Polymer Degradation and Stability 147 (2018) 64–75

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Polymer Degradation and Stability

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

Thermal degradation of SBS in bitumen during storage: Influence of T

temperature, SBS concentration, polymer type and base bitumen
Sumit K. Singh, Yogesh Kumar, Sham S. Ravindranath∗
Department of Polymer and Process Engineering, Indian Institute of Technology Roorkee, Uttarakhand, India

A R T I C L E I N F O A B S T R A C T

Keywords: One of the major issues that manufacturers and suppliers of styrene-butadiene-styrene (SBS) modified bitumen
SBS face is erosion in its properties during storage and transportation. If appropriate controls are not in place,
Styrene butadiene styrene properties of SBS modified bitumen can erode significantly during storage and transportation, resulting in
PMB substandard quality of roads when constructed using such products. We report a comprehensive study of the
Polymer modified bitumen
effect of storage temperature, SBS concentration, polymer type and base bitumen on the properties of polymer
SP
Softening point
modified bitumen during storage at elevated temperatures in sealed aluminium tubes. Our results show that
TD storage temperature, SBS concentration and polymer type play a major role in the observed property erosion,
Thermal degradation while type of base bitumen has a lesser effect. The samples were stored in sealed aluminium tubes at tem-
PG peratures of 150 °C, 180 °C and 210 °C for up to 21 days. At 150 °C, the properties of PMB's remained intact even
Performance grading after storing for 21 days. But, significant erosion in conventional and rheological properties of SBS modified
MSCR bitumen takes place within the first 3 days of storage at temperatures ≥ 180 °C. At 210 °C, the PMB properties
Multi stress creep recovery degrade to the base bitumen values within 1 day. Gel permeation chromatography and rheological results clearly
R
show degradation of SBS molecules. The property loss is most significant when the SBS concentration is between
Rheology
3% and 6%, in the steep middle region of the S-curve (softening point vs. polymer concentration). 3% SBS
content is close to the network formation threshold of the polymer molecules in bitumen. Conventional polymer
grades such as D1101, D1184, LG411 and Elvaloy 4170 showed maximum erosion in properties, while D1192
grade (with higher vinyl content > 35%) showed significantly lower drop. The newer polymer grade in-
troduced by Kraton, MD0243, remained completely stable at 180 °C even after 21 days. Among PMBs with
different base bitumens, noticeable differences were observed only when the SBS concentration was in the steep
middle region of the S-curve (3–6%). We have discussed all the results in the background of the S-curve, there by
highlighting the major role played by SBS concentration in property erosion during storage. Our results have
important implications for storage and handling guidelines for polymer modified bitumens.

1. Introduction
Polymer modified bitumens (PMBs) enhance pavement performance
over a wide temperature range [1–4]. Roads constructed with PMBs
have longer service life and lower maintenance requirements. Styr-
ene–butadiene–styrene (SBS) is one of the most commonly used poly-
mers for bitumen modification. The combination of styrene and buta-
diene molecule offer excellent stiffness and elastic recovery
characteristics over a wide temperature range. The interaction of SBS
with bitumen is mostly physical. The smaller aromatic fractions present
in bitumen diffuse into SBS molecules causing an increase in its volume
by about 3–5 times to its original volume. At sufficient concentration of
SBS, a 3D network is formed that significantly enhances the load
bearing capacity of the modified bitumen. Other polymers such as
styrene butadiene rubber (SBR), Elvaloy, ethylene vinyl acetate (EVA),
ethylene glycydyl acrylate (EGA) etc. are also used for bitumen mod-
ification [1–5]. But, SBS modified bitumen dominate the PMB market
because of its superior performance.
One of the drawbacks of SBS is its limited thermal and oxidative
stability [6–12]. Literature studies have concentrated on the thermal
stability of the SBS polymer in presence of excess air, mimicking the
conditions prevalent during road construction (studies in rolling thin
film oven, pressurized ageing vessel, thin films, open containers and
extraction of bitumen from asphalt) [13–20]. In presence of excess air,
the base bitumen hardens excessively and SBS molecules will degrade
faster. The changes in the properties of the modified bitumen and SBS
molecules after ageing can be monitored through FTIR spectroscopy,
gel permeation chromatography and rheology. In the thermal oxidative

∗
Corresponding author.
E-mail address: shamrfps@iitr.ac.in (S.S. Ravindranath).

https://doi.org/10.1016/j.polymdegradstab.2017.11.008
Received 12 July 2017; Received in revised form 24 October 2017; Accepted 12 November 2017
Available online 21 November 2017
0141-3910/ © 2017 Elsevier Ltd. All rights reserved.
S.K. Singh et al. Polymer Degradation and Stability 147 (2018) 64–75

aging process of SBS modified bitumen, C=C bond in SBS polymer is
fractured and C=O bond is generated due to large absorption of
oxygen. Other products such as phenols, carboxylic acids (O-H peak),
carboxylic compounds (C=O) and esters can also be generated
[13–20].
But after manufacturing, the SBS modified bitumens are first ex-
posed to elevated temperatures (120 °C to 200 °C) during storage and
transportation in closed metal containers with vents for exit of built-up
gases [21–26]. The temperature and duration of exposure to elevated
temperatures depends on the mode of storage/transportation, distance
between the PMB manufacturing plant and customer site, and road
construction scenarios. Exposure to elevated temperatures can result in
property erosion of the SBS modified bitumen. If proper quality control
measures are not taken, roads constructed using such PMB's may fail
prematurely.
Studies in closed metal containers, mimicking the storage and
transportation conditions, are few and are just limited to knowing the
effect of storage temperature on the properties of the SBS modified
bitumen [27–29]. There is a lack of clear understanding as to how
various parameters, such as storage temperature, SBS concentration,
polymer type and base bitumen, together influence the properties of
SBS modified bitumen during storage and transportation. A compre-
hensive study will act as or help in improving storage and transporta-
tion guidelines for commercial suppliers and manufacturers of SBS
modified bitumen.
Here, we report a comprehensive study of the effect of various
parameters on the properties of SBS modified bitumen during storage at
elevated temperatures in sealed aluminium tubes [30].
From this study, we can systematically address some of the com-
mercially relevant questions, such as
• How the properties of SBS modified bitumens are affected at dif-
ferent storage temperature?
• How oil heated vs. flame heated system affect product properties?
• By increasing SBS concentration, can we compensate for the loss in
properties?
• For the same storage conditions, can SBS degrade significantly in
one base bitumen, while in another it remain stable?
• How does the conventional grade of SBS polymer perform compared
newer grade and Elvaloy polymer?
• Will elastic recovery and performance grade be affected similar to
softening point?
2. Materials and methods
2.1. Polymers
Table 1 provides the basic information of the 6 polymers used for
bitumen modification. The 5 styrene-butadiene based block copolymers
(D1101, D1192, D1184, MD0243 and LG411) and 1 reactive elasto-
meric terpolymer (Elvaloy 4170) vary in their physical structure (linear
vs. branched) and chemical composition (15% vinyl content vs. 35%
vinyl content, triblock vs. diblock, styrene-butadiene vs. reactive ter-
polymer). Through these 6 polymers, we can understand how the
physical architecture and chemical composition of the polymers influ-
ences its thermal stability in bitumen during storage. Detailed proper-
ties of the polymers can be obtained from the product data sheet
available on the company's website and hence we avoid duplication
here. Kraton's D1101, having bound styrene of 30%–32% mass, is one
of the most commonly used linear SBS polymers for bitumen mod-
ification. The polymer was purchased from RishiChem distributors,
India. Comprehensive thermal and rheological studies have been car-
ried out on D1101 polymer modified bitumens.
2.2. Base bitumens
4 bitumen samples from different sources were used in the study.
The details of the source and basic properties of the 4 bitumens are
given in Table 2. The 4 bitumen samples belong to two different pe-
netration grades, 80–100 and 60–70 dmm. In penetration grading
method, bitumens are graded based on the hardness of the samples.
Harder the bitumen sample, lower will the penetration value and higher
will be its softening point. In our study, the 4 bitumen samples are
named A(80–100), B(80–100), A(60–70) and B(60–70). The spread in
bitumen samples (source and basic properties) though limited will help
us to know if base bitumen plays any significant role in the property
erosion of polymer modified bitumens during storage.
2.3. Preparation of polymer modified bitumens (PMB)
Base bitumen was first heated at 180 °C in a tin container and the
required amount of polymer was slowly added into the liquefied bi-
tumen. Homogeneous mixing of the polymer was done at 180 °C using
Silverson high shear mixer (Model: L4RT) at 4000 rpm for 120 min.
After mixing the polymer under high shear, the PMB was further
homogenized at 180 °C using an IKA-Werke low shear mixer (Model:
RW20) at 600 rpm for 120 min. To prevent phase separation of SBS
molecules from bitumen, the polymer was crosslinked by addition of
0.12% sulphur at the start of low shear mixing. The PMB's thus pre-
pared were stored inside an oven at 180 °C for 24 h, for stabilization.
2.4. Properties of polymer modified bitumens (PMBs)
We have examined 3 series of PMB samples: first where the D1101
SBS polymer concentration is varied (3%, 4.5% and 7%) in A(80–100)
bitumen, second where four different base bitumens are used at a fixed
D1101 concentration of 4.5 wt % and third where 6 different polymers
are used in A(80–100) bitumen. Thus, the effect of storage temperature,
SBS concentration, base bitumen and polymer type has been evaluated
in detail. In total, the thermal stability of 11 PMB samples has been
studied.
The basic properties of the first series of PMB samples where the
D1101 concentration is varied is given in Table 3. A(80–100) represent
the bitumen and the percent following bitumen naming represent the
D1101 concentration. In-depth study on the effect of storage tempera-
ture and polymer concentration was carried out on these 3 PMBs.
The properties of the second series of PMB samples where different
base bitumens are used is given in Table 4. The 4 PMB samples

Table 1
Source and properties of the 6 polymers used in the study.

Polymer Supplier Company Properties

D1101 RishiChem, India Kraton Linear SBS triblock copolymer, Styrene content: 30–32%, MFI < 1 g
D1192 Linear SBS triblock copolymer, Styrene content: 28.5–32.5%, MFI < 1 g, Vinyl content > 35%, Triblock
content > 90%, Mw: 138–162 kg/mol
D1184 Branched SBS triblock copolymer, Styrene content: 29–31%, MFI < 1 g
D0243 Linear SB diblock copolymer, Styrene content: 31–35%, MFI: 20 g, Vinyl content > 35%, Diblock content: 75%
LG411 Tiki Tar Industries, India LG Chemicals Branched SBS triblock copolymer, Styrene content: 29–31%, MFI < 1 g
Elvaloy 4170 Tiki Tar Industries, India DuPont Reactive Elastomeric Terpolymer, MFI = 8 g

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S.K. Singh et al. Polymer Degradation and Stability 147 (2018) 64–75

Table 2
Source and basic properties of the 4 base bitumens.

Bitumen Source Refinery Penetration @ 25 °C (dmm) Softening point (°C) PG temp. (°C) (G*/sinδ = 1 kPa)

A(80–100) Tiki Tar Industries Koyali, Indian Oil 92 48 62

B(80–100) Hincol Mahul, Hindustan Petroleum 98 46 63
A(60–70) Tiki Tar Industries Koyali, Indian Oil 66 52 65
B(60–70) Juno Bitumen Jey Oil, Iran 68 51 64

Table 3 2.6. Selection of storage temperature

Properties of the 3 PMBs with different concentration of D1101 SBS polymer in
A(80–100) bitumen.
PMB Base bitumen D1101 Softening Penetration
(wt %) point (°C) @ 25 °C
(dmm)
A(80–100)/ A(80–100) 3 61 75
3%
A(80–100)/ 4.5 84 60
4.5%
A(80–100)/ 7 98 45
7%
mentioned in Table 4 will help us to determine if base bitumen plays a
significant role or not.
The properties of the third series of PMB samples where different
polymers were used in A(80–100) bitumen is given in Table 5. The 6
PMB samples mentioned in Table 5 will help us to determine how
physical architecture and chemical composition of the polymers influ-
ences PMBs thermal stability during storage. The concentration of the
Elvaloy polymer was limited to 1.8 wt %, since at higher concentrations
the sample became gel-like.
2.5. Storage protocol
The goal of our study is to know the extent of property erosion, if
any, in styrene-butadiene and Elvaloy modified bitumen during storage
and transportation at elevated temperatures after manufacturing. For
this purpose, the storage protocol should mimic the storage and
transportation conditions prevalent commercially, wherein the mod-
ified bitumen is exposed to minimum amount of air. In this study, we
have utilized aluminium toothpaste tubes (35 mm diameter and
180 mm length), that are used to determine the phase stability of
polymer modified bitumens [30]. After preparation of the PMB, about
100 g of the sample was poured into the aluminium toothpaste tubes.
The open end of the tube was then sealed by first crimping it, thereby
minimizing the space inside, and then folding it onto itself. The sealed
tubes were placed vertically inside ovens set at the required tempera-
ture. After 1, 3, 7, 14 and 21 days of storage inside the ovens, one sealed
tube was removed and the properties of the PMB were determined.
Changes in the properties of the PMB would be due to exposure to
elevated temperatures in absence or limited presence of air, conditions
that are prevalent during commercial storage and transportation of
PMB's. It is important to note that the phase stability of the polymers in
bitumen was checked after 3, 7 and 21 days of storage by measuring the
properties of the sample at the top and bottom 1/3 part of the tube. In
our study, all the PMB's showed phase stability.
In practice, after manufacturing, the polymer modified bitumens are
PG temp. (°C)
exposed to a wide range of temperatures (120 °C–200 °C) during storage
(G*/ and transportation. The duration of exposure to elevated temperatures
sinδ = 1 kPa) depends on the type of storage/transportation containers (metal drums,
bitutainers, shipping containers etc.), heating system (oil vs. flame),
72
distance between the PMB manufacturing plant and customer site, and
81 road construction scenarios. Commercially, if the polymer modified
bitumens are to be stored for more than 1 week, then it is usually stored
105 at temperatures between 120 °C and 150 °C [23–26]. Reheating the
PMB becomes extremely difficult and time consuming process if it is
stored at very low temperatures. If the PMBs are to be used within 1
week, then it is usually stored at temperatures between 150 °C and
180 °C. During reheating process, especially with flame heating sys-
tems, the PMBs can be exposed to temperatures around 200 °C for short
periods of time. Taking commercial scenario into account, in our study,
the storage temperatures were selected to be 150 °C, 180 °C and 210 °C.
2.7. Test methods
The effect of storage on softening point (SP), elastic recovery (ER),
performance grading (PG) and rheological properties of the PMBs were
studied. The SP and ER properties of the PMBs are sensitive to state of
polymer molecules in bitumen. ER properties were measured by mul-
tiple stress creep and recovery (MSCR) tests using an Anton Paar dy-
namic shear rheometer (DSR). Penetration @ 25 °C, SP, PG grading and
ER were measured in accordance to ASTM D5, ASTM D36, ASTM
D6373 and ASTM D7405, respectively.
The molecular weight of the polymer was determined using gel
permeation chromatography (GPC). Waters equipment, operating at
40 °C column compartment temperature with a 515 series pump and
refractive index detector, was used. The flow rate of the solvent tetra-
hydrofuran (THF) was 0.75 ml/min. The sample was dissolved in THF
to a known concentration of 25 mg/ml and 100 μl of diluted sample was
injected.
Table 6 provides information about the tests, instruments utilized
and respective ASTM standard employed. Our aim was to determine ER
value of the PMBs at 10 °C below upper PG temperature. But, for the 7%
PMB sample, at 95 °C, the ER value was just 60% and hence experiment
was carried out at 85 °C that is 20 °C below its upper PG temperature.
The ER properties of PMBs with 3% and 4.5% polymer content were
measured at 60 °C and 70 °C, respectively. Frequency sweep measure-
ments were also carried out on some samples to characterize the state of
the polymer network after storage. Frequency sweep measurements
were carried out in the linear viscoelastic regime using 25 mm parallel
plate geometry. 1 mm gap was maintained during the measurements. In

Table 4
Properties of 4 PMBs with 4.5% D1101 in 4 different base bitumens.

PMB Base bitumen D1101 (wt %) Softening point (°C) Penetration @ 25 °C (dmm) PG temp. (°C) (G*/sinδ = 1 kPa)

A(80–100)/4.5% A(80–100) 4.5 84 60 81

B(80–100)/4.5% B(80–100) 81 55 77
A(60–70)/4.5% A(60–70) 85 46 80
B(60–70)/4.5% B(60–70) 86 44 82

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S.K. Singh et al. Polymer Degradation and Stability 147 (2018) 64–75

Table 5
Properties of 6 PMBs with different polymers in A(80–100) bitumen.

Polymer Base bitumen Polymer (wt %) Softening point (°C) Penetration @ 25 °C (dmm) PG temp. (°C) (G*/sinδ = 1 kPa)

D1101 A(80–100) 4.5 84 60 81

D1192 89 53 84
D1184 91 50 86
MD0243 79 55 78
LG411 87 48 82
Elvaloy 4170 1.8 64 55 74

Table 6
Tests, instruments and corresponding ASTM standards.

Test Instrument Standard

Penetration at 25 °C, (dmm) Aimil 512 ASTM D5

Softening Point, (°C) Aimil 561 ASTM D36
PG Grading Anton Paar - Physica ASTM D6373
MCR102
Multi Stress Creep Recovery Anton Paar - Physica ASTM D7405
(MSCR) MCR102
Gel Permeation Chromatography Waters 515 HPLC Pump –

order to identify the state of the polymer network at temperature near

its SP, frequency sweeps of PMBs with 3%, 4.5% and 7% polymer
content were measured at 60 °C, 80 °C and 100 °C, respectively.

3. Results and discussions

3.1. Effect of storage temperature Fig. 2. Softening point as a function of storage time at 180 °C for the 3 PMBs with 3%,
4.5% and 7% SBS content.

3.1.1. Softening point (SP)

The effect of storage temperature (150 °C, 180 °C and 210 °C) on the
softening point (SP) of the three PMBs with 3%, 4.5% and 7% D1101
polymer in A(80–100) bitumen is shown in Figs. 1–3, respectively. The
three PMBs have been labelled A(80–100)/3%, A(80–100)/4.5% and
A(80–100)/7%. The initial properties of the three PMBs are given in
Table 3.
It can be seen in Fig. 1 that at storage temperature of 150 °C, the SP
of the three PMBs remain stable during the first week of storage, fol-
lowed by just couple of degrees drop over a period of 21 days. The
result implies that the polymer network remains intact. Commercially,
if the PMB has to be stored for prolong period of time, most of the PMB
suppliers and governing bodies recommend storage temperatures below

Fig. 3. Softening point as a function of storage time at 210 °C for the 3 PMBs with 3%,
4.5% and 7% SBS content.

Fig. 1. Softening point as a function of storage time at 150 °C for the 3 PMBs with 3%,
4.5% and 7% SBS content.
160 °C, not only to prevent property erosion but also to reduce costs
associated with heating.
Increasing the storage temperature to 180 °C has a profound influ-
ence on the softening point (SP) of the three PMBs, as shown in Fig. 2.
The SP decreases by upto 5 °C within 3 days of storage and the drop
continues with increase in storage time. For A(80–100)/4.5%, SP drops
by nearly 5 °C and 13 °C within first 3 and 7 days of storage, respec-
tively. Given the fact that the PMB sample was stored in a sealed tube,
where exposure to air would have been negligible, the drop in SP is
surprising. 13 °C drop in SP within the first 7 days can lead to the
sample going out of specification, and construction of roads with such
PMBs can lead to premature failure. For A(80–100)/3% and

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S.K. Singh et al. Polymer Degradation and Stability 147 (2018) 64–75

A(80–100)/4.5% PMBs, the SP nearly reaches that of base bitumen

(48 °C) when stored for 21 days. In practice, it is unlikely and also not
recommended to store PMBs at 180 °C for such long periods of time (3
weeks), but our results indicate that steps needed to be taken to avoid
PMBs from getting exposed to 180 °C even for couple of days. The
erosion in the properties within the first 3 days of storage at 180 °C is
quite significant.
Storing the PMB at 210 °C has dramatic effect on its properties, as
shown in Fig. 3. Within 6 h of storage at 210 °C, up to 5 °C drop in SP is
observed. During coating of aggregates and heating using flame heaters,
the PMBs can be exposed to such high temperatures momentarily. The
SP of A(80–100)/3% and A(80–100)/4.5% PMBs almost reaches to that
of the base bitumen (48 °C) within 1 day of storage.

3.1.2. Gel permeation chromatography (GPC)

The strong influence of temperature on the properties of PMB's in
presence of excess air, such as ageing in open containers or in rolling
thin film oven (RTFO), has been widely reported in literature [13–20].
Gel permeation chromatography (GPC) studies have clearly shown
chain scission at such elevated temperatures [13,14,17]. In our study,
GPC studies were carried out on our PMB samples and the results are
shown in Fig. 4. It can be seen in Fig. 4 that at 180 °C, a clear decline in
the polymer peak is observed after 3 days of storage. As the time of
storage increases (7 days and 14 days), the polymer peak reduces
considerably. The GPC results clearly show that at storage temperatures
≥180 °C, chain scission of SBS molecules takes place even in absence of
air. In a sealed environment, it is likely that the bitumen molecules
causes the chain scission when it interacts with the C=C moiety present
in the butadiene segment. We show in subsequent section 3.4.2 that
with increase in vinyl content, the extent of erosion is significantly
reduced. The decrease in molecular weight of the polymer leads to a
weaker polymer network which in turn causes the drop in SP and
changes to the rheological properties. The effect of polymer degrada-
tion on the properties of the PMB will be more pronounced when the
polymer content falls in the middle of the S-curve. It is the region where
the SP increases drastically with increasing polymer content.
3.1.3. Frequency sweep
The GPC result is supported by rheological measurements. The re-
sults of the frequency sweep on A(80–100)/4.5% PMB sample stored at
180 °C is shown in Fig. 5. Frequency sweep was carried out at 80 °C in
Fig. 5. Complex viscosity (η*) at 80 °C vs. angular frequency (ω) for A(80–100)/4.5%
PMB stored at 180 °C. Inset shows phase angle (δ) vs. angular frequency (ω).
the linear viscoelastic regime using 25 mm parallel plate geometry. The
rheological measurements were made at 80 °C in order to identify the
state of the polymer network around the SP of the PMB. In Fig. 5,
complex viscosity (η*) is plotted against angular frequency (ω). It can
be seen that after 3 days of storage at 180 °C, the η* value decreases
considerably, especially at lower frequencies of measurement. At higher
frequencies the bitumen molecules dominate the rheological response
while the response of polymer molecules is more evident at lower fre-
quencies, due to their longer relaxation time. More insight into the
status of the network can be obtained when phase angle (δ) is plotted
against angular frequency, as shown in Fig. 5 as inset. As storage time at
180 °C increases, δ approaches 90° at lower frequencies, exhibiting
behaviour of non-modified bitumen. The significant drop in η* and
increase in δ at lower frequencies clearly shows loss in polymer net-
work, which caused the drop in SP. For the A(80–100)/3% PMB, the
decrease in the complex viscosity and phase angle due to storage at
180 °C is not as drastic, as shown in Fig. 6. This is mainly due to the fact
that addition of 3 wt % polymer does not significantly alter the rheo-
logical properties. For the A(80–100)/7% PMB, at storage temperature
of 180 °C, the complex viscosity at 0.1 rad/s decreases from nearly
900 Pa s to 300 Pa s after 21 days of storage as shown in Fig. 7. Thus
frequency sweep measurements prove to be a sensitive tool in detecting
the status of the polymer in the bitumen. The viscosity of the PMB in

Fig. 6. Complex viscosity (η*) at 60 °C vs. angular frequency (ω) for A(80–100)/3% PMB
Fig. 4. Gel permeation chromatography results of A(80–100)/4.5% PMB. stored at 180 °C. Inset shows phase angle (δ) vs. angular frequency (ω).

68
S.K. Singh et al.
Fig. 7. Complex viscosity (η*) at 100 °C vs. angular frequency (ω) for A(80–100)/7%
PMB stored at 180 °C. Inset shows phase angle (δ) vs. angular frequency (ω).
particular is significantly enhanced with increasing polymer content.
3.1.4. Temperature switch - 180 °C to 150 °C
An important question to be answered is; Will the polymers mole-
cules continue to degrade at 150 °C, after first being exposed to 180 °C?
Thus, in a second storage protocol, the A(80–100)/4.5% PMB was first
stored at 180 °C and then shifted to 150 °C. It can be seen from Fig. 8
that the erosion in SP diminished once the PMB sample was shifted to
150 °C. All the 4 samples that was stored first at 180 °C for 1 day, 3 day,
7 day and 14 day, respectively and then shifted to 150 °C showed si-
milar behaviour.
3.2. Effect of polymer concentration: S-curve
It can also be observed in Figs. 2 and 3 that the maximum drop in SP
takes places for the PMB with 4.5% D1101 content at both 180 °C and
210 °C. Why does A(80–100)/4.5% show significantly greater drop in
SP than A(80–100)/3% and A(80–100)/7%?. With increase in polymer
content, the initial SP of A(80–100)/4.5% is much higher than
A(80–100)/3% and hence the decrease in SP is higher as the SBS mo-
lecules degrade. But, why does A(80–100)/4.5% show greater erosion
in properties than A(80–100)/7%?. The answer to the question can be
obtained with the understanding of the softening point vs. polymer
Fig. 8. Second storage protocol: A(80–100)/4.5% PMB was first stored at 180 °C for 1
day, 3 days, 7 days and 14 days. Then the samples were stored at 150 °C (open symbols).
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Polymer Degradation and Stability 147 (2018) 64–75
Fig. 9. Softening point vs. SBS content in A(80–100) bitumen.
concentration curve, also called as S-curve.
In PMBs, S-shaped curve is obtained when softening point (SP) is
plotted against the polymer concentration [31]. Fig. 9 shows the S-
curve obtained when A(80–100) base bitumen was modified with dif-
ferent wt % of D1101 SBS polymer. The S-curve is seen as having three
regions; Lower plateau, steep middle and upper plateau regions. The
lower region is usually observed when SBS concentrations are ≤3%. In
this region, the SP increased by a mere 13 °C even after addition of 3 wt
% of polymer in A(80–100) bitumen. At lower polymer content, the
three dimensional network is not strongly formed by the dispersed
polymer molecules. The three dimensional network once formed, sig-
nificantly increases the load carrying capacity of the PMB as observed
in the steep middle region (3%–6%). In the middle region, the SP raises
by almost 35 °C on increasing the polymer content from 3% to 6%. In
this region, a two phase system is usually seen under fluorescence mi-
croscopy [32,33]. Due to the formation of a three dimensional polymer
network, the rheological properties of the PMB (elastic recovery, visc-
osity, modulus, phase angle etc.) are also considerably altered. Above
6%, a plateau is again seen in the curve, where SP does not change
much with increasing polymer content. At polymer content > 6%, the
polymer phase increases eventually forming the continuous phase. Most
probably, the added polymer goes into the polymer phase rather than
increase the network density within the bitumen. In practice, de-
pending upon the requirement, PMBs with different polymer content
are used in road construction.
A(80–100)/3%, A(80–100)/4.5% and A(80–100)/7% PMBs lies in
the lower, middle and upper regions, respectively. The SP of the
A(80–100)/3% bitumen increased by a mere 13 °C after addition of
3 wt % of SBS. Since the upside in the properties is limited, the
downside due to storage at elevated temperatures will also be limited in
comparison to the PMBs with higher polymer content. From the S-
curve, it can be anticipated that in the steep middle region even minor
alterations to the polymer network can result in substantial changes to
PMB properties. Since A(80–100)/4.5% lies in the steep middle region,
loss of polymer network due to polymer degradation results in a steeper
fall in its properties compared to A(80–100)/7%. For A(80–100)/7%
PMB, there is still enough polymer network in the system after storage
that can withstand the applied stresses as is the case during SP mea-
surement.
3.3. Effect of base bitumen
To know if base bitumen plays a significant role in property erosion
during storage, the behaviour is studied in 4 different base bitumens
{A(80–100), B(80–100), A(60–70) and B(60–70)}. The 4 base bitumen
S.K. Singh et al. Polymer Degradation and Stability 147 (2018) 64–75

Fig. 12. Softening point as a function of storage time at 180 °C for the 4 PMBs with 4.5%
Fig. 10. S-curve obtained when 4 different base bitumens were modified with different wt
D1101 content in A(80–100), B(80–100), B(60–70), and A(60–70) base bitumen. Data in
% of D1101 SBS polymer.
1 L tin container also plotted for comparison.

samples, from three different sources are of two different penetration

grades, 80–100 and 60-70 dmm. The basic properties of these 4 bitu-
mens are given in Table 2.

3.3.1. Effect of base bitumen on S-curve

Before proceeding onto knowing how the base bitumen affects the
PMB properties during storage, it is all the more important to first know
how the S-curve is affected by the four bitumens, because the differ-
ences observed during storage may be just due to differences in S-
curves. Fig. 10 presents the S-curves obtained when the 4 bitumens
were modified with different wt % of D1101 SBS polymer. It can be
seen from Fig. 10 that except for B(80–100), all the other three bitu-
mens showed similar S-curves. The S-curve of B(80–100) bitumen de-
viated after D1101 content of ≥4%, showing a much lower value of SP
after manufacturing.

3.3.2. Base bitumen: Comparison at 3%, 4.5% and 7% D1101

Concentration
The 4 base bitumens were modified with 3%, 4.5% and 7% con-
centration of D1101 SBS polymer. The PMB samples were stored at
180 °C and the drift in SP was compared among the samples. In
Figs. 11–13, SP is plotted against storage time for the PMB samples with
3%, 4.5% and 7% D1101 content. It can be clearly seen from the figures
Fig. 11. Softening point as a function of storage time at 180 °C for the 4 PMBs with 3%
D1101 content in A(80–100), B(80–100), B(60–70), and A(60–70) base bitumen.
Fig. 13. Softening point as a function of storage time at 180 °C for the 4 PMBs with 7%
D1101 content in A(80–100), B(80–100), B(60–70), and A(60–70) base bitumen.
that though the degree of drop in SP varies from bitumen to bitumen,
they all show a similar trend. The variations among the PMB's were not
such that in one base bitumen we see 10 °C drop in SP while in another
base bitumen no drop in SP is observed after 1 week of storage. The
PMBs with 3% and 7% D1101 content showed almost identical beha-
viour. The maximum difference among the samples was seen for PMBs
with 4.5% D1101, which again lie in the steep middle region of the S-
curve. From Fig. 12, it can be seen that softening point of the 4 PMBs
decreases by 5–10 °C during first 3 days of storage at 180 °C. The
maximum drop in SP is observed in B(80–100)/4.5% PMB where nearly
10 °C drop is observed, while the least drop is seen in the case of
A(60–70)/4.5% PMB. Further increase in storage time leads to more
drop in SP in all the 4 PMBs. Except A(60–70)/4.5%, the other 3 PMBs
showed in excess of 20 °C drop in SP over a period of 21 days of storage.
Experiments were also carried out in a closed 1 L tin container.
Around 700 g of A(80–100)/4.5% PMB was taken in 1 L tin container,
its lid tightly closed and then kept inside the oven at 180 °C. After 1, 3,
7, 14 and 21 days of storage, about 100 g of PMB sample was taken out
from the tin container and it's SP determined. It can be seen from
Fig. 12 that the drop in SP in aluminium tube and 1 L tin container was
similar.

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S.K. Singh et al. Polymer Degradation and Stability 147 (2018) 64–75

Fig. 14. Softening point and penetration values of base bitumens A(80–100) and B Fig. 15. S-curve obtained when A(80–100) bitumen was modified with 4 different
(60–70) as a function of storage time at 180 °C. styrene-butadiene based polymers.

3.3.3. Stability of base bitumen

The stability of two base bitumens, A(80–100) and B(60–70), was
determined by storing them in aluminium tubes at 180 °C. The SP and
penetration values of the two base bitumens, as a function of storage
time at 180 °C have been presented in Fig. 14, respectively. It can be
seen from Fig. 14 that the softening point and penetration values of the
two base bitumens does not change, implying that the bitumens remain
stable during storage. Thus in case of PMBs, the erosion in properties is
mainly due to loss of polymer network.

3.4. Effect of polymer type

Our study would be incomplete if the effect of polymer type on the

thermal stability is not addressed. 6 polymers were used to understand
how variation in physical structure and chemical composition of the
polymer affects its thermal stability in bitumen. The basic properties of
these polymers are provided in Table 5 styrene-butadiene based block
copolymers (D1101, D1192, D1184, MD0243 and LG411) and 1 re-
active elastomeric terpolymer (Elvaloy 4170) were compared for its Fig. 16. Softening point as a function of storage time at 180 °C for the 6 PMBs with 4.5%
of various polymers in A(80–100) base bitumen.
stability at storage temperature of 180 °C.

3.4.1. Effect of polymer type on S-curve
As was the case with base bitumen studies, first the influence of the
various polymers on the S-curve was studied. Fig. 15 presents the S-
curves obtained when A(80–100) base bitumen was modified with
different wt % of D1101, D1192, D1184 and MD0243 SBS polymers.
LG411 is similar in chemistry and architecture compared to D1184,
hence its S-curve was not generated. The S-curve of Elvaloy polymer
was not possible to generate because the PMB became gel-like at con-
centration higher than 2 wt %. It can be seen from Fig. 15 that the S-
curves are significantly affected by the four polymers utilized. D1184,
branched SBS polymer, resulted in highest SP value after manufacturing
at all concentrations followed by D1192 polymer which has higher
vinyl content. From Fig. 15, it can be observed that the S-curve is more
dependent on the polymer type rather than the base bitumen, even
among styrene-butadiene based polymers. It will be interesting to know
how the SP values are affected due to storage at 180 °C.
3.4.2. Polymer type: Comparison at 4.5% concentration
The effect of storage at 180 °C on the SP of the 6 PMBs obtained by
modifying A(80–100) bitumen with different polymers is shown in
Fig. 16. Unlike the base bitumen effect, the PMBs with different poly-
mers showed drastically different thermal stability behaviour. While
D1101, D1184 and LG411 showed maximum drop in SP, MD0243 re-
mained stable throughout and D1192 showed just 7 °C drop in SP after
21 days of storage. The initial SP of Elvaloy polymer was just 64 °C and
hence appears to show lower drop in SP on the normalised scale. In fact
for PMB with Elvaloy polymer, the SP reaches that of base bitumen
values after just 7 days of storage at 180 °C. Now, why do D1192 and
MD0243 show the least or no drop in SP. One of the reasons is that both
of these polymers have high vinyl content (> 35%) in its structure
[34,35]. MD0243 is one of the newer grades of styrene-butadiene
polymer introduced by Kraton for bitumen modification whose che-
mical composition is not known completely [35]. Thus, the thermal
stability of the PMB during storage and transportation is much more
strongly influenced by polymer type. Storage temperature, polymer
concentration and polymer type plays a major role in controlling
property erosion during storage, while base bitumen plays a minor role.
In Fig. 17, the complex viscosity η* at 0.1 rad/s measured at 80 °C is
plotted against storage time. It can be seen from Fig. 17 that, similar to
SP values, the complex viscosity η* of conventional SBS grades also
decreases significantly, while that of MD0243 grade remains steady
throughout.

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S.K. Singh et al. Polymer Degradation and Stability 147 (2018) 64–75

Fig. 17. Complex viscosity η* at 0.1 rad/s measured at 80 °C as a function of storage time
Fig. 19. Average % ER at 70 °C as determined through MSCR test against storage time at
at 180 °C for the 6 PMBs with 4.5% of various polymers in A(80–100) base bitumen.
three different storage temperatures for A(80–100)/4.5% PMB.

3.5. Effect on elastic recovery (ER) and performance grading (PG)

In this section, we present the influence of storage temperature

(150 °C, 180 °C and 210 °C on the elastic recovery and performance
grade properties of the A(80–100) base bitumen modified with 3%,
4.5% and 7% D1101 polymer.

3.5.1. Steep middle region of S-curve: 4.5% SBS content

The effect of storage temperature (150 °C, 180 °C and 210 °C) on the
softening point (SP) elastic recovery (ER) and performance grading
(PG) of A(80–100)/4.5% PMB is presented in Figs. 18–21, respectively.
It can be seen from the figures that at 150 °C storage all the properties
of the modified bitumen remained intact.
Elastic Recovery (ER): Changes to the elastic recovery (ER) prop-
erty of the PMB, as determined through multi stress creep and recovery
(MSCR) test carried out at 70 °C, are shown in Figs. 19 and 20. The
MSCR test was carried out in accordance to ASTM D7405 and the
average ER of the 10 cycles are reported in Fig. 19. The results follow a
similar trend to that of SP, as shown in Fig. 18. At 150 °C, the ER value
hardly changes with storage time. But at 180 °C, the ER drastically Fig. 20. % ER after individual cycles at 70 °C for A(80–100)/4.5% PMB stored at 180 °C.
decreases from 95% to 65% with only 3 days of storage. Such a sharp
decrease in ER is of serious concern because many specifications require
the PMB to have a minimum of 75% recovery. At 210 °C, within one day

Fig. 21. Performance grading of A(80–100)/4.5% PMB vs. storage time at three different
storage temperatures.
Fig. 18. Softening point as a function of storage time at three different storage tem-
peratures for A(80–100)/4.5% PMB.

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S.K. Singh et al. Polymer Degradation and Stability 147 (2018) 64–75

of storage elastic recovery decreases to 50%. In Fig. 20, the ER value of

the individual creep cycles of the sample stored at 180 °C is shown.
Performance Grade (PG): PG of the PMB samples was carried out
and the results are shown in Fig. 21. In the PG system, the loss com-
pliance (1/J” = G*/sinδ) measured at frequency ω = 10 rad/s in the
linear viscoelastic regime (LVR) is adopted as the specification criteria
for rutting [36,37]. It can be seen from Fig. 21 that the PMB sample
before storage meets the PG specification condition of G*/
sinδ = 1 kPa at 80.5 °C which we designate as upper PG temperature
(Tu). As expected, the Tu of the PMB does not change due to storage at
150 °C. Surprisingly, Tu decreases by just 2 °C even after storage at
180 °C for 21 days in contradiction to the substantial decrease in other
properties. The reason for the contradictory behaviour can be estab-
lished in the frequency sweep data shown in Fig. 5. In PG grading, the
Tu is determined at an angular frequency of 10 rad/s, where appreci-
able difference in the rheological properties is not observed. At such
high angular frequency, the bitumen molecules dominate the rheolo-
gical response; hence any change in polymer network is not detected
during PG measurements. The difference in the rheological properties
Fig. 23. Average % ER at 60 °C as determined through MSCR test against storage time at
becomes noticeable only at lower frequencies. Thus, if Tu was de-
three different storage temperatures for A(80–100)/3% PMB.
termined at lower frequencies, then significant drop would have taken
place. At 210 °C, the loss in Tu is eventually detected.

3.5.2. Lower plateau region of S-Curve: 3% SBS content

The effect of storage temperature on the SP, ER, and PG of
A(80–100)/3% PMB is presented in Figs. 22–24, respectively. It can be
seen from the figures that similar to A(80–100)/4.5% PMB, at 150 °C
storage all the properties of the modified bitumen remained intact. At
storage temperature of 180 °C, SP, ER and upper PG of the PMB de-
creases by 5 °C, 15% and 0.7 °C, respectively, within first 3 days of
storage. With increase in storage time, ER properties continue to de-
crease and almost reach that of base bitumen values. Since upper PG
properties are measured at ω = 10 rad/s, the changes in rheological
properties are not seen, as shown in Fig. 6. At 210 °C storage, the SP, ER
and PG properties of the A(80–100)/3% PMB started to decline within
few hours of storage and reach that of base bitumen values within 1
day, similar to A(80–100)/4.5% PMB.

3.5.3. Upper plateau region: 7% SBS content

Studies were also carried out on the PMB with 7 wt % D1101 SBS
content. It can been seen from the S-curve (Fig. 9) that A(80–100)/7% Fig. 24. Performance grading of A(80–100)/3% PMB vs. storage time at three different
PMB is in the upper plateau regime. The effect of storage temperature storage temperatures.
on the SP, ER and PG of A(80–100)/7% PMB is presented in
Figs. 25–27, respectively. Similar to observations till now, it can be seen

Fig. 25. Softening point as a function of storage time at three different storage tem-
peratures for A(80–100)/7% PMB.

Fig. 22. Softening point as a function of storage time at three different storage tem-
peratures for A(80–100)/3% PMB.

73
S.K. Singh et al.
SBS concentration and polymer type play a significant role in the ob-
served property erosion, while type of base bitumen has a lesser effect.
Fig. 26. Average % ER at 85 °C as determined through MSCR test against storage time at
three different storage temperatures for A(80–100)/7% PMB.
Fig. 27. Performance grading of A(80–100)/7% PMB vs. storage time at three different
storage temperatures.
from Figs. 25–27 that all the properties of the modified bitumen re-
mained intact at 150 °C storage. At the intermediate storage tempera-
ture of 180 °C, the loss in SP, ER and PG were less severe compared to
A(80–100)/4.5% PMB. This is mostly likely due to the fact that at 7 wt
% polymer content, there is still enough polymer network in the system
that could withstand the applied stresses as is the case during SP and ER
measurements. Increasing the temperature to 210 °C did not spare the
highly modified bitumen, wherein property loss is again seen within
few hours of storage.
4. Conclusions
In this comprehensive study, the effect of storage temperature
(150 °C, 180 °C and 210 °C), SBS concentration, polymer type and base
bitumen on softening point (SP), elastic recovery (ER), performance
grade (PG) and rheological properties of styrene-butadiene polymer
modified bitumen was studied in sealed aluminium tubes, mimicking
the commercial storage and transportation practice. We have discussed
all the results in the background of the S-curve (SP vs. polymer con-
centration), there by highlighting the major role played by SBS con-
centration in property erosion during storage. Many salient conclusions
can be made from our study. Our results show that storage temperature,
74
Polymer Degradation and Stability 147 (2018) 64–75
• Effect of Storage Temperature: How the properties of SBS modified
bitumens are affected at different storage temperature? How oil
heated vs. flame heated system affect product properties?
Temperature of storage has a profound influence on the property
erosion in SBS modified bitumens even in “sealed containers”.
At 150 °C, properties of all SBS modified bitumens remained intact
even after storing for 21 days. At 180 °C, property drop is observed
within the first 3 days of storage for all the SBS modified bitumen,
except for MD0243 grade. Gel permeation chromatography and
rheological results clearly show degradation of SBS molecules. At
210 °C, properties start to erode within few hours of storage and
nearly reach that of base bitumen within 1 day. In flame heated
systems, the modified bitumens will likely be exposed to tempera-
tures ≥200 °C and thus have severe effect.
• Effect of SBS Concentration: By increasing SBS concentration, can we
compensate for the loss in properties?
Increasing SBS content can help if the new SBS concentration takes
the PMB to the upper plateau region (> 6%). But, the erosion in the
properties will be much higher if the new SBS concentration lands
the PMB in the steep middle region (3–6%).
Our results have clearly shown that, similar to storage temperature,
SBS concentration plays a major role in property erosion in the
modified bitumen.
Lower plateau region: At 3% SBS content, the three dimensional
network is not strongly formed by the dispersed polymer. Thus, the
property decrease though noticeable, will be limited.
Steep middle region (3% to 6% SBS content): The loss is most sig-
nificant in the samples that are in the steep middle region of the S-
curve. In this region, even minor alterations to the three dimen-
sional polymer network results in significant property erosion. For
PMBs with 4.5% SBS content, 5–10 °C drop in SP was observed
within the first 3 days of storage and up to 20 °C drop over a period
of 21 days. Complex viscosity decreased significantly, while phase
angle increased.
Upper plateau region ( > 6% SBS content): The drop in properties was
lower compared to the steep middle region due to the presence of
abundant polymer molecules in the system that can withstand the
applied stresses as is the case during SP measurement.
•
Polymer Type: How does the conventional grade of SBS polymer
perform compared newer grade and Elvaloy polymer?
Conventional polymer grades such as D1101, D1184, LG411 and
Elvaloy 4170 showed maximum erosion in properties, while D1192
grade (with higher vinyl content > 35%) showed significantly
lower drop. The newer polymer grade introduced by Kraton,
MD0243, remained completely stable at 180 °C even after 21 days.
MD0243 polymer will be the ideal option if thermal stability is of
utmost importance.
• Base Bitumen: For the same storage conditions, can SBS degrade
significantly in one base bitumen, while in another it remain stable?
Among the 4 different base bitumen samples analysed, major dif-
ferences was not seen when the SBS content is in the lower and
upper plateau region of the S-curve. But, noticeable differences were
observed in the steep middle region of the S-curve (3–6%).
• Elastic Recovery (ER) and Performance Grade (PG): Will elastic re-
covery and performance grade be affected similar to softening
point?
Similar to softening point, elastic recover (ER) properties will be
significantly affected. On the other hand, changes to the PG will not
be substantial.
For 4.5% SBS content, at 180 °C, ER values dropped to 65% from
95% over a period of 7 days of storage. The performance grade (PG)
measurements are carried out at 10 rad/s angular frequency,
wherein the bitumen molecules dominate the rheological response
S.K. Singh et al.
and hence any change in polymer network is not detected during PG
measurements. This is an area of concern because in North America,
PG system is used to evaluate bitumen samples.
Acknowledgement
This work is supported, in part, by the ‘Faculty Initiation’ grant
provided by Indian Institute of technology, Roorkee and by an ‘Early
Career Research’ grant from Science and Engineering Research Board
(SERB), India (ECR/2016/001427). Authors also thank Ministry of
Human Resource Development, India for providing student scholarship.
We like to acknowledge useful comments from Dr. K. Guruswamy, NCL
Pune.
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