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Assessing impact of chemical compatibility of additives used in asphalt

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DOI: 10.1016/j.conbuildmat.2022.129349

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 Construction and Building Materials 359 (2022) 129349

Contents lists available at ScienceDirect

Construction and Building Materials

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

Assessing impact of chemical compatibility of additives used in asphalt

binders: A case study using plastics
Anand Sreeram a ,∗, Angelo Filonzi a , Satyavati Komaragiri a , K. Lakshmi Roja b , Eyad Masad b ,
Amit Bhasin a
a
Department of Civil, Architectural and Environmental Engineering, The University of Texas at Austin, Austin, TX, USA
b Department of Mechanical Engineering, Texas A&M University at Qatar, Doha, Qatar

ARTICLE INFO ABSTRACT

Keywords: Economic and environmental factors mandate the use of engineered materials as well other waste or industrial
Waste plastics by-products as an additive or extender in asphalt binders and mixtures. In most cases, the impact of these
Compatibility materials on the long-term performance of asphalt binders and concomitant mixtures is evaluated on an ad hoc
Modified asphalt
basis. This study explores the use of chemical compatibility based on the Hansen Solubility Parameters (HSP)
Hansen solubility parameters
to better understand and predict the performance of modified asphalt binder blends. Specifically, this approach
Recycling
is applied to the case of plastic materials that are increasingly being evaluated as a value-added extender for
binders. In order to investigate the role of chemical compatibility on the macroscopic performance of such
modified blends, two different types of polyethylene (PE) plastics with varied compositional characteristics
were studied, referred to as PE-1 and PE-2. Additionally, the impact of using elastomeric polymers as co-
modifiers with plastics were also examined. From a solubility perspective, the results indicated that PE-1
and asphalt binders show reasonable compatibility, whereas PE-2 was incompatible. Further analyses were
conducted to correlate these results using microscopic and rheological tools. PE-1 modified binders were
seen to be well dispersed in the binder matrix and had acceptable performance, particularly with the
combined use of co-modifiers. On the other hand, all PE-2 modified binders showed poor dispersion and
consequently inferior rheological performance. The results also indicated that the addition of co-modifiers will
only improve the compatibility of plastics in blends on a selective basis. Overall, the work conducted in this
study demonstrates the impact of chemical compatibility on the macroscopic performance of different plastic
modified blends. The approach used in this study can also be extended for use with other additives used in
asphalt binders to better understand the chemo-mechanics of the different additive-binder blends and impact on
performance.

1. Introduction and overview
The modification of asphalt binders or bitumen is a common prac-
tice to increase its resilience and performance. This modification can
occur at the mixing terminal or at the hot mix plant prior to the
construction of a pavement. The most frequently used modifiers include
polymers, chemical additives such as warm mix additives (WMA),
and rejuvenating agents or a combination of these. The impetus on
sustainability in the pavement engineering field has pushed the use of
other non-engineered waste products such as waste plastic, ground tire
rubber etc. into the asphalt mix [1,2]. The addition of such materials
in asphalt binders and by extension in asphalt mixes adds complexity
and changes its expected performance as a result of the different
physicochemical interactions between the materials. In most cases,
the impact of such additives have been evaluated on a macroscopic
engineering scale, which is both relevant and important. However, a
better insight from material science perspectives is required to engineer
high performance paving materials. In spite of different studies looking
at the various aspects of using waste plastics for asphalt applications,
there has been little work looking at the fundamental material com-
patibility between asphalt binders and plastics. Such an insight is
especially important to explain and improve the observed macroscopic
performance of such blends. The main goal of this study is to utilize
the Hansen Solubility Parameters (HSP) to examine the fundamental
material compatibility between an asphalt binder and an additive.
Specifically, for the purposes of this study the additive being considered
are polyethylene based plastics from different sources with and without
co-modifiers.

∗ Corresponding author.
E-mail address: anand.sreeram@austin.utexas.edu (A. Sreeram).

https://doi.org/10.1016/j.conbuildmat.2022.129349
Received 23 June 2022; Received in revised form 19 September 2022; Accepted 3 October 2022
Available online 24 October 2022
0950-0618/© 2022 Elsevier Ltd. All rights reserved.
A. Sreeram et al.
2. Background
2.1. HSP and its application to bitumen
The HSP method was developed by Charles Hansen and evaluates
the compatibility of materials based on the basic principle of ‘‘like dis-
solves like’’. The HSP methodology is grounded in the thermodynamics
of materials and its in-depth theoretical background has been provided
in several different works [3]. Other studies have also used different
solubility based parameters to develop thermodynamic models to study
diffusivity and related phenomena in binders [4].
In brief, HSP is an extension of the Hildebrand solubility parameter
(𝛿) and is principally based on the assumption that the cohesive inter
molecular forces of a material can be conveyed as the sum of three
components: dispersive interactions (𝛿𝐷 ), polar interactions (𝛿𝑃 ), and
hydrogen-bonding interactions (𝛿𝐻 ), all expressed per molar volume
in MPa1∕2 . The dispersive forces comprise of interactions between
induced dipoles (London forces), while polar forces embody the interac-
tions between permanent dipoles (Keesom forces) and forces between
permanent and induced dipoles (Debye forces). The final interaction
influencing the cohesive energy is hydrogen bonding interactions [5].
The Hansen three dimensional equation can be represented as shown
in Eq. (1).
𝛿𝑇2 = 𝛿𝐷
2
+ 𝛿𝑃2 + 𝛿𝐻
2
(1)
Where 𝛿𝑇 represents the total solubility parameter of a material. For
any given material, these three points can be represented in a three-
dimensional coordinate system corresponding to the HSP in three-
dimensional space, referred to as ‘‘Hansen Space’’. Using these points, a
sphere entailing its entire solubility in Hansen space can be graphically
represented. A more detailed procedure and mathematics involved is
presented in subsequent sections.
Related to asphalt binders, Redelius first introduced the bitumen
solubility model to describe the solubility of different molecules of
asphalt binders [6]. Fig. 1 shows the example of bitumen or asphalt
binder and several solvents based on a prior work by the authors [7,8].
The solubility sphere of bitumen is shown along with a good solvent
toluene and non solvents iso-octane, 2-butanone and 2-ethyl-1-hexanol.
It can be seen that the center of the bitumen sphere is close to that
of toluene indicating compatibility (and solubility) whereas the non-
solvents are further apart which indicates non compatibility and poor
dissolution. This concept can be further extended to the use of additives
and binder extenders. In theory, the solubility parameters of any modi-
fying agent must be close to bitumen to ensure maximum compatibility
and stability as a composite. Mixing of binders with incompatible
materials could be accompanied by phase separation tendencies and
importantly a loss of functional properties of the binder. Prior studies in
this domain have already established the possibility of using HSP based
models to evaluate the different solubility properties of binders such as
the mutual compatibility of mixing differently aged bitumen [6,9]. This
work will expand on these concepts and extend it to the use of additives
and extenders, using two types of plastics as an example.
2.2. Use of plastics as a binder extender
Over the past few years, there has been widespread interest in the
pavement engineering community regarding the incorporation of differ-
ent types of waste plastics in asphalt binders for roadway construction.
The usage of such materials are expected to bring about significant
environmental benefits by providing a recycling outlet for plastics
and reducing the burden on landfills. Many different types of plas-
tics have been investigated as binder extenders including low density
polyethylene (LDPE), high density polyethylene (HDPE), polyethylene
terephthalate (PET), polyvinyl chloride (PVC), polypropylene (PP) and
polystyrene (PS). Of these, PE and PET based plastics have been the
2
Construction and Building Materials 359 (2022) 129349
Table 1
Properties of plastics used.
Plastic Form Melt flow index Melting point
PE−1 Pellet 70 g/min 104 ◦ C
PE−2 Pellet 1–4 g/min 127 ◦ C and 162 ◦ C
most extensively studied as compared to others. Laboratory studies in
this domain have indicated variable results and details regarding these
can be referred to in the extensive literature reviews that have been
conducted [10–12].
When considering the use of different plastics as binder extenders,
one of the main concerns that has been reported is related to phase
separation due to the incompatibility of plastics with bitumen due to
its non-polar nature. Such phase separation would lead to practical
concerns such as issues with storage stability and loss of ductility,
particularly in the case of wet processes (i.e. plastics pre-blended with
the asphalt binder). Therefore, many studies have also looked at incor-
porating secondary additives such as reactive co-modifiers, elastomers
and sulfur to the mix to improve compatibility, binder stability and
overall performance [13,14]. An example of a reactive polymer would
include ter-polymers which has been widely studied and shown to
have benefits on performance and compatibility [15,16]. In spite of
these studies, there has been little work looking at the fundamental
material compatibility between asphalt binders and plastics. Therefore,
the use of plastics in asphalt binders is an ideal case to investigate the
use of techniques such as HSP to investigate the underlying nature of
physicochemical interactions and provide insights into the attributes of
such complex composites.
3. Scope
This study primarily explored the use of HSP to examine the funda-
mental material compatibility between plastics and asphalt binder. To
illustrate this concept, two different types polyethylene (PE) plastics
with varied compositional characteristics were studied, referred to as
PE-1 and PE-2. Additionally, the use of elastomeric and reactive co-
modifiers were also examined. Following solubility analyses, blends
composed of the additives with binders were comprehensively evalu-
ated using a suite of binder tests including fluorescence microscopy,
separation tests, Superpave performance grading, and ductility us-
ing poker-chip testing methodology. Overall, the work conducted is
expected to shed significant insights into fundamental issues of com-
patibility when incorporating additives and extenders in binders and
help guide material selection in the future.
4. Materials and blends
Two different plastics were used in this study. The first plastic
material was low density polyethylene (PE-1) obtained locally, which
had a density value of 0.918 g/cc. The second material was industrially
produced recycled post-consumer plastic, which was largely polyethy-
lene (PE-2) with a density value of 0.993 g/cc. Hence, it is likely that
PE-2 has non-uniform composition and could be mixture of different
types of recycled plastics.
The use of two different types of plastics is intended to study the
effect of compositional variance when considering its practical use in
paving applications. Both plastics were obtained in pellet form and the
melt flow index of PE-1 and PE-2 were 70 g/10 min and 1–4 g/10 min,
respectively. Apart from that, PE-1 had a melting point of 104 ◦ C and
a large portion of PE-2 had a melting point of 127 ◦ C and a smaller
portion had a melting point of 162 ◦ C. The available properties of the
plastics are also listed in Table 1.
Conventional elastomeric and reactive additives were also used to
evaluate the influence of co-modifiers on the different properties of
plastic modified asphalt binders. The co-modifiers included a reactive
A. Sreeram et al. Construction and Building Materials 359 (2022) 129349

Fig. 1. Solvents and non-solvents in the Hansen sphere of bitumen.

Source: Adapted from [7].

Table 2
Properties of blends.
Binder no Description Code (used in this study)
1 Control binder Q Control
2 Q Control + 3% PE−1 by weight of the binder Q + PE−1

3 Q Control + 3% PE−1 by weight of the binder + 1.25% ter-polymer +0.25% CL−1 Q + PE−1 + E1

4 Q Control + 3% PE−1 by weight of the binder + 1.5% SBS elastomer + 0.225% CL−2 Q + PE−1 + E2

5 Q Control + 4.5% PE−2 by weight of the binder Q + PE−2

6 Q Control + 3.5% PE−2 by weight of the binder + 0.225% CL−2 Q+PE−2+S

7 Q Control + 3.5% PE−2 by weight of the binder + 0.25% CL−1 Q+PE−2+P1

8 Q Control + 2.25%PE−2 by weight of the binder + 2.25% PE−1 + 0.225% CL−2 Q+PE−2+P2

ter-polymer and a SBS elastomer. Additionally, two different crosslink-
ers (CL-1, CL-2) were used along with the co-modifiers. An asphalt
binder of PG grade 64-22 obtained from a local supplier in Qatar
was used for the binder modification and rheological analysis in this
study. Lastly, all chemicals used in this study were laboratory grade
and purchased from Thermo Fisher Scientific. It should be noted that
the quantity of different additives and plastics used in this study were
based on manufacturer recommendations and preliminary lab testing.
Further, this work is not intended to optimize the design, type and
quantity (%) of modifiers used in a mix but rather to illustrate the effect
of modifiers and appropriate co-modifiers on binder compatibility and
rheology. Names and other details of the co-modifiers and crosslinkers
used are not provided as they were proprietary products and are not
considered essential to the objective of this work.
Table 2 shows the combinations of materials and blends along with
a short notation used to identify them in this study.
For the initial blending of binders with plastic, a high shear mixer
was used at 2000 rpm for 2 h at 180 ◦ C. In the case of the SBS modifier
(4), 1.5% of SBS and 0.225% of CL-2 was added to the blended binder
(by weight of binder). CL-2 was added after initial blending of the
SBS with the binder. In the case of the ter-polymer (3), 1.25% of the
polymer with 0.25% of CL-1 was added to the blended binder (by
weight of the binder). For (6), (7) and (8), the additives (CL-1 and CL-2)
were added during the initial blending of PE-2 and binder.
5. Measurement of HSP
The HSP parameters of the materials were determined using 29
different laboratory grade solvents as shown in Table 3. These solvents
were chosen specifically to cover a wide range of HSPs in order to
approximately determine the solubility parameters of the different
materials used in this study [3]. This approach followed the standard
procedure i.e. to select a set of solvents with a known and wide range
of solubility parameters and to test the solubility of the experimental
materials in each of them. Choosing such a wide variety of solvents (25-
35) with varying HSPs is sufficient to give a reasonably good accuracy
for the determination of HSP of a given material [17].
A small amount of the target material (e.g. asphalt binder, plastic,
or co-modifier) was dissolved separately in 5 ml of each solvent in a test
tube. The test tubes were secured with a stopper to avert evaporation
of the solvent. To allow time for complete dissolution, the test tubes
were stored for 24 h at room temperature. Additionally, the tubes were
carefully shaken recurrently and the solubility was recorded in each
test tube and classified into two categories: soluble and not soluble.
The division of solvents into these categories is chosen to ensure that a
reasonable percentage of the total number of solvents being considered
as being ‘‘good’’ solvents. This data was processed using HSPiP™ soft-
ware to attain the HSPs and the radius value, R𝑜 . Using these, a sphere

3
A. Sreeram et al. Construction and Building Materials 359 (2022) 129349

Table 3 Table 4
List of solvents. Calculated values of HSP.
Solvent list Material HSP values
1.4-Dioxane Di-propylene Glycol D P H Radius (Approx)
1-Butanol Ethanol
Bitumen 20.41 5.39 2.7 12.7
2-Phenoxy Ethanol Ethyl Acetate
SBS 15.56 5.47 8.8 10.5
Acetone Hexane
PE−1 18.03 2.26 3.85 2.1
Acetonitrile Methyl ethyl ketone
Ter-Polymer 18.06 2.24 3.88 2.1
Chloroform Methanol
Cyclohexane Methyl Isobutyl Ketone PE−2 Cannot be determined
Cyclohexanol Methylene Dichloride
Dibasic Ester N-Butyl Acetate
Diacetone Alcohol N-Methyl Pyrrolidone
Diethylene Glycol Propylene glycol methyl ether 6.3. Binder stiffness
Dimethyl Formamide Methoxy Propyl Acetate
Dimethyl Sulfoxide Propylene Carbonate
Stiffness measurements were conducted for the original (unaged),
Tetrahydrofuran Tetrachloroethylene
Toluene RTFO aged, and PAV aged samples to evaluate the Performance Grade
(PG) of asphalt binders. The high temperature PG of the different
binders were determined using a TA Instruments dynamic shear
rheometer (DSR) using a 25 mm parallel plate geometry and testing
of interaction for the evaluated materials can be drawn, termed in this gap of 1 mm. To assess the complex shear modulus, a frequency of 10
study as the ‘‘solubility sphere’’ and encompasses its entire solubility rad/s was used on the different binders. Lastly, in order to assess the
in Hansen space [17]. To estimate if a solvent fits into a sphere of impact of the plastic additives on the low temperature grade of the PAV
interaction, the distance R𝑎 between the solvent and the material can aged binders, BBR tests were conducted at −6 ◦ C, −12 ◦ C and −18 ◦ C
be computed as per Eq. (2), where 𝛿𝐷 , 𝛿𝑃 and 𝛿𝐻 , respectively, refer to using a Cannon TE-BBR instrument.
the dispersion, polar and hydrogen bonding parameters. The subscript
1 refers to the studied material and subscript 2 refers to the solvent. The 6.4. Binder strength and ductility
ratio of 𝑅𝑎 and 𝑅𝑜 is termed as the relative energy difference (RED) as
shown in Eq. (3). Good solvents will lie in the sphere of affinity and The poker-chip test was used to evaluate the tensile strength and
have a RED number of less than 1.0. Greater RED numbers for solvents ductility of control and modified binders at the RTFO aged condition.
would indicate lower affinity. Prior works have demonstrated the use of this method to identify differ-
ences in the tensile strength of asphalt binders and as a direct measure
𝑅2𝑎 = 4(𝛿𝐷
2 2 2
− 𝛿𝐷 ) + (𝛿𝑃2 − 𝛿𝑃2 )2 + (𝛿𝐻
2 2 2
− 𝛿𝐻 ) (2)
1 2 1 2 1 2 of ductility that is strongly correlated with the cracking susceptibility
𝑅𝑎 of asphalt mixtures in the field [19,20]. The test was conducted by
𝑅𝐸𝐷 = (3) testing a 1.59 mm thin film of asphalt binder confined between two
𝑅𝑜
metal plates of 50 mm diameter in tension at loading rate of 2 N/sec.
6. Measurement of physical and mechanical properties The main steps involved in the test are illustrated in Fig. 2.

6.1. Fluorescence microscopy 7. Results

In this study, a fluorescence trinocular compound laboratory micro-
scope manufactured by Omax™ was used to examine the dispersion of
the modifiers in the binder. The extent of dispersion and binder homo-
geneity is an important consideration when evaluating the feasibility of
polymer modified binders. The test involved placing a very thin amount
of heated binder on a glass slide and then covering it with another glass
slide, similar to the methods adopted in other studies [13,18] The low
thickness of the samples prepared in this manner allowed for light to
freely pass through and is critical for proper characterization using this
method. The samples were illuminated using a blue light for excitation
(in the range 390–490 nm) and the fluorescent light re-emitted by the
sample was observed under the microscope. A magnification of 100x
was used to view the samples, which allowed for the dispersion of the
modifiers in the binder to be studied in the micrometer range (μm).
6.2. Binder stability
The high temperature stability of the asphalt binder was evaluated
using the ASTM D7173 (2011) test method. In summary, this test
involved placing the binder blend in an aluminum tube (25 mm in
diameter and 125 mm in height) at 163 ◦ C for a duration of 48 h
in a vertical position. Subsequently, the tube is kept in a freezer for
a minimum of 4 h and the binder from the top and bottom third
of the tube were evaluated using a dynamic shear rheometer (DSR)
to determine its complex modulus (G⋆ ) and compared to serve as an
indicator of separation. The tests were conducted at a temperature of
64 ◦ C and a frequency of 10 rad/s at 10% strain level.
7.1. HSP
The HSP values of the different materials were calculated as de-
scribed in Section 5 and the results are shown in Table 4. The values
of the HSP calculated for bitumen were 20.41 (𝛿𝐷 ), 5.39 (𝛿𝑃 ) and 2.7
(𝛿𝐻 ) respectively. Similar range of values were reported in a study
by Redelius, which used 15 different binders and a wider variety
of solvents [21]. Although the quantitative parameters of HSP are
extremely useful indices, it may be unfamiliar for asphalt researchers.
A more powerful and simpler visualization of compatibility between
materials can be obtained using the solubility sphere which entails the
entire solubility of a material in Hansen space. This concept is used to
evaluate the solubility tendencies between the materials.
As an example, consider the HSP of SBS elastomer. It is important
to note that SBS is composed of two different types of polymers:
butadiene and polystyrene which will have different HSP. In this case,
the solubility testing of SBS was conducted as a whole and the solubility
sphere of SBS with respect to bitumen is shown in Fig. 3. It is evident
from Fig. 3 that SBS has partial solubility in bitumen and is therefore
a suitable modifier of adequate compatibility when added in small
amounts.
The solubility studies on the plastics used in this study yielded
interesting results. The HSP of PE-1 and ter-polymer were by coin-
cidence identical which indicates high compatibility between these
two materials and suitability for synergistic use. When comparing the
solubility spheres of bitumen and PE-1, it can be seen from Fig. 4
that these materials have overlapping regions with centers located
in similar Hansen space. This suggests that these two materials are

4
A. Sreeram et al. Construction and Building Materials 359 (2022) 129349

Fig. 2. Key steps in sample preparation (top row) and testing (bottom row) using the poker-chip method.

Fig. 3. HSP of SBS and bitumen.

generally compatible with each other from a solubility perspective. In
fact, both materials also show similar HSP values for dispersive (𝛿𝐷 )
and hydrogen bonding (𝛿𝐻 ) interactions. However, it must be noted
that the R𝑜 of the LDPE solubility sphere is small which suggests that
it is generally not a highly soluble material or not soluble in a wide
variety of materials. Therefore, the use of secondary additives such
as ter-polymers which may increase the compatibility of PE-1 with
bitumen through chemical linkages can be considered a good option
for further composite modification and optimization. Lastly, the HSP
of the PE-2 could not be determined using the range of solvents used
in this study. This indicates that its solubility properties are entirely
in a different Hansen space than the materials used in this study.
Hence, PE-2 would be generally incompatible with bitumen and its
dispersibility when used as a modifier is questionable. This may be have
serious implications in terms of binder rheology and performance and
is discussed in the next sections.
7.2. Fluorescence microscopy
Fluorescence microscopy was used to evaluate the dispersion of the
modifiers in the binder matrix. The extent of dispersion is an important

5
A. Sreeram et al.
Fig. 4. HSP of PE-1 and bitumen.
Fig. 5. Fluorescence microscopy images of binders.
design consideration as heterogeneity can introduce stress localization
and long term phase separation. Fig. 5 shows that the PE-1 and PE-2
modified binders have two different phases. As described in prior works
in this domain, the aromatic phase of binders is the most fluorescent
phase and once the polymeric additives (plastics in this case) absorb
aromatics, they become bright when exposed to fluorescent light [22].
It was seen that the PE-1 modifier has generally good dispersion in
the binder matrix and this dispersion is even further improved with
the addition of E1 (c) and E2 (d). Overall, the PE-1 modified binders
exhibit uniform distribution of modifiers and there is a presence of
a continuous asphalt rich phase along with a dispersed polymer rich
phase.
However, in the case of PE-2 modified binders (e-h), the polymeric
phase of the modifier is seen to be in excess which results in a dis-
proportionate amount of swelling and may subsequently lead to phase
separation issues in practice. Such images indicate that the PE-2 is not
effectively dispersed in binders and may potentially act more as a filler
than an additive. Additionally, usage at high concentrations could even
lead to phase inversion wherein bitumen would be dispersed in the
polymer matrix.
6
Construction and Building Materials 359 (2022) 129349
Overall, the observations using microscopy are in excellent agree-
ment with the HSP parameters in three different ways: (i) PE-1 is
compatible with the bitumen and therefore tends to disperse well; (ii)
addition of ter-polymer as a co-modifier enhances the compatibility
of PE-1; and (iii) PE-2 is highly incompatible and therefore tends to
agglomerate within the asphalt binder.
7.3. Binder stability and separation
The separation tests were conducted for the different binders as
described in Section 6.2 and the results are presented in Fig. 6. The
results show the separation i.e. the difference (in %) in the value of
𝐺∗ between the top and bottom portion of the cigar tube. Firstly, it is
important to note that in practical paving conditions, such modified
binders would likely need to undergo continuous agitation in the
storage tank prior to its mixing with aggregates, similar to conventional
modified binders with ground tire rubber (GTR) for example [23]. This
test was carried out without any agitation and therefore the results
will naturally exaggerate the separation that may occur in the binder
storage tank [24]. Nevertheless, the results from the test can be good
A. Sreeram et al. Construction and Building Materials 359 (2022) 129349

Table 5
PG results of binders.
Binder High temperature true grade Low temperature true grade
Original [◦ C] RTFO [◦ C] Stiffness [◦ C] m-value [◦ C]
Q Control 70.7 68.1 −22.3 −22.0

Q+PE−1 75.6 73.9 −22.4 −16.7

Q+PE−1+E1 79.4 78.0 −21.4 −18.4
Q+PE−1+E2 76.7 76.5 −21.9 −19.9

Q+PE−2 82.8 81.1 n/aa n/aa

Q+PE−2+S 80.6 80.8 n/aa n/aa
Q+PE−2+P1 84.1 83.9 n/aa n/aa
Q+PE−2+P2 84.7 81.9 n/aa n/aa
a The results could not be obtained at the standard continuous testing temperatures
(−6 ◦ C to −18 ◦ C).

Fig. 6. Separation % (based of G* of top and bottom).

Correspondingly, 10 ◦ C below the minimum temperature where the m-

indicator to assess the material compatibility between the recycled
plastics and bitumen including the effect of secondary additives.
The density of PE-1 is slightly lower than that of bitumen and
at high storage temperatures, PE particles which are initially well
dispersed in the bitumen matrix flocculate, coalesce and then cream
to the top of the sample tube over time. This can be observed from
the results with the Q+PE-1 sample which showed a separation of
around 44%. The addition of the secondary additives (E1 and E2)
reduced this value to 25% and 23% respectively. As a polyolefin ma-
terial, PE will not chemically interact with the components of binder.
However, through the addition of secondary reactive and elastomeric
additives, chemical cross-links are likely formed in the bitumen matrix
which increases compatibility of the materials as evidenced from the
stability results. All PE-2 modified binders on the other hand showed
separation values ranging from 85% to 99%. This indicates that PE-2
is completely separated from the binder during the test, and signifies
that these materials could be generally incompatible. Even though this
separation could be mitigated by agitation during storage, the long term
compatibility and phase separation issues in field would likely remain.
Whilst PE-2 is fundamentally incompatible in asphalt binder, further
analysis may be considered for smaller dosages of PE-2 such as 1%–
2% modification to understand its effect on stability and dispersion.
However, this is beyond the scope of this study.
7.4. High and low temperature grade
The high and low temperature true grades of the binders were eval-
uated using a DSR and BBR respectively and the results are presented
in Table 5. The high temperature PG of the binders were calculated
based on the 𝐺∗ ∕ sin 𝛿 parameter for the unaged and RTFO aged binders
as per the criterion listed in AASHTO T316. A higher value of high
temperature PG generally indicates a relatively stiffer binder which in
this case could be attributed to the addition of the modifiers.
A few key observations are as follows. It was seen that the addition
of PE-1 increased the high PG of the control binder which signifies
that these modified binders would be less susceptible to rutting or
permanent deformation at high temperatures. The addition of E1 and
E2 increased the high PG of the PE-1 modified binders but only to a
limited extent. When considering the modification of the control binder
by PE-2, it was seen that the stiffness of the binders were drastically
increased. An increase of up to two performance grades in high PG
could be observed by this modification.
The low temperature properties of the binders were also evaluated
using a BBR and the stiffness and m-value true grades of the binder
are presented in Table 5. According to AASHTO T313 standards, 10 ◦ C
below the minimum temperature where the stiffness does not surpass
300 MPa for any given binder is defined as the stiffness true grade.
values surpasses a value of 0.3 is defined as the m-value true grade
It was observed that the PE-1 modification did not change the low
temperature PG of the binders. This is an interesting result consider-
ing that these binders were stiffer as seen from the high PG results.
Therefore, it can be implied that this modification imparts certain
relaxation properties akin to other polymer modified binders or at
the very least does not significantly negatively impact the ability of
the binder to relax. In terms of the PE-2 modified binders, the low
temperature PG could not be evaluated using the standard continuous
testing temperatures (−6 ◦ C to −18 ◦ C) utilized in this study. This
indicates that these binder would have generally poor low temperature
properties with true grades lower than −16 ◦ C.
7.5. Binder strength and ductility
The strength and ductility of the binders were evaluated using the
Poker chip test method as described in Section 6.4. This is particularly
important due to the concern that the addition of waste plastics can
deteriorate the cracking resistance of asphalt binders. The results of
the tensile strength and failure strain as a measure of ductility are
presented in Fig. 7. The failure strain in this test is defined as the
post-peak strain that corresponds to 80% of the tensile strength of the
binder [20]. For the PE-1 modified binders, it was observed that the
addition of PE-1 increased the tensile strength of the binder and slightly
reduced the ductility. The addition of modifier E1 was seen to increase
the ductility value to a level higher than the control binder. In general,
increased tensile strength with no loss or higher ductility is an indicator
for improved resistance to fatigue cracking. In the case of the PE-2
modified binders, there was no increase in tensile strength that was
observed as a result of this modification. Additionally, these binders
showed very poor values for ductility indicating high susceptibility
to fatigue cracking. Fig. 8 presents typical results showing the stress–
strain behavior from the tests. The lack of ductility at peak stress and
slight to no change in tensile strength due to the PE-2 modifiers can be
observed from this figure. Inversely, the increased ductility and tensile
strength is visible for the PE-1 modified binders. To put this further into
perspective, Fig. 9 shows the tensile strength versus ductility for typical
PG binders as shaded ellipses. The discrete points show the values for
the binders modified using PE-1 and PE-2. The constructive effect of
PE-1 modification and the adverse effect of PE-2 modification on the
ductility of the control binder is clearly visible.
8. Findings and conclusion
This study investigated the use of the Hansen Solubility Parameters
(HSP) as a fundamental metric that dictates the compatibility between
an asphalt binder and an additive as well as the impact of good and
poor compatibility on performance related properties. Specifically, this
work utilized the modification of asphalt binders with two PE based

7
A. Sreeram et al. Construction and Building Materials 359 (2022) 129349

Fig. 7. Tensile strength and failure strain (defined as the post-peak strain at 80% of peak stress).

Fig. 8. Tensile strength and failure strain (defined as the post-peak strain at 80% of peak stress).

Fig. 9. Range of Typical tensile strength vs ductility

Legend in figure indicated as C:Q Control, L:Q+PE-1, LE1:Q+PE-1+E1, LE2:Q+PE-1+E2, R:Q+PE-2, RS:Q+PE-2+S, RP:Q+PE-2+P1, RLS:Q+PE-2+P2.

8
A. Sreeram et al.
plastics with compositional differences (PE-1, PE-2) as the basis to
examine compatibility using HSP and its impact on the properties of
the blend. The following findings could be drawn from the laboratory
tests:
• Based on solubility analyses, PE-1 showed partial solubility with
bitumen which indicates that it would be compatible as a modifier
when used in limited amounts. The solubility properties of PE-2
could not be determined using a wide range of solvents, which
suggests that it would be generally incompatible with bitumen.
• PE-1 was seen to be well dispersed inside the binder matrix and
the use of co-modifiers further improved its dispersion. PE-2 on
the other hand showed poor dispersion and excessive swelling
of the polymeric phase. These observations were based on mi-
croscopy and separation tests and were consistent with the expec-
tations based on the HSP for the component materials. The results
also suggest that the addition of co-modifiers will likely improve
the compatibility of plastics in blends on a selective basis.
• The rheological properties of the binders suggest that plastic
modification generally help to increase the stiffness and tensile
strength of the binders. The addition of PE-1 was seen to generally
aid the ductility and fatigue cracking properties of the binder.
However, the addition of PE-2 proved to be detrimental in those
aspects.
• Analyses through various chemo-mechanical perspectives showed
that PE-1 has considerable promise to be used as an effective
modifier and its performance may be enhanced by suitable co-
modifiers and mix design. PE-2 was seen to be generally incom-
patible and more research efforts would be required to enable its
use as a binder modifier.
Overall, the work conducted in this study illustrated the issue of
material compatibility between plastic modifiers and binders using
fundamental physicochemical perspectives. Although the use of plas-
tics as a binder extender can bring about added benefits in terms of
sustainability, a closer look at the materials used is required when
considering the design of high quality mixes. Depending on material
compatibility, certain plastics or combination of plastics would be more
or less suitable to be used as binder modifiers. It is recommended that
further studies be conducted towards optimizing the content of plastics
used with respect to performance and also evaluate the effect of plastic
variability on rheology and chemistry.
CRediT authorship contribution statement
Anand Sreeram: Conceptualization, Methodology, Investigation,
Formal analysis, Writing – original draft, Writing – review & editing.
Angelo Filonzi: Investigation, Formal analysis. Satyavati Komara-
giri: Investigation, Formal analysis. K. Lakshmi Roja: Investigation,
Formal analysis, Writing – review & editing. Eyad Masad: Conceptu-
alization, Investigation, Formal analysis, Writing – review & editing.
Amit Bhasin: Conceptualization, Methodology, Investigation, Formal
analysis, Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Data availability
Data will be made available on request.
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Construction and Building Materials 359 (2022) 129349
Acknowledgments
This work was supported by the Qatar National Research Fund
(QNRF): NPRP11S-1128-170041. The authors also acknowledge the co-
funding of Qatar Petrochemical Company (QAPCO) and RAETEX Doha
company, Qatar. All statements are those of the authors.
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