Morphological Study of Polymer Modified Binders Ageing

Bhupendra Singha, Nikhil Saboob, Praveen Kumarc

a: Research Scholar, Department of Civil Engineering, Indian Institute of Technology Roorkee, India, Email:
bhupendrasingh.iitr@gmail.com
b: Assistant Professor, Department of Civil Engineering, Indian Institute of Technology (BHU), Varanasi, India,
Email: niks.iitkgp88@gmail.com
c: Professor, Department of Civil Engineering, Indian Institute of Technology Roorkee, India, Email:
pkaerfce@iitr.ac.in
Abstract: Asphalt binder modification is one of the most widely used measure to increase the functional and
structural life of the flexible pavements. Ageing of the asphalt binder is a major and inevitable phenomenon
which contributes to the deterioration of the pavement. Ageing behaviour of PMBs is found to be more complex
than the conventional binders. Present study aims at quantifying the effect of ageing on the morphology of the
asphalt binders. Scanning electron microscopy (SEM) has been used to study the morphological changes due to
short-term as well as long-term ageing of the conventional asphalt binders and PMBs. Based on the results of
the tests, comparisons are made and conclusions are given.

Keywords: Polymer Modified Binder (PMB), Ageing, Scanning Electron Microscopy (SEM).

1. Background

Asphalt binder is one of the most widely used construction material. Most of the roads worldwide are flexible
pavements constructed using asphalt binders. It is a complex hydrocarbon whose composition can majorly be
divided into four main components, lighter components such as aromatic and saturates and heavier components,
asphaltenes and resins. Aromatics, saturates and resins are collectively known as maltenes [1-3]. Asphaltenes
are suspended into the maltenes, forming a colloidal solution. Apart from these, bitumen also contains very
small quantities of metals such as Vanadium, nickel, iron magnesium and calcium. New axle configurations,
increasing axle loads, extreme weather conditions have almost made it mandatory to modify the conventional
binders. Among various types of modifications, polymer modification is most popular all over the world.
Polymer modification increases the elasticity of the binders and reduces the stress and temperature susceptibility
[4–8]. It increases the stiffness of the binders at higher temperature improving its rutting properties while
maintaining elasticity at lower temperature which improves fatigue response of the binder. Polymers used for
binder modification can be broadly classified into two categories, elastomers and plastomers. styrene–butadiene-
styrene (SBS) and ethylene vinyl acetate (EVA) are most popular elastomer and plastomer respectively which
are used to modify the paving asphalt binder. Polymer modification creates three-dimensional polymer network
inside the base binders which on the higher temperature imparts the higher stiffness to the binders improving its
rutting resistance, on the other hand, at lower temperatures it increases the elasticity of the binder, decreasing its
fatigue susceptibility [9].
Ageing is one of the most common phenomenon which affects the mechanical, physical as well as chemical
properties of the binders [10]. Ageing is broadly classified in two categories; short-term ageing occurs during
the construction stage of the pavement whereas long term ageing occurs during the service life of the
pavements. At high temperature during mixing, transportation, laying and rolling of bituminous mixture,
bitumen loses its oily components in the form of volatilization [11] and exudation [12] which in addition with
high-temperature oxidation [13] contributes to the overall increased hardness of the binders. This increased
hardness proves to be helpful in pavement performance at higher temperatures whereas on lower temperatures it
makes binder brittle which makes pavement more susceptible to cracking failures. Ageing changes bitumen
chemistry significantly. Short-term ageing increases the amount of heavier components which results in
increased hardness [14]. Ageing causes the formation of carbonyl compounds and sulfoxides, transformation of
generic fractions (maltenes) and increases in amount of large molecules (asphaltenes), molecular weight and
polydispersity [15]. Ageing affects the mixture properties significantly and therefore pavement performance also
[16-18]. Polymerisation changes the properties of the binder significantly. Moreover, many researches have
reported that ageing characteristics of modified is different than those of conventional binders [14, 19-21].
Over the years researchers have used different methods to examine effects of ageing on the binder properties.
Scanning Electron Microscopy (SEM) which are used by researchers over the years to study the morphology of
the materials and found to be very effective. So, the present study aims at studying the effect of polymer
modification on the ageing characteristics of asphalt using scanning electron microscopy.

2. Materials and experimental procedure

Viscosity grade VG-10 asphalt binder was used as the base binder in the study. EVA and SBS polymers were
used to prepare polymer modified binders (PMBs). EVA copolymer (Evatane®) was provided in the form of 2-3
mm pallets. Evatane® 2805 contains vinyl acetate content of 27–29%. It is a highly flexible plastomer designed
especially for bitumen modification for road construction. The SBS polymer used in the study, was Kraton D-
1101 which is a linear SBS polymer in powder form that consists of different combinations made from blocks of
polystyrene (31%) and polybutadiene of a very precise molecular weight. SBS and EVA absorbs the oily
components i.e. maltenes present in the asphalt binders and form a continuous polymer network which enhances
the properties of the binders. Lower polymer concentrations result in underutilisation of polymer modification
whereas higher concentrations will cause separation of polymer and asphalt phase. So, in order to get good
quality PMBs, using optimum dosage of polymer is of prime importance. Previous study by the author (Saboo
2016) have shown that interlock phase of polymer with the base binder can be obtained at 3% SBS and 5%
EVA. So, in the present study same has been adopted. The details of modified binder preparation have been
given below in table 1:

Table 1: Modified Binder Preparation Detail

Modified Base Modifier Modifier Mixing Mixing

Shear rate
Binder Binder used Dosage temperature Duration
PMB(E) VG-10 SBS 3% by wt. 180°C 60 Minutes 1500 RPM
PMB(P) VG-10 EVA 5% by wt. 190°C 30 Minutes 600 M

3. Experimental Procedure

In order to simulate ageing procedure in the laboratory conditions, first unaged binders were short term aged
using Rolling thin film oven test (RTFOT) following standard ASTM D2872 – 12e1. Then long-term ageing
was performed on short term aged binder samples using pressure ageing vessel (PAV) following standard
ASTM D6521 – 13. A number of conventional tests i.e. penetration test, softening point test, viscosity test,
ductility tests and elastic recovery test were performed on unaged, short term aged and long term aged binder
samples to characterise the materials. Results of the conventional tests are given below in table 2:

Table 2: Conventional Properties of Binders

VG-10 PMB (E) PMB (P)

Binder
Unaged RTFOT PAV Unaged RTFOT PAV Unaged RTFOT PAV
Penetration Values
94 52 30 44 30 22 50 29 20
(IS:1203)
Softening Point (ºC)
46 51 60 65 68 75 63 67 78
(IS:1205)
Penetration Index 0.010 0.031 -0.13 1.65 1.28 1.71 1.61 1.05 1.94
Ductility Value
>100 >100 92 - - - - - -
(IS:1208)
Elastic Recovery (%)
- - - 66 52 38 60 45 32
(IRC SP53: 2010)
Absolute Viscosity at
980 1356 2049 20800 22640 28458 59670 63850 74830
60 ºC (Poise) (IS:1206)

3.1 Scanning Electron Microscope (SEM)

Morphology of the binder samples was examined using Leo 435 VP SEM. In SEM, an electron beam is made to
strike the sample at ground potential. This causes radiation of back scattered electrons, X-rays, secondary
electrons etc. Then secondary electrons are used to produce the image on the computer screen. Since bitumen is
a non-conductive material, a thin conducting layer of Au (Gold) is sputtered to make it conducting, to avoid
charging. Test samples before and after sputtering is shown in figure 1(a) and figure 1(b) respectively.

(a) (b)
Figure 1: Sample Preparation

4. Results and Analysis

Following figure 2 (a-e) gives the SEM images of all the three binders in un-aged, RTFOT and PAV conditions.
Thermo-oxidative ageing increases the content of large molecules and decreases the content of small molecules
leading to an increase in the hardness of the binders [22]. Same behaviour was observed from the analysis of
SEM images of the base binder figure 2 (a-c). After RTFOT, number of large molecules increased, the process
was further accelerated after PAV. Figure 2(c) shows cluster of aromatic rings after PAV which is caused by
aromatisation of perhydroaromatic rings. Aromatisation takes place in order to attain more molecular stability.
In the process, aromatic rings get allied with each other forming a cluster. This results in increased viscosity of
the binders [23] which was also seen from the conventional test results.

(a) (b)
 (d) (e)

(g) (h)

(i)
Figure 2: SEM Images of Binders in Un-aged, Short-term Aged and Long-term Aged Conditions

Comparing the SEM images of base binders (figure 2(a-c)) with that of PMBs (figure 2(d-i)), it was observed
that PMBs resists the formation of carbonyl and sulfoxide compound. This can be credited to the blending
process of base binder and polymer. During the mixing and blending process polymers (SBS and EVA) absorbs
light oily constituents (maltenes) of the binders and swell 4-9 times their original volume. This hamper the
interaction of bitumen molecules and oxygen. Due to lack of interaction between oxygen and bitumen
molecules, lesser oxidation of asphalt binder takes place and hence PMBs shows better resistance to ageing than
conventional binders. During the laboratory ageing process bitumen experiences high temperature and pressure
for prolonged durations (85 minutes for RTFOT and 20 hours for PAV) so at higher temperature and pressure
degradation of SBS polymer network in PMB(E) takes place. Figure 2(d) shows a continuous binder and
polymer phase with a well-developed polymer network. After RTFOT degradation of polymer network takes
place and instead of a continuous polymer bitumen phase, a bitumen rich phase with some segregated polymer
patches can be seen in figure 2(e). After PAV polymer network was further degraded and a bitumen rich phase
with almost no polymer network was obtained (Figure 2(f)). This degradation of polymer network, causes the
degradation of binder properties also. In case of PMB(P), EVA network shows more stability as compared to
PMB(E). Previous research work conducted to assess the thermal-oxidative performance of EVA [24-26]
concluded that EVA copolymer is able to resist the PAV ageing upto 25 hours. EVA experiences chemical
degradation and oxidation at a temperature of 180 °C. Same behaviour was also observed in the SEM images of
PMB(P). From figure 2(g-i) it can be seen that although after RTFOT and PAV there is some amount of
polymer network degradation took place but when we compare it with PMB(E), it is very minimal. So, it can be
concluded that in SBS modified asphalt binder ageing causes both polymer degradation and bitumen oxidation
whereas in EVA modified asphalt binder the ageing results majorly in oxidative hardening of the binders.

5. Conclusions

Scanning electron microscopy (SEM) gave an idea about changes at microscopic levels occurring due to
polymer modification as well as ageing. After increased the amount of larger molecules in the conventional
binders, which was seen by the SEM images of conventional binders. PMBs were found to resist the formation
of larger molecules. However higher temperature and pressure diminished the polymer network of SBS which
resulted in degradation of polymer properties also. On the other hand, EVA was able to resist the degradation
due to high temperature and pressure although oxidative hardening took place which resulted in changes in
binder properties.

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