PA roads
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becomes crucial and the rate of aging in PA is higher than that of conventional asphalt
mixtures. Aging in asphalt binders is a natural phenomenon which results in early
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the cooling process [7]. Physical aging processes causes an increase in the asphalt’s
viscosity deprived of chemical alteration of components. The rate of aging is
influenced by ultraviolet (UV) radiation, weather, temperature and oxygen. The last
factor is affected by the physical characteristics of the material used: layer thickness,
asphalt type, aggregates and voids content. Therefore, the durability of the asphalt is
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closely related to the asphalt’s ability to resist physical hardening or oxidation
reactions.
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The most important cause of extreme binder aging can be attributed to greater
permeability, excessive void contents and a somewhat thin coating of binder
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(expected mastic thickness of 0.45 mm) of the aggregate [8, 9]. The influence of
aging in the PA mixtures can be detected over the whole thickness of the asphalt layer.
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Usually the damage appears under repeated traffic loading and complex weather
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environments which lead to ravelling, inelastic cracking, pitting or a combination of
these factors [9]. This is mainly because of the exposure of the road surface to oxygen,
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UV radiations which changes the binder’s properties [10]. Excessive void contents
facilitate the binder’s oxidative aging deeper into the asphalt pavement.
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To reduce such failures and maintain the internal porous structure, polymer
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modified binders are frequently used in the PA. Compared with the base binders, the
polymer modified binders possess a higher viscosity and softening point which
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improve aging resistance properties. They are considered to increase the lifespan of
the PA by improving adhesion and cohesion in the blends and by increasing the
binder film thickness without causing the material segregation. The most commonly
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used polymer modifiers are rubber from scrap tires, styrene butadiene styrene (SBS)
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and ethylene vinyl acetate (EVA) [11]. To increase the adhesive and cohesive
properties highly modified asphalt (>6.0 wt% SBS) is often used. Chen et al. [12]
studied the special effects of different binders on the engineering properties and
overall performance of PA mixtures and came to the conclusion that highly modified
polymer binder diminishes ravelling and rutting of PA as compared with conventional
asphalt binder. Hagos et al. [13] showed the advantages of using the polymer
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modified binder in PA, as it is expected to coat the aggregates with relatively thick
binder films and therefore reduce susceptibility to aging. The changes in the
rheological properties of modified binder due to aging are a result of a combination of
asphalt oxidation as well as polymer degradation, which differs with the type of
asphalt and polymer in addition to polymer content. Punith et al. [14] described that, it
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is easier to get a thicken binder film by the use of polymer modified asphalt, which
improves the cracking resistance, cohesion, friction and durability of the PA mixtures.
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In China, investigation on the PA pavements began in the 1980s. Early tests,
which were originally conducted on small scale, were not successful. At the beginning
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of 21st century, when high-viscosity modified asphalt or highly modified asphalt was
adopted as binder for PA, the anti-raveling property and high temperature
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performance of the PA were improved considerably. Consequently, research related to
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the PA was brought forward following the rapid growth of urban transportation and
these types of pavements then started to applied in highways in China [15]. Numerous
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researchers have evaluated the influences of aging on the properties of binders as their
properties can be simply accessed using several conventional test methods, via the use
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other techniques [16-18]. However, studies on the PA binders are rather limited;
especially with regards to long term in-field aging behavior and the mechanism of
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on core samples taken from the field sections of in-service PA pavements, which had
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aged by 6 years and 9 years outdoors; a sample that had aged 6 years indoors was
selected as a control. To attain an insightful overview of the aging characteristics of
the PA, the present research program has been developed to monitor a number of
parameters that are related to aging. On the one hand, chemical tests were performed
on the recovered binders to identify the compositional changes over time; while on
the other hand, tests were performed to investigate the rheological and thermal
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properties of the materials in order to determine the driving mechanism behind aging,
as well as to explore the possible relationship between them. A morphological study
was also attempted by using optical polarizing microscopy (OPM) and scanning
electron microscope (SEM) to examine the impact of the physico-chemical interfaces
between asphalt, SBS and filler over the course of the real aging process.
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2. Experimental
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2.1.Materials and preparation
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A standard test procedure was adopted for collecting samples by using a coring
method. The core sample diameter was 101.6±0.2 mm with a thickness of 250 mm
comprising 20 % voids content. Base asphalts were all from Shell Bitumen, and the
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penetration grade was 70#. The modified asphalt binders with SBS (S/B=30/70,
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molecular weight 120000g/mol, LG501) were used in the PA mixture which were
prepared by dry process. The pre-swelled SBS copolymer was added into hot
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aggregates and further mixed with asphalts at 180 °C, and mixed for 50 seconds to get
hot mix asphalt. 7.0 wt % SBS in the asphalt as calculated and metered.
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pavement that took place in the field, samples were taken from sections of the
Shanghai Zhangheng Highway which had aged by 6 years and 9 years. One section
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that had aged indoors for 6 years was taken for comparison with those samples that
had aged outdoors. All of the samples used the same type of SBS and asphalt.
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All the field core samples were cut horizontally into three layers. A smooth
finishing cut was obtained with the rock cutting machine (XGDQ-1/4P, Xingjian
electromechanical equipment company Jiangyan, Jiangsu) using a wet process. The
machine functions via the use of an enclosed fan ventilated motor with a geared head
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drive. The speed of the cutting wheel was estimated to be approximately 2200 rpm. A
water supply pump is used to cool the samples during the cutting process. Samples
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were cut with a thickness of 1.2±0.2 cm at different levels (top, middle and bottom
layers) as shown in Table 1.
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Table 1. Different layers of PA field cores
Service Top layers Middle layers Bottom layers
Aging
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Time (T) (M) (B)
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6 years
Indoor
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6 years
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Outdoor
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9 years
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2.3.Binder extraction
Firstly, the aged samples were cleaned with water to remove any dirt. The binders
were extracted separately from the top, middle and bottom sections of the core
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samples. The top section of the PA was considered to be the most important, because
of the prominent aging present at the surface of the pavement. A standard test method
related to EN 12697-3 was followed for recovery of the binders [19]. Toluene
(C6H5-CH3) solvent was used for extraction of the binders from the mixtures and the
solvent finally removed by rotary evaporator to evaporation. The samples of different
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layers were named as following: 6-IT, 6-IM, 6-IB (indoor aging), 6-OT, 6-OM, 6-OB
(outdoor aging) and 9-OT, 9-OM, 9-OB (outdoor aging), respectively.
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2.4.Characterization techniques
The following characterization techniques were used on the recovered binders.
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2.4.1. Structural characterization by FTIR analysis
Fourier transform infrared spectroscopy (FTIR) is a frequently employed
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technique to detect the chemical functional groups present in polymer chains. One can
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infer the functional groups in the sample from the relative strength of the peaks. FTIR
(Thermo Nicolet Model Nexus spectrophotometer, USA) was used to take spectra of
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all samples in transmission mode. The wavenumber range was from 4000 cm-1 to 600
cm-1. To assess the degree of aging of the asphalt binders, the transmission spectra
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of the variation of molecular weight distribution of the modified asphalt over the
course of the aging process [20]. It is a chromatographic technique which not only
analyzes the separation of constituent parts of the binders based on their molecular
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sample was 2.0 mg/ml, and a total 100 µl of sample was inserted into the columns.
2.4.3. Dynamic rheological measurements
The aging properties of the asphalt binders can be described by an increase in
their viscosity and stiffness because of asphalt oxidation and decrease in these
properties by the degradation of polymer modifier. A dynamic shear rheometer (DSR)
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test can be performed to check the variations in mechanical behavior. In this test
method, a sinusoidal loading was applied at a fixed frequency and the deformation
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was measured under loading [21]. Asphalt is a viscoelastic material, so there is a time
delay between loading and deformation; this is termed as phase change. Therefore the
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results from this test were analyzed by G*/sinδ factor, which collectively give an
imprint of the viscoelastic behavior throughout the aging process.
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A DSR rotary rheometer (Gemini 200 HR, UK) aligned in a parallel plate was
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utilized to assess the viscoelastic properties of the recovered binders. Temperature
sweep tests were performed on all samples in a continual strain fluctuation mode at a
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to be 1 mm.
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gravimetric analyzer.
2.4.5. Morphological analysis by optical polarizing microscope (OPM)
An optical polarizing microscope (OPM, Leica, Germany) was utilized to
perceive the morphological changes of recovered binders under a magnification of
100 times. A small droplet of sample was placed on a glass slide and covered by
cover slips to make a thin film. The morphology images of all samples could be
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The specimens of the samples were cryogenically split in liquid nitrogen to assure
a sharp delicate fracture, and were effectively coated with a very thin gold film prior
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to SEM observation [22]. A low voltage of 5 kV was used at a working space of
approximately 8-9 mm from the final lens. The dimensions of the observed surface
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were directly read from the SEM image.
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3. Results and Discussion
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The structural characterization, rheology, thermal analysis and morphology of the
recovered binders of the PA and the effect of long term aging on these properties are
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The long term outdoor aging of asphalt binders is due to the effects of sunlight, air
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exposure, temperature, water and loading. A combination of all these dynamic factors
influences the structure on pavement. FTIR was used for the evaluation of structural
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reactions, creating carbonyl (C=O centered in 1700 cm-1) and sulfoxide (S=O
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centered in 1030 cm-1) functional groups. These groups modify the asphalt
composition (increase the molecular size, aromaticity and asphalt polarity) and the
asphalt binders become more brittle [23, 24]. Carbonyl absorption peaks are
considered to be an important indicator for measuring the degree of asphalt aging and
a higher absorption represents deeper aging. Due to the crude oil refinery process,
sulfoxide is produced more rapidly during weathering than carbonyl groups [23]. The
assignations of all absorption peaks are listed in Table 2.
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1600-1615 ν C=C aromatic
1460 δ C-H of aliphatic index -(CH2)n-
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840, 1450 ν CaCO3 ( CO3 )
1370 δ C-H of CH3
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1030 ν S=O (sulfoxide)
700-721 δ C-H (aromatic)
966
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δ C-H (butadiene C-H of SBS)
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740, 695 δ C-H (mono substituted styrene block)
sketch, the first step follows the formation of peroxy intermediate which can oxidize
sulfur to form sulfoxide and alcohol fragments. Beyond this, the intermediate may
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form carbonyl by one of several paths. Alcohols fragments are hard to detect and
might represent some portion of the absent oxygen [26].
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absorption peaks was measured via integration. The sulfoxide index (SI) and carbonyl
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index (CI) were used to illustrate the comparative content of sulfoxide and carbonyl
groups, which can be calculated by the following equation:
SI = (1)
CI = (2)
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Where, is the area of the sulfoxide absorption peak, is the area of the
carbonyl absorption peak, and is the reference absorption peak area of aliphatic
C-H stretching. The results of both sulfoxide and carbonyl indices are recorded in
Table 3.
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Fig. 2. Proposed pathway for carbonyl and sulfoxide formation during oxidative aging
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The FTIR spectra of recovered modified binders are display in Fig. 3. The
distinction of absorption peaks driven by aging generally appeared in the range of
650–1750 cm–1, and the strength of peaks of specific functional groups (sulfoxide,
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carbonyl and hydroxyl etc.) is altered with weather aging. The presence of a typical
peak at 1650 cm-1 suggests that the oxidation reactions take place during the aging
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process. The existences of these peaks arise from the scissions of molecules that are
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prominent with outdoor aging period, which indicated that the variant trend for
modified binders was similar with indoor aging period. This creates an excessive
number of fragments and a short-range rise in the carbonyl content, increasing the
polarity and reactivity of the asphalt which increases the CI. This may be well
explained as follows: during the aging process, the oxidation, crosslinking reactions
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and dehydrogenation occur concurrently, which causes the formation of carbonyl
groups [27]. The severe oxidation reaction leads to the generation of more carbonyl
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groups which remarkably increase the CI during the outdoor aging process.
Furthermore, the increase in the SI suggests the reaction of sulfur with oxygen to form
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sulfoxide. The characteristic peak centered around 966 cm-1 indicates the C-H
stretching of butadiene in SBS. The peaks placed around 1420 cm-1 and 875 cm-1 can
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be attributed to CO3 group vibrations indicating the presence of some lime in all the
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recovered samples. The weak and broad peaks in the wavelength region of 3250-3435
cm-1 are due to O-H stretching vibrations in the asphalt molecules.
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As shown in Fig 3. (a, b, c) and the calculated indices of C=O and S=O in Table 3,
it can be seen that the modified binders in the top layers aged more than those in the
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middle layers. The recovered samples from the top part of the outdoor samples have
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more intense peaks than the indoor samples. Compared with indoor aging, the
sulfoxide and carbonyl absorption peaks of PA are more prominent after 6 years of
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outdoor aging as shown in Fig. 3(a, b). Meanwhile, from Fig. 3(c) the growing
number of sulfoxide and carbonyl groups tends to increase as the aging time is
prolonged to 9 years; however the trend for all these samples is very similar. On the
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one hand, during the aging process of modified binders, there is an increase in the
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viscosity of modified binders; on the other hand, the exposure of aging causes a
breakdown of some SBS bonds which leads to the degradation of SBS. The properties
of the modified binders are reliant on these two concurrent aging processes.
The lower part (middle and bottom) of all samples possess similar peaks at the
S=O and C=O bands compared with the top part of the samples, but the intensities of
peaks are lower, demonstrating that the top part of the PA is more expose to real
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weather aging. Moreover, CI stability is not observed but the study reveals that
oxidation still occurs in the aging process. These results can be further explained and
verified by GPC characterization.
(a) (b)
Top layer C=O Top layer
-CH=CH- C=O
-CH=CH-
Transmittance
Middle layer Middle layer
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Transmittance
Bottom layer
Bottom layer
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S=O S=O
6-IT
6-IM 6-OT
CaCO3 ν (C-H)
6-IB νas(C-H) 6-OM as CaCO3
6-OB
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4000 3500 3000 2500 2000 1500 1000 4000 3500 3000 2500 2000 1500 1000
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(c)
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Top layer C=O
-CH=CH-
Transmittance
Middle layer
M
Bottom layer
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9-OT S=O
9-OM ν (C-H)
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as
9-OB CaCO3
4000 3500 3000 2500 2000 1500 1000
-1
Wavenumber (cm )
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Fig. 3. FTIR spectra of the recovered binders from different layers of the PA; (a) after
6 years of indoor aging, (b) after 6 years of outdoor aging, (c) after 9 years of outdoor
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aging.
AC
Aging Samples SI CI
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6-OT 5.122 0.977 32.361 0.030 0.158
6 years (Outdoor) 6-OM 2.019 0.424 28.682 0.014 0.070
6-OB 1.216 0.394 28.711 0.013 0.042
9-OT 5.688 1.221 34.786 0.035 0.163
9 years (Outdoor) 9-OM 2.887 0.869 40.646 0.021 0.071
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9-OB 2.049 0.712 36.929 0.019 0.009
The integral range of S=O was ( 1025 cm-1, 1033 cm-1),the integral range of C=O was (1650 cm-1, 1745
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cm-1); the integral range Aref was (2845 cm-1, 2850 cm-1).
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GPC technique is commonly used to assess the aging mechanism of asphalt.
Researchers categorize the molecular weight distribution of asphalt into three groups
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of the same retention time. The molecules present in the mixture are observed on the
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GPC column according to their molecular size. The first 1/3 of the retention time
covers large molecular weight components, the second 1/3 covers components with
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moderate molecular weights and the last 1/3 part covers small molecular weight
components [28]. The distribution is formed according to the calibration data of the
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standard solutions.
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weight (lgM) on the x-axis. It can be seen from Fig. 4 that, the GPC profile of all
samples exhibit three distinct peaks. According to the principles of GPC, the
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components of the sample are eluted in order of increasing molecular weight. The first
peak represents small molecular weight substances (SMW) in the asphalt mixture; the
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second peak presents medium size molecular weight substance (MMW), which
corresponds to the molecular weight distribution of asphalt, while the third peak
shows molecular weight substances (LMW) that are large in size, which corresponds
to the molecular weight distribution of the SBS polymer. It is clear that the SBS
polymer experiences considerable degradation during aging throughout all the layers.
Exposure to high temperature in the presence of oxygen may also cause cross-linking
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reactions in the SBS polymer. However, due to the presence of free radicals and
diluents in asphalt composition, the net result is degradation (scission) of the SBS
polymer, as confirmed in the GPC profiles. Fig. 4 also indicates that, the content of
the large molecules of asphalt increases and their molecular weight shifts towards
higher differential distribution values because of oxidation reactions. These changes
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in molecular weight are a result of the indoor aging and outdoor aging times.
It can be deduced on the basis of GPC data that there is a clear difference in aging
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behavior of the asphalt binder components among the top, middle and the bottom
layers of the mixture. Both the middle and bottom layers aged more slowly than the
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top layers of the PA samples. As seen in the Fig. 4 (b) and (c), the GPC results reveal
a significant reduction of SBS following an increase in aging time for the top layers of
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the core field samples.
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The changes in the molecular weights of the modified binders were studied to
gain a deeper understanding of the aging mechanism. In general, the number average
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molecular weight (Mn) specifies the small and normal molecular weight fractions
while the weight average molecular weight (Mw) specifies the quantity of larger
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molecules [29]. The formation of higher molecular weight fragments influences the
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Mw value more than that of the Mn; this prompts a rise in the Mw/Mn ratio [30]. The
detailed values of the Mn, Mw and dispersion are listed in Table 4. It can be seen
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clearly from these data that the Mn increases after long term outdoor aging, which
means that a number of condensations reactions along with evaporation of low
molecular weight components of the asphalt occurred during aging process. This
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the field aging doesn’t seem to change the polymer contents too much; the fragments
formed in degradation process are still act as low molecules which may decrease Mn
values after 9 years out door aging. Furthermore, the increase in Mw of the binders
shows that the small molecules in asphalt are converted into large molecules. This Mw
increases more rapidly for the top layer compared with the middle and bottom layer.
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(a) MMW
Differential Distribution
6-IT
6-IM
6-IB
SMW
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LMW
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2.5 3.0 3.5 4.0 4.5 5.0 5.5
lgM
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(b) MMW
6-OT
Differential Distribution
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6-OM
6-OB
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SMW
M
LMW
D
lgM
(c) MMW
EP Differential Distribution
9-OT
C
9-OM
SMW 9-OB
AC
LMW
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6-IB 642 2743 4.27
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6-OM 6 years 707 3006 4.25
(Outdoor)
6-OB 703 2973 4.23
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9-OT 640 3676 5.74
9-OM 9 years 634 3304 5.21
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(Outdoor)
9-OB 616 3145 5.10
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3.3.In-field aging and rheological properties
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DSR was employed to describe the rheology of the recovered binders of the PA
after different in-service aging periods. The viscoelastic properties of the asphalt were
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altered considerably after real weather aging, which could prompt the progression of
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A temperature sweep test was applied to obtain results in the form of master curve
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rheograms. A key aspect is that the responses fluctuate from elastic to viscous in a
uniform manner as the strain rate decreases or the temperature increases. Inside the
linear viscoelastic section, the interrelation of strain and stress is linear, and is
inclined by time and temperature. Fig. 5 shows an obvious influence of temperature
on the rheological parameters. According to the Superpave asphalt specification,
G*/sinδ (rutting factor) at a frequency of 10 rad/s has been employed to estimate
long-term deformation. For instance, long-term deformation in asphalt pavement can
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be controlled by the loading time and viscosity of the asphalt binders. The viscosity in
the stable state is a principal indicator of permanent deformation. In general, a higher
G*/sinδ ratio signifies improved rutting resistance of the asphalt binders. From the Fig.
5, it can be seen that following an increase in temperature, the G*/sinδ value declines
for all of the samples after outdoor aging. The reason behind this is the presence of
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allylic hydrogen and C=C groups in SBS, which are more susceptible to in-service
aging. This fact is already clarified by FTIR analysis and GPC studies. In addition to
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this, an increase in the G*/sinδ is seen for the top layer binders of all the samples and
is more prominent for the 6 years and 9 years outdoor aged samples. Prediction of the
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aging process in the bottom layers is simpler; the aging process correlates to aging
caused by heat and sunlight in summer during in-service use, which corresponds with
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an increase in G*. Hence, it can be concluded that aging causes the asphalt act in a
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more elastic way [31].
M
D
TE
C EP
AC
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(a)
5x103
6-IT
G∗/sinδ (kPa)
4x103 6-IM
6-IB
3x103
2x103
1x103
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0
50 60 70 80 90
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Temperature (°C)
(b)
2.0x10 4 6-OT
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6-OM
6-OB
G∗/sinδ (kPa)
4
1.5x10
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1.0x104 AN
5.0x103
0.0
50 60 70 80 90
M
Temperature (°C)
5x104 (c)
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9-OT
4x104 9-OM
G∗/sinδ (kPa)
TE
9-OB
3x104
2x104
EP
1x104
0
C
50 60 70 80 90
Temperature (°C)
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Fig. 5. Changes of G*/sinδ (rutting factor) of the recovered binders from different
layers of the PA cores; (a) after 6 years of indoor aging, (b) after 6 years of outdoor
aging and (c) after 9 years of outdoor aging.
3.4.Thermal analysis
The aging of modified binders leads to molecular degradation or the formation of
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transitional molecules such as alcohols and ketones from small molecular weight
fractions. These structural changes can be perceived by the thermal analysis which
distress their thermal stability [32]. Thermo gravimetric analysis (TGA) is a technique
used to evaluate weight changes as a function of temperature. Differential thermo
gravimetric analysis (DTG) specifies an obvious point of weight loss [33]. Generally,
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it is employed to describe various characteristics of polymer materials, such as
temperatures of degradation, moisture content absorbed by the materials, and the level
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of organic and inorganic fragments in the materials.
Thermal analysis of the modified binders from indoor and outdoor samples is
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shown in Fig. 6. The results demonstrate three different stages; (1st), (2nd), and (3rd)
due to thermal decompositions of the asphalt binder. The 1st stage is characterized by
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the continuous weight loss of volatile components from the asphalt binders, such as
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polar aromatics compounds and saturates, which terminates at 380 ºC. The 2nd stage
arises in the range of 378 ºC to 465 ºC, during which the volatilization and
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decomposition of the resins including SBS, and a few asphaltenes and aromatics
become highly prominent. The 3rd stage is completed at a high temperature of 750 ºC,
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where the weight loss is faster following the decomposition of CaCO3. Along these
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lines, the decomposition of larger molecules goes to smaller molecules occur in the
gaseous phase. The remaining residue is generated by free radical condensation
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shown in the TGA curves of Fig. 6 (a). At about temperature of 465 °C, the binders
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exhibited a mass loss of 40%. Regarding to the DTG curves, two exothermic peaks
were found specifying that an adverse weather conditions can speed up the SBS
decomposition along with the burning of organic fragments. Fig. 6 (b) and (c) show
the results of the thermal analysis of the recovered binders after 6 years and 9 years
outdoor aging. The light components in all outdoor aged samples are more susceptible
to dehydration and oxidation than indoor aged samples. This result is expected
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higher Tonset indicating the decomposition of high molecular weight or more polar
content which were formed because of oxidation reactions during aging. Also
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comprehended from Table 5, the initial degradation temperature decreases in the start,
and rate of SBS modified binder decomposition increases respectively, the maximum
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decomposition temperature (Tmax) and rate of decomposition both decrease as the
aging period increases. This clarifies that the adverse environmental factors
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accelerates the SBS decomposition into lower molecular weight oxidative products.
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Table 5. Characteristic parameters for recovered modified binders from TG and DTG
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plots
Samples Tonset (ºC) Tmax (ºC) R onset (%/min) Rmax (%/min)
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6-OM
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70
0.2
60
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40
30 0.0
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
Temperature (°C) Temperature (°C)
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(b) 1st stage 3rd stage 0.4 (b')
100
2nd
Exo
stage
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90
0.3 Endo
80
Weight (%)
70 0.2
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60
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
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0.5
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90
Endo
80 0.4
Weight (%)
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70
0.3
60
0.2
50 9-OT 9-OT
0.1 9-OM
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40 9-OM
30 0.0
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
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Fig. 6. Thermal analysis curves (TGA/DTG) of the recovered binders from different
layers of the PA cores; (a, a’) after 6 years of indoor aging, (b, b’) after 6 years of
outdoor aging and (c, c’) after 9 years of outdoor aging
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distribution and filler interaction within the asphalt matrix. The compatibility between
SBS and asphalt is crucial for the properties of the modified asphalt [34]. Optical
polarizing microscopy (OPM) was used to analyze the morphology of the recovered
binders from the PA mixture after 6 years of indoor aging, and 6 and 9 years of
outdoor aging. It allows characterizing the nature (continuous and discontinuous or
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dispersed phase) of the polymer in the asphalt matrix [35].
The effect of indoor and outdoor aging on the surface morphology is shown in Fig.
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7. A continuous asphalt phase with masses consisting of the dispersed phase of SBS
particles can be seen in all the micrographs. The dispersed SBS particles appear as
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bright yellow spots which act as a discontinuous phase in the overall morphology,
while the gray rough spots are lime particles. Compared with Fig. 7(a), the top layer
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of the indoor aged sample shown in Fig. 7 (a’), and shows that an increase in the
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amount of SBS polymer particles dispersed in the asphalt is observed because of
swelling with maltene that is fused from the asphalt. Their dimensions decrease after
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6 years of outdoor aging, indicating the degradation of SBS and enriching the
compatibility between the asphalt and SBS. As shown in Fig. 7 (a’’), it can be seen
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that the sizes of the particles decrease further because of an increase in the brittleness
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of the binders and the frameworks become uncertain after 9 years of outdoor aging.
Similarly, the influence of aging on the morphology of the middle and bottom
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layers is shown in Fig. 7 (b, b’, b”) and in Fig. 7 (c, c’, c”) for all the samples. The
number of SBS polymer particles increases and the size of the particles evidently rises,
which shows that aging has little impact on these layers compared to the top layers
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which are more exposed to weathering; this also suggests a high degree of
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the PA; [top layer (a), middle layer (b) and bottom layer (c)] after 6 years of indoor
aging, [top layer (a’), middle layer (b’) and bottom layer (c’)] after 6 years of outdoor
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aging and [top layer (a”), middle layer (b”) and bottom layer (c”)] after 9 years of
outdoor aging.
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SEM was used in this study to analyze the dispersion of SBS in the top layers of
PA mixture, with the aim of better exploring the microstructural changes following
indoor and outdoor aging. For this evaluation, their surface textures were analyzed in
order to examine the reactivity and distribution of SBS polymer particles within the
asphalt matrix.
The chemical variation exists among asphalt and SBS because of the differences
in polarity, molecular weight and structure. The mutual interface of asphalt and SBS
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gives morphology and is influenced by content and nature of polymer and asphalt
composition. From Fig. 8 (a) to Fig. 8 (b) and Fig. 8 (c), it can be seen that the
fractured surface changed from tough (more rough) to brittle (more smooth),
illustrates their durable compatibility and reactivity within the modified asphalt
matrix.
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Generally speaking, the dispersed SBS phase improves the engineering properties
of asphalt at both high and low service temperatures. However, the fracture surface
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of modified binders gradually become smooth after aging, which indicates the binder
become brittle at lower temperature after 6 years and 9 years outdoor aging.
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Fig. 8. SEM images of the recovered binders of the PA, (a) after 6 years of indoor
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aging, (b) after 6 years of outdoor aging and (c) after 9 years of outdoor aging.
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(Magnification 1000x)
4. Conclusion
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while the others were field cores that had aged for 6 years and 9 years of outdoors.
Therefore, the in-field aging mechanism of PA binders with long service life can be
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investigated in detail. The Following conclusions can be drawn from the present
research.
1) All layers of the PA binders have similar peaks corresponding to C=O and S=O
bands but the peak intensities became weaker due to lesser exposure to natural
weather aging.
2) GPC results showed that possible evaporation of lower molecular weight
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and therefore the rheological properties of modified binders are a mutual result of
SBS degradation and asphalt oxidation.
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4) Degradation of SBS mostly takes place during production (mixing) and at the
early stages of pavement service. The rheological assessment showed that the
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high temperature properties of highly modified binders will continue to perform
well even after outdoor aging.
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5) A thermal analysis study specified that, higher Tonset indicating the decomposition
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of high molecular weight or more polar content which were formed because of
oxidation reactions during natural aging.
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6) The results obtained from the morphology study showed that the highly modified
asphalt binders experienced considerable morphological changes following both
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indoor and outdoor aging, thus showing the effects of weather, temperature and
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UV radiation throughout the aging process. The aging results in the brittleness of
the SBS modified binder.
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7) During the aging process, the degradation of the SBS copolymer does not suggest
a decline in the positive effects of the modified asphalt. In fact, the degradation
process due to the oxidative aging of asphalt components may result in the
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over the service time of the PA pavement. It is believed that for a durable porous
asphalt pavement, appropriate base asphalt is important for ensuring the stability
of the modified binders.
Acknowledgements
The authors are grateful for the research foundation provided by the Jiangsu Science
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HIGHLIGHTS
The chemical structure evolution of highly modified asphalts reflected their evolution of
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Top layer (1.2 cm) of porous asphalt showed obvious aging in SBS degradation and
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asphalt oxidation than other layers.
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