Article

Chemical, Thermal, and Rheological Performance of Asphalt

Binder Containing Plastic Waste
Rosa Veropalumbo 1, Francesca Russo 1, Cristina Oreto 1, Giovanna Giuliana Buonocore 2, Letizia Verdolotti 2,*,
Herminio Muiambo 3, Salvatore Antonio Biancardo 1 and Nunzio Viscione 1

1 Department of Civil, Construction and Environmental Engineering, Federico II University of Naples,

Via Claudio 21, 80125 Naples, Italy; [email protected] (R.V.); [email protected] (F.R.);
[email protected] (C.O.); [email protected] (S.A.B.); [email protected] (N.V.)
2 Institute of Composites, Polymers and Biomaterials—National Research Council, P.le E. Fermi, 1,

80055 Naples, Italy; [email protected]

3 Chemistry Department, Eduardo Mondlane University, Maputo P.O. Box 257, Mozambique;

[email protected]
* Correspondence: [email protected]; Tel.: +39-081-7758839

Abstract: In order to meet the environmental needs caused by large plastic waste accumulation, in
the road construction sector, an effort is being made to integrate plastic waste with the function of
polymer into asphalt mixtures; with the purpose of improving the mechanical performance of the
pavement layers. This study focuses on the effect of a recycled mixture of plastic waste on the chem-
ical, thermal, and rheological properties of designed asphalt blends and on the identification of the
Citation: Veropalumbo, R.; most suitable composition blend to be proposed for making asphalt mixture through a dry modifi-
Russo, F.; Oreto, C.; cation method. Thermo-gravimetric analysis, differential scanning calorimetry, and Fourier trans-
Buonocore, G.G.; Verdolotti, L.; form infrared spectroscopy analysis were carried out to investigate the effect of various concentra-
Muiambo, H.; Biancardo, S.A.; tions and dimensions of plastic waste (PW) on the neat binder (NB). The frequency sweep test and
Viscione, N. Chemical, Thermal, and
the multiple stress creep and recovery test were performed to analyze the viscoelastic behavior of
Rheological Performance of Asphalt
the asphalt blends made up of PW in comparison with NB and a commercial modified bitumen
Binder Containing Plastic Waste.
(MB). It has been observed that the presence of various types of plastic materials having different
Sustainability 2021, 13, 13887. https://
melting temperatures does not allow a total melting of PW powder at the mixing temperatures.
doi.org/10.3390/su132413887
However, the addition of PW in the asphalt blend significantly improved the aging resistance with-
Academic Editors: Michael Wistuba, out affecting the oxidation process of the plastic compound present in the asphalt blend. Further-
Di Wang, Chiara Riccardi, Libo Yan, more, when the asphalt blend mixed with 20% PW by the weight of bitumen is adopted into the
Zhanping You, Lily Poulikakos asphalt mixture as polymer, it improves the elasticity and strengthens the mixture better than the
and Ana Jiménez del Barco Carrión mixture containing MB.

Received: 26 October 2021 Keywords: plastic waste; recycled asphalt blends; rheological analysis; asphalt mixture; FTIR; dif-
Accepted: 6 December 2021 ferential scanning calorimetry
Published: 15 December 2021

Publisher’s Note: MDPI stays neu-

tral with regard to jurisdictional
1. Introduction
claims in published maps and institu-
tional affiliations. The global plastics economy is mainly linear: plastics are produced, used, and gen-
erally disposed of with no recovery. In order to preserve the environment while meeting
consumption demands, a global effort to shift the linear economy into a circular model
must be made [1,2]. A circular economy model suggests the promotion and revalorization
Copyright: © 2021 by the authors. Li- of plastics already in circulation [3]. To date one of the main environmental problems is
censee MDPI, Basel, Switzerland. pollution due to plastic waste: it degrades in a very long time and consequently ends up
This article is an open access article filling beaches, seas, and other natural places, when not correctly recycled or reused. In-
distributed under the terms and con- deed, the COVID-19 pandemic has highlighted the need for single-use plastics since po-
ditions of the Creative Commons At- tential health risks and societal fears concerning virus-contaminated products introduce
tribution (CC BY) license (https://cre- consumer fears of reuse [3]. Nevertheless, these socio-material challenges need a system-
ativecommons.org/licenses/by/4.0/).
atic approach to plastic waste management. On this basis, the sector of asphalt pavement

Sustainability 2021, 13, 13887. https://doi.org/10.3390/su132413887 www.mdpi.com/journal/sustainability

Sustainability 2021, 13, 13887 2 of 22

construction has provided a good opportunity to recycle, reuse, and reduce plastic waste.
For this reason, many researchers in the road construction sector are investigating the re-
use of plastics/polymers into bituminous mixtures [4]. The employment of polymers as
bitumen modifiers has been generally studied for decades. Polymer modification of bitu-
men is already practiced by the asphalt industry with the aim to improve the properties
related to road pavement resistance. Indeed, it has been proved that the addition of poly-
mer into binder enhances its stiffness at high temperature, its moisture resistance, and its
fatigue life [5].
Some authors have shown that using a 4.5% of SBS polymer with high-vinyl content
by weight of the binder increase the number of fatigue cycles to failure when compared
to a commercial polymer-modified bitumen and a virgin bitumen at any strain level [6].
Furthermore, it was found that the modification of neat bitumen using a hybrid combina-
tion of styrene-ethylene/propylene-styrene (SEPS) and montmorillonite (MMT) clay im-
proves not only its performance at high temperature but also the aging resistance due to
a lower increase in carbonyl functional groups when exposed to oxidation [7].
As a consequence of the massive plastic waste that is generated worldwide, the use
of waste plastics/polymers has been also investigated. According to Wu and Montalvo [8]
and Vargas and Hanandeh [9], the major types of waste polymers used to modify bitu-
mens are polyethylene teraphthalate (PET) [10,11], which not only reduced the amount of
binder required for the optimization of an asphalt mixture but also produced a significant
decrease in plastic deformations; high-density polyethylene (HDPE) [12], whose optimum
content between 6 and 10% was found to improve the fatigue phenomenon where the
number of loading cycles increases; polyvinyl chloride (PVC) [13], which increases the
strength and stability of the mix; low-density polyethylene (LDPE) [14–16], which has
been found to play important roles in asphalt’s low-temperature properties and hot stor-
age stability; polypropylene (PP) [17], which produced increases of viscosity, softening
point, flash point, and the decreasing of density when added to a commercial neat bitu-
men, penetration, and solubility, and polystyrene (PS) [18] that can be reduced 1% of bi-
tumen in mixture replacing it producing an extra-rigidity on the final asphalt mixture.
Other polymers that are attracting researchers’ attention are ethylene-vinyl acetate (EVA)
[19–21], polyurethane (PU) [22–24], acrylonitrile butadiene styrene (ABS) [25], and poly-
carbonate [26].
Among the waste plastic polymers, polyethylene (PE) is considered the most effec-
tive for bitumen modification [27,28].
For example, Padhan and Sreeram [29] evaluated the effect of adding PE into a neat
commercial-grade VG 10 binder with a 2:1 ratio to modify it. Better performances were
obtained, in particular, the addition of PE exhibited higher softening point and rotational
viscosity values, and lower penetration values than the neat binder.
Kakar et al. [30] showed that the addition of 5% PE by mass to the binder lead to an
increase in the resistance to the rutting with respect to commercial polymer-modified
binders.
Brasiliero et al. [31] analyzed the feasibility of using two percentages (6.5 and 12.5%
by the weight of binder) of flakes made from recycled PE as binder modifiers. It was found
that as the amount of PE increases the binder shows similar properties of a modified
binder manufactured in the refinery, leading to an increase of the complex modulus and
at the same time a reduction of the phase angle at high temperature.
Some studies were focused on the effect of mixing high-density polyethylene (HDPE)
(melting point at 180 °C), low-density polyethylene (LDPE) (melting point at 160 °C), and
polypropylene (PP) (melting point at 190 °C) on the viscoelastic performance of a tradi-
tional binder [32]. It has been shown that the addition of LDPE at loading above 2% by
the weight of binder increase the viscoelastic behavior of the bitumen [33] while the addi-
tion of PE at loading between 2% and 8% by the weight of the binder [34] improves the
fatigue performance of the binder with an increase of the failure values (Nf).
Sustainability 2021, 13, 13887 3 of 22

Nizamuddin et al. [5] reported that the addition of recycled LDPE as a modifier for
bitumen showed significant improvements in the physical, chemical, rheological and ther-
mal properties of base bitumen. Specifically, a concentration between 3 and 6% by the
weight of bitumen is suggested to enhance sustainability and increase performance, thus
favoring its use during construction. Other researchers have studied different plastic
waste blends to find the optimum compositions for pavements that could withstand heav-
ily loaded vehicles and hot climates. Particularly, several studies have been conducted on
the reuse of PET widely used in the production of beverage containers and polyester tex-
tiles [35]. Merkel et al. [35] showed that additives made from deconstructed PET wastes,
chemically modified through aminolysis to obtain terephthalic amides, improve the per-
formance properties of asphalt at various experimental conditions.
It has already been proven that the mixtures containing waste plastic bottles have
lower optimum asphalt content compared to the conventional mixture, which could re-
duce the amount of asphalt binder used in road construction [36]. When plastic wastes are
used as modifiers into asphalt mixtures [37], the performance properties of the asphalt
mixture are enhanced, in particular, the mixture turns to be less sensitive to moisture dam-
age.
Given the above scenario, the aim of the present research is to investigate the effect
of various concentrations and dimensions of plastic waste (PW), mainly composed of a
mixture of PET and PE, on the structural, thermal, and rheological properties of asphalt
blends, and, in a preliminary analysis, the feasibility to introduce PW into asphalt mixture
through a dry method, to obtain performance similar to those of mixture containing com-
mercial modified bitumen. A series of tests have been carried out as synthetized in the
experimental program shown in Figure 1. The first phase of the research deals with the
investigation of the main properties of the materials that are adopted for making the as-
phalt blends, and the asphalt mixtures, i.e., neat bitumen (NB) 50/70 penetration grade,
modified bitumen 10/40–70 (MB), plastic waste, and limestone aggregates. After that, the
asphalt blends containing PW were prepared, and jointly the basic properties in terms of
ring and ball (EN 1427 [38]) and viscosity (EN 13702 [39]) were analyzed. Chemical char-
acterization and a thermal degradation analysis were carried out on the asphalt blends to
explore the effect of PW when mixed at a high temperature of 150 °C with NB. Subse-
quently, the main rheological properties were assessed, including the two binders (NB
and MB), by means of a dynamic shear rheometer (DSR) and performing a frequency
sweep (FS) test (EN 14770 [40]) and a multiple stress creep and recovery (MSCR) test (EN
16659 [41]). After the identification of the most suitable asphalt blend with PW among
those analyzed, the same amount of PW corresponding to this blend was used for the
preparation of an asphalt mixture optimized according to the Superpave procedures
through the dry method, in compliance with the same volumetric properties of a tradi-
tional hot mix asphalt with NB and a hot mix asphalt prepared with MB, used as control
mixes. On the three obtained mixtures, the indirect tensile strength (EN 12697-23 [42]) and
the moisture damage (EN 12697-12 [43]) tests were performed to investigate the effect of
PW within an asphalt mixture.
Sustainability 2021, 13, 13887 4 of 22

Figure 1. Summary of the experimental program.

2. Materials and Methods

2.1. Materials
2.1.1. Binders
The neat bitumen (NB), 50/70 penetration grade, was obtained from an oil refinery in
Southern Italy. The blends were prepared using NB while a modified bitumen 10/40–70
(MB) was used as a control binder. Table 1 gives a summary of the results of some tests
performed on the two bitumens.

Table 1. Bitumen basic properties.

Bitumen
Properties Unit Standard
NB MB
Penetration at 25 °C dmm EN 1426 [44] 68 52
Softening point (R&B) °C EN 1427 [38] 46 87
Dynamic viscosity at 135 °C 0.25 1.38
Dynamic viscosity at 100 °C Pa s EN 13702 [39] 4.10 9.18
Dynamic viscosity at 60 °C 185 1560

2.1.2. Plastic Waste

The plastic waste (PW) used as a modifier was obtained from the mechanical shred-
ding of plastic bottles and made up of different plastic waste types, PET, HDPE, LDPE,
and PE (see Figure 2a). The shredded plastic was washed and then dried by centrifugation
and airstream ventilation for the removal of non-plastic residual material. The final size
was obtained by an extruder equipped with a series of perforated plates whose diameter
range from 4 to 0.125 mm.
Sustainability 2021, 13, 13887 5 of 22

2.1.3. Preparation of the Bituminous Blends

Two different samples of PW were adopted to obtain the modified bituminous
blends: (a) PW with size/diameter ranging from 4 mm to 0.063 mm, and (b) PW with
size/diameter ranging from 4 mm to 0.25 mm.
Therefore, three bituminous blends were prepared as follows:
• NB mixed with 10% PW by the weight of NB whose size ranges between 4 and 0.25
mm, (B1).
• NB mixed with 10% PW by the weight of NB whose size ranges between 4 and 0.063
mm, (B2).
• NB mixed with 20% PW by the weight of NB whose size ranges between 4 and 0.063
mm, (B3).
An asphalt blend with NB plus 20% PW by the weight of NB whose size ranges be-
tween 4 and 0.25 mm was not studied, since the obtained compound was not workable.
The blend preparation consisted of the following steps [45]: first of all, the bitumen
was preheated in a metal container at 150 °C for 1 h, and then poured into a steel container
previously oven heated to 150 °C. A known amount of PW was slowly added to the bitu-
men and then mixed in the mixer at 4500 rpm speed for approximately 10 min (see Figure
2b), until a homogeneous compound was reached (see Figure 2c).

(a) (b) (c)

Figure 2. Blend preparation: (a) plastic waste powder with a size between 4 and 0.063 mm; (b) mix-
ing phase; (c) final blend.

A preliminary analysis was made in terms of ring and ball (R&B) by comparing NB
with the obtained three mixtures (B1, B2, and B3) to assess the effect derived from the
addition of PW. As can be seen from the results reported in Table 2, R&B values of B1, B2,
and B3 samples have been improved by 23, 20, and 88%, respectively, in comparison with
NB.
As expected, the viscosity values (see Table 2) of the three blends B1, B2, and B3 are
higher than those of NB, at both 100 °C and 135 °C. In particular, at 100 °C, the lowest
increase (115%) was shown by the B2 sample while the highest (381%) was obtained by
the B1 sample, while at 135 °C keeping constant the PW amount at 10%, B1 shows a lower
viscosity value (68%) compared to B2.
It is worth noting that, both at 100 °C and 135 °C, the 10% PW blends show viscoe-
lastic properties similar to the MB sample, in particular, the B2 sample at 100 °C and the
B1 sample at 135 °C.
It is noticeable from the above results that the increase of the PW content with a nar-
rower size range gives rise to blends more sensitive to the temperature and, therefore,
more workable during the blending operation at temperatures around 150 °C.
Sustainability 2021, 13, 13887 6 of 22

Table 2. Basic properties of studied materials: ring and ball and viscosity at 100 °C and 135 °C.

R&B Viscosity at 100 °C Viscosity at 135 °C

Sample
(°C) (Pa × s) (Pa × s)
MB 87.0 9.18 1.38
NB 46.0 4.10 0.25
B1 56.8 19.73 1.56
B2 55.2 8.83 4.93
B3 86.3 15.62 2.45

2.1.4. Grading Curve with Limestone Aggregates

An asphalt concrete (AC) grading curve with a maximum size of 20 mm (AC20) for
a binder layer was designed in this study by adopting four different sizes of limestone
aggregates provided by a local quarry in southern Italy; Table 3 shows the mechanical and
volumetric properties (apparent specific gravity (Gsa) and bulk specific gravity (Gsb)) of
the limestone aggregates.

Table 3. Aggregate main properties.

Los Angeles Shape Index Flat Index Sand Equivalent Gsa Gsb
(%) (%) (%) (%) (g/cm )
3 (g/cm3)
EN 1097-2 [46] EN 933-4 [47] EN 933-3 [48] EN 933-8 [49] EN 1097-6 [50] EN 1097-6 [51]
Coarse aggregate
Limestone 10/18 20.6 4 8 n.d. * 2.694 2.686
Limestone 6/12 20.1 8 11 n.d. 2.713 2.687
Fine aggregate
Limestone sand n.d. n.d. n.d. 95.3 2.718 2.679
Limestone filler n.d. n.d. n.d. n.d. 2.737 2.737
* n.d. = not determined.

The design of the grading curve was defined according to the following require-
ments:
• EN 13108-1 [51] (see Table 1 in EN 13108-1);
• Special tender documents of southern Italy for a binder layer;
• Superpave requirements, according to the control points, defined for a nominal max-
imum aggregate size of 19 mm, and a sand restricted zone to be avoided for compat-
ibility problems [52];
• Maximum-density gradation, according to the Fuller and Thompson equation, to be
avoided (n = 0.45) [53].
The obtained design curve is reported in Figure 3.
Sustainability 2021, 13, 13887 7 of 22

Figure 3. Grading curve for the binder layer.

2.1.5. Mix Design

According to the purpose of the study, to carry out the analysis on the asphalt mix-
ture when PW is added using the dry method, it was necessary to optimize, in the first
analysis, a hot mix asphalt with NB (HMANB) and a hot mix asphalt made up of MB
(HMAMB), with the same volumetric properties [54]. The Superpave protocol was followed
for the mix design phase, adopting a gyratory compactor to make cylindrical specimens
(see Figure 4b) in compliance with EN 12697-31 [55].
The mixing procedure adopted to define the optimum binder content (OBC) for both
HMANB and HMAMB was as follows:
• The aggregates were oven heated at 180 °C, and since NB and MB showed different
viscosity values (see Section 2.1.3) and therefore required different mixing tempera-
tures, NB, and MB were preheated respectively at 150 and 185 °C.
• The coarse aggregates and sand were blended with the bitumen for 4 min at the mix-
ing temperature depending on binder type, after that the filler was added and the
mixing continued for others 5 min (see Figure 4a).
After the mixing phase, the mixture was put in the oven for 2 h to reach a uniformity
compaction temperature of 150 and 175 °C for HMANB and HMAPMB, respectively. To sat-
isfy the Superpave requirement for a Va equal to 4% at Ndes, 100 and 112 were found to
be the appropriate Ndes for HMANB and HMAMB respectively. The results of the mix de-
sign are shown in Table 4.

Table 4. Superpave optimization: HMANB vs. HMAPMB volumetric properties.

Va VMA VFA %Gmm at Ndes Dust Portion

Mixture
(%) (%) (%) (%) (-)
HMANB 4.0 14.2 70.6 85.57% 1.1
HMAMB 4.1 14.4 71.8 95.90% 1.1
Sustainability 2021, 13, 13887 8 of 22

(a) (b)
Figure 4. (a) Asphalt mixing phase and (b) gyratory compaction.

2.2. Methods
2.2.1. Chemical Characterization: Fourier Transform Infrared Spectroscopy-FTIR
FTIR spectra were recorded at room temperature by using an infrared spectrometer
(model Frontier Dual Ranger, PerkinElmer, Waltham, MA, USA) in attenuated total re-
flectance (ATR) mode from 650 to 4000 cm−1 [2,56]. Spectra were recorded at 4 cm−1 reso-
lutions and reported the average of 64 scans. It has been proved by several researchers
[57] that infrared spectroscopy (FTIR) in ATR mode is an efficient and reliable method to
investigate and monitor the chemical arrangement (i.e., oxidative phenomena) and struc-
ture of asphalt samples. Hence, it has been used to analyze NB, its composite samples, B1,
B2, B3, and MB.
In the region ranging from 2000 to 600 cm−1, the main vibration peaks, which are in-
dicators of asphalt binder oxidation level, absorb namely carbonyl (C=O, around 1700 to
1740 cm−1), sulfoxide functional groups (S=O, around 1030 cm−1), along with butadiene
(−CH=CH−, 960 cm−1) and styrene (aromatic groups, around 690–750 cm−1) peaks [2].
In order to better understand the influence of PW filler on the chemistry of bitumen,
we performed the FTIR characterization of the “neat” PW and of the PW after thermal
treatment at 150 °C, which represents the average temperature used for the preparation
of bitumen composites. All the spectra were baseline corrected by using Perkin Elmer
Spectrum software.

2.2.2. Thermal Degradation Properties (TGA and DSC)

The thermal degradation behavior was evaluated by thermo-gravimetric analysis
(TGA) and differential scanning calorimetry (DSC). TGA was carried out in air and in
nitrogen flow (flow rate = 40 mL/min) using a TGAQ500 TA instrument, at a heating rate
of 10 °C/min in the temperature range from 30 °C to 1000 °C, with sample mass of approx-
imately 10 mg [58,59].
DSC analyses were conducted on Q1000 TA instruments. Samples were first heated
from −80 °C to 200 °C and then subjected to cooling up to −80 °C, and finally reheated to
200 °C. The rates of heating and cooling were 10 °C/min.

2.2.3. Properties Investigation of Asphalt Binders and Mixtures

The rheological investigation of the asphalt binders was carried out by means of the
frequency sweep (FS) test (EN 14770 [40]) and multiple stress creep and recovery (MSCR)
test (EN 16659 [41]).
Sustainability 2021, 13, 13887 9 of 22

The FS test was carried out using frequency values falling within a range from 0.1 to
10 Hz (a total of 20 observations were made with a gap of 0.1 for frequencies from 0.1 to 1
Hz, and a gap of 1 Hz for frequencies from 1 to 10 Hz, passing through 1.59 Hz) at six test
temperatures (0, 10, 20, 30, 40, and 50 °C). A Dynamic Shear Rheometer (DSR, Anton Paar
Smart PAVE 102 type) was used.
A “25 mm plate-plate geometry” with a 1 mm gap was adopted to carry out the rhe-
ological analysis at test temperatures above 30 °C, and an “8 mm plate-plate geometry”
with a 2 mm gap as the DSR configuration was used to investigate all the specimens at
test temperatures below 30 °C.
The ratio between the maximum shear stress (𝜏𝑚𝑎𝑥 ) and the maximum shear strain
(γmax) determined the complex shear modulus (|G*|) (see Equations (1) and (2)), while the
lag between τmax and γmax obtained the phase angle (δ).
𝜏𝑚𝑎𝑥
|𝐺 ∗ | = (1)
𝛾𝑚𝑎𝑥

|𝐺 ∗ | = √𝐺′2 + 𝐺′′2 = |𝐺 ∗ | ∙ 𝑐𝑜𝑠𝜑 + |𝐺 ∗ | ∙ 𝑠𝑒𝑛𝜑 (2)

where G′ is the storage modulus and G″ is the loss modulus, both in kPa.
The MSCR test was carried out using DSR. Non-recoverable creep compliance (Jnr),
which is one of the parameters that give a measure of the degree of resistance of a bitumi-
nous mastic and/or binder to permanent deformations under repeated loading–unloading
cycles was established in accordance with EN 16659 [41]: two stress levels of 0.1 kPa and
3.2 kPa, and two test temperatures (40 and 50 °C) were used.
𝑁
The mean value of non-recoverable creep compliance at the N-th cycle (𝐽𝑛𝑟 , see Equa-
𝑁
tion (3)) and the mean value of the total creep compliance at the N-th cycle (𝐽𝑡𝑜𝑡 , see Equa-
tion (4)) over ten cycles of creep and recovery was calculated for each temperature under
0.1 and 3.2 kPa.
𝑁
𝑁 𝜀10⁄𝜏 (kPa−1 ) (3)
𝐽𝑛𝑟 =

𝑁 𝜀1𝑁⁄ −1 (4)
𝐽𝑡𝑜𝑡 = 𝜏 (kPa )
𝑁
where 𝜀10 is the strain value at the end of the recovery phase (after 10 s) of the N-th cycle,
𝜏 is the applied stress, 0.1 kPa and 3.2 kPa and 𝜀1𝑁 is the strain value at the end of the
creep phase (after 1 s) of the N-th cycle.
The indirect tensile strength (ITS) and the indirect tensile stiffness modulus (ITSM)
were adopted for the mechanical characterization of the asphalt mixtures.
The ITS was carried out according to EN 12697-23 [42]. The cylindrical specimen to
be tested is brought to the specified test temperature of 10 °C, placed in the compression
testing machine between the loading strips, and loaded diametrically along the direction
of the cylinder axis with a constant speed of displacement until it breaks. The ITS is the
maximum tensile stress calculated from the peak load applied at break and the dimen-
sions of the specimen, calculated by using Equation (5).
2𝑃
𝐼𝑇𝑆 = (5)
𝜋𝐷𝐻
where ITS is the indirect tensile strength (GPa), P is the peak load (kN), D is the diameter
of the specimen (mm), and H is the height of the specimen (mm).
A total of three specimens were tested and the final ITS value was obtained as a mean
value of the three determinations.
The stiffness modulus conducted at three different temperatures of 10, 20, and 40 °C
was calculated using an indirect tensile load configuration, in compliance with ANNEX
C of the EN 12697-26. Since the standard requires that the peak load value shall be ad-
justed to achieve a target peak transient horizontal deformation of 0.005% of the specimen
diameter when the test temperature is 10 °C, the test was conducted under strain control
Sustainability 2021, 13, 13887 10 of 22

to keep constant the strain level below 50 με for each temperature. The ITSM was calcu-
lated using Equation (6).
𝐹 × (𝜈 + 0.27)
𝐼𝑇𝑀 = (6)
𝑧×ℎ
where F is the peak value of the applied vertical load (N), z is the amplitude of the hori-
zontal deformation obtained during the load cycle (mm), h is the mean thickness of the
specimen (mm), and 𝜈 is Poisson’s ratio (assumed to be 0.35).

3. Results and Discussion

3.1. FTIR Characterization
In order to better understand the role of PW in the development of bituminous com-
posites and on their chemistry, the FTIR characterization of “neat” PW and of PW after
thermal treatment at 150 °C, which represents the processing temperature for the produc-
tion of bitumen composites, has been performed. From the analysis of the FTIR spectra
related to the PW powders before and after the thermal treatment (see Figure 5), the main
characteristic absorption peaks correlated to the various plastic materials contained in the
PW (PET, HDPE, LDPE, PP) have been identified. For instance, the C-H stretching vibra-
tion absorption, in the range 2964–2910 cm−1, which is from a bond uniquely identified in
polymeric materials, along with the stretching vibrations of C-C and C-O-C bonds around
1016 cm−1 and 1100 cm−1 and the bending vibrations of CH2 at 1293 cm−3 were identified.
Yet, the specific C=O (carbonyl functional group) vibration peaks, mainly related to the
abundant presence of polyesters in the investigated PW, such as PET, were identified at
around 1716 cm−1. Moreover, a further sharp peak at 3435 cm−1 was ascribed to the O-H
and/or N-H stretching vibrations, attributed to the hydrolytic and oxidizing processes oc-
curring on the surface of the PW [2,60]. The comparison of the spectra before (green curve)
and after (red curve) the thermal treatment at 150 °C also shows an increase in the inten-
sity of the carbonyl absorption group (C=O) in the thermally treated sample. This is
mainly due to the oxidation of polyolefins (LDPE, HDPE, PP) exposed at high tempera-
tures [2,60].

(a) (b)
Figure 5. FTIR spectra of plastic waste, before and after thermal treatment at 150 °C (a) complete investigation range (b)
magnification in the range 700–1900.

Figure 6 reports the FTIR spectra of neat and composite bitumen samples (MB, NB,
B1, B2, and B3), and Table 5 summarizes the main vibrational assignments. The assign-
ments around 2850 cm−1 and 2920 cm−1 were ascribed to the stretching vibrations of the
aliphatic C-H bonds and the corresponding bending vibrations were identified at 1460
Sustainability 2021, 13, 13887 11 of 22

cm−1. Additionally, the C=C ring vibration bands from aromatic species were recorded at
around 1605–1590 cm−1.
In the vibrational range 1500–1800 cm−1, MB showed some oxidized species which
come from the aging of SBS moieties contained in the bitumen [57], i.e., the C=O vibration
peaks, at 1741 cm−1, are correlated to the free carbonyl, and at 1690 cm−1, are associated to
the conjugate carbonyl. This vibration peak was not observed for the NB, thus indicating
that the NB is not oxidized. For the samples B1, B2, and B3, the stretching vibrations of
free-carbonyl group C=O were recorded at lower wavenumbers, namely around 1716
cm−1. This peak can be correlated to the carbonyl stretching of PW as observed in the spec-
tra reported in Figure 5. This means that the addition of PW in the bitumen blends does
not affect the oxidation/aging process of bitumen.
Additionally, for the MB sample and for NB, a new characteristic oxidation peak at
around 1030 cm−1 has been observed and identified as the S=O bond in sulfoxide. Instead,
in the case of the B1, B2, and B3 blends, in addition to the S=O slight peak (~1033 cm−1), a
vibrational peak at 1018 cm−1, attributed to the C-O-C bond of plastic waste, was also ob-
served (Figure 6b).
Furthermore, the vibration peaks associated with the trans-di-substituted –CH=CH−
butadiene block (968 cm−1) and to the C-H aromatic mono-substituted (styrene block, at
748 cm−1) have been highlighted in the spectra of MB samples and NB. At the same wave-
number values, a small shoulder has been also recorded for the investigated blends (B1,
B2, and B3).
Moreover, a slight band at around 3400 cm−1 (correlated to the -OH-stretching) has
been observed for MB samples (mainly for B3), likely related to the oxidation of the poly-
butadiene portion in the copolymer.

(a) (b)
Figure 6. FTIR spectra of MB, NB, B1, B2, and B3 bitumen samples (a) all ranges; (b) range between 1800 and 600 cm−1.

Table 5. Assignments of the main IR bands of bitumen samples and their composites.

Samples
Assignment Groups Assignment
MB NB B1 B2 B3
υst C-H Aliphatic species 2900 2900 2900 2900 2900
υst C=O Free carbonyl 1741 n.d. 1716 1716 1716
υst C=O Conjugate carbonyl 1685 n.d. n.d. n.d. n.d.
υst C=C Aromatic ring vibration 1605 1601 1590
Wavenumber (cm-1) 1590 1590
δ C-H Methylene 1373 1373 1373 1373 1373
υst S=O Sufoxide 1033 1030 1031 1031 1031
υst C-O-C Ether n.d. n.d. 1015 1015 1015
Sustainability 2021, 13, 13887 12 of 22

υst -HC=CH- Trans-butadiene block 965 n.d. 968 968 968

δ C-H Styrene block 748 748 748 748 748
δ C=C Aromatic ring vibration 813 815 815 815 815

From the discussion above, it can be concluded that the addition of PW does not
affect the oxidation process of SBS-based bitumen, but its presence significantly improves
the aging resistance if compared to results obtained using other fillers such the crumb
rubber, as also observed by other authors [60].

3.2. Thermal Analysis (TGA and DSC) of Neat Plastic Waste, Neat Bitumen, and Their
Composites
To better evaluate the effect of PW on the thermal behavior of composite bitumen,
thermal degradation properties of neat PW through TGA (in both air and N2 atmosphere)
and DSC analysis have been carried out and the results are reported in Figure 7. In partic-
ular, TGA in a N2 atmosphere of the PW sample (Figure 7a) showed a degradation step
in the range 360–420 °C with an onset temperature at 361 °C, and a corresponding weight
loss of about 90%, that is likely related to the thermal degradation of PET. As already
evidenced by FTIR analysis, DSC results (see Figure 7b) clearly show that the main com-
ponent of the mixture is PET, with its typical melting temperature observed at 248 °C. In
addition, from TGA under air atmosphere (reported in Figure 7c) the thermogram shows
three separate portions of the mass loss curve: the first one correlated to the HDPE/PP mix
(around 3 wt% of mass loss) and the second one to the PET (around 84 wt% of weight
loss), both degrade quickly into char and volatiles at around 150–250 °C and 377–527 °C,
respectively [61]. In the third part, further increase in temperature slowly decomposed
(~13%) the char, which is combusted by reacting with oxygen. From this last analysis, it is
possible to assume that in the PW mixture there are 96.5 wt% of PET and 3.5 wt% of
HDPE/PP mix.

(a) (b) (c)

Figure 7. (a) TGA and DTGA in N2 atmosphere, (b) DSC analysis, and (c) TGA in air atmosphere of PW sample.

In Figure 8 the thermograms of the MB, NB, and their derivatives are reported. The
DTG (see Figure 8b) was used to identify the point at which weight loss is more evident
and to determine: (i) the onset degradation temperature (Tonset), (ii) the maximum decom-
position temperature (Tmax), and (iii) the corresponding weight loss as well as (iv) the yield
of residual char. The main data are summarized in Table 6. For all the investigated sys-
tems, an intense degradation event related to the random break/rupture process and sub-
sequent pyrolysis of the components present in the bitumen samples was observed [62].
The DTG curves (see Figure 8b), showed that MB has the lowest thermal stability with
respect to all the other samples, whereas the NB sample exhibited higher thermal stability
with respect to its composites. This is due to the presence of the polymeric waste (PET-
HDPE-LDPE-PP) which, with its Tmax equal to 427 °C, slightly decreases the Tmax value of
NB from 456 °C to 442, 434, and 435 °C, for the three investigated blends B1, B2, and B3,
respectively.
Sustainability 2021, 13, 13887 13 of 22

(a) (b)
Figure 8. (a) Thermograms with the inset of two main sections of the graph zoomed in and (b) derivative thermograms of
bitumen samples and their composites.

Table 6. Thermal properties of bitumen samples.

Sample Tonset (°C) Tmax (°C) Loss Weight (wt%) Char (wt%)
PW 361 427 90% 10.20
MB 200 452 84.00 16.00
NB 276 456 85.75 14.25
NBat150°-10 min 278 456 87.00 13.00
B1 275 442 86.20 13.80
B2 275 434 85.00 15.00
B3 276 435 85.30 14.30

In Figure 9, DSC thermograms of all the investigated samples are reported. MB and
NB samples showed glass transition temperature (Tg) values of −20 °C, 10 °C, and 60 °C
which Özdemir et al. [63] associated, respectively, to the saturate, aromatic, and resin com-
ponents of the bitumen. During the evaluation of possible interactions among the compo-
nents in the bituminous blend, the obtained DSC results showed that the presence of PW
does not bring any significant change in the Tg of the composites, whereas some differ-
ences can still be observed in the melting temperatures. Indeed, DSC curves revealed two
sharp melting peaks (Tm = 246 °C and 256 °C) which indicates, as expected, the presence
of plastic components in the blend and, particularly, the presence of different types of
polymers in the PW including PET whose crystalline melting temperature is about ∼260
°C. It is worth noting that the blend of bitumen and PW is incompatible in nature [63].
They observed that, at low PW content (up to 5%), the presence of small melting peaks
has been observed, indicating some level of compatibility. However, at higher loading
content (i.e., 7%), two distinct and sharp melting peaks have been observed, thus indicat-
ing a high level of incompatibility of polymers in the bituminous matrix. Similar behavior
was observed in the DSC curves of the samples investigated in the present work, thus
confirming the incompatibility of the blends.
Sustainability 2021, 13, 13887 14 of 22

Figure 9. DSC curves of asphalt samples and their composites.

3.3. Performance Results of Asphalt Binder and Mixtures

In the first analysis, to evaluate the FS results the master curves have been designed
(see Figure 10) [32].
In Figure 10 it can first be observed that the three blends show different behavior as
the temperature increases if compared to NB. At low temperatures, the B2 and B3 blends
behave in the same way as NB in terms of |G*|, while B1 showed a 47% higher |G*| than
NB; at high test temperatures, the behavior of B2 and B3 is changed, resulting in a |G*|
value respectively 80 and 333% higher compared to NB.
For test temperatures below 30 °C, B1 returned a |G*| value on average 77% higher
than that of NB, while for test temperatures above 30 °C, B3 achieved a |G*| on average
333% higher than NB.
Comparing the three blends (B1, B2, and B3) it is possible to notice that the complex
shear modulus of B1 for temperatures below 30 °C is on average 31 and 34% higher than
B2 and B3 respectively; at test temperatures above 30 °C B1 is kept above B2 on average
by 20%, while compared to B3 is reduced of 37%.
In order to identify if the performance of the three blends matched the modified bi-
tumen (MB), a further comparison between MB and the three blends was carried out. It is
noticeable from Figure 10 that MB returned for test temperatures below 40 °C a |G*| value
on average 40% lower than the three asphalt blends, instead for temperatures above 40
°C, MB achieved the best performance, in particular |G*| is slightly higher of 5% than B3
that returned the highest |G*| values for high test temperatures in comparison to the re-
maining blends with PW (B1 and B2).
Sustainability 2021, 13, 13887 15 of 22

Figure 10. Comparing asphalt blends and binders in terms of master curves.

At high temperatures, the asphalt binders behave like viscous fluids with no capacity
for recovering with no viscous component of |G*|, since δ = 0°. Under normal pavement
temperature and traffic loading, bituminous binders act with the characteristics of both
viscous liquids and elastic solids; when the binders are loaded, part of their deformation
is elastic and part is viscous. Even if two binders are viscoelastic and have the same |G*|,
the smaller δ value establishes which one is more elastic than the other, and the defor-
mation could be recovered much more from an applied load.
Therefore, an analysis of the phase angle was carried out. First of all, as reported in
Figure 10, it is noticeable that the phase angles of the three blends are on average 11%
lower than NB; looking in more detail the single blends B1 and B2 returned, in particular,
a constant decrease of 8% regardless of the temperatures, while B3 until 30 °C is 14% lower
than NB decreasing even more of 19% and 29% at 40 and 50 °C, respectively. In this case,
it is evident that the elasticity of the blends is given by the amount of PW that for B3
resulted higher than B1 and B2 and it is not dependent on the PW size since B1 and B3
returned the same δ values.
Comparing the blends with the modified bitumen at 0 °C, the δ values of B1, B2, and
MB matched, while B3 returned a 9% lower phase angle values.
Since 30 °C resulted in a change of behavior for all the solutions so far analyzed, a
Cole–Cole diagram at 30 °C was designed to evaluate in more detail the elastic component
in the function of the viscous one (see Figure 11).
The elastic degree of the blends, as is shown in Figure 11, was 10%, 8%, and 21%
higher than NB for B1, B2, and B3, respectively. The modified bitumen instead, as previ-
ously shown by phase angle analysis through the mater curve, returned the highest de-
gree of elasticity between the two bitumen and the three blends.
Sustainability 2021, 13, 13887 16 of 22

Figure 11. Cole֪–Cole diagram at 30 °C.

The measure of the binder’s contribution to mixture permanent deformation is cal-

culated through Jnr. The lower value of Jnr confirms the better performance of the asphalt
binder sample against permanent deformation. The results reported in Table 7 reveal that
by adding the PW the Jnr decreased compared to the neat binder; in fact, taking into ac-
count the average at both test temperatures (40 and 50 °C) and both stress levels (0.1 and
3.2 kPa), overall the Jnr values of the three blends (B1, B2, and B3) are on average 82%
lower than NB.
Looking into detail at the Jnr value of the three blends at 40 °C, under both 0.1 and
3.2 kPa, B3 was 71% lower than B1 and B2; at the same time, B1 had a 17% lower Jnr value
with respect to B2 at 0.1 kPa, while no substantial difference occurs between them at 3.2
kPa.
At the test temperature of 50 °C, under both stress levels, B3 showed lower Jnr values
than B1 and B2, 72% and 65%, respectively. Comparing B1 and B2, B1 returned a Jnr value
on average 22% lower.
A further comparison was made with the modified bitumen (MB), that compared to
NB returned on average 92% lower Jnr values. Among all blends, B3 returned 55% and
2% lower Jnr value compared to MB under 0.1 kPa respectively at 40 and 50 °C.

Table 7. MSCR results: Jnr and Jtot both at 40 and 50 °C.

Jnr Jtot
Sample 40 °C 50 °C 40 °C 50 °C
0.1 kPa 3.2 kPa 0.1 kPa 3.2 kPa 0.1 kPa 3.2 kPa 0.1 kPa 3.2 kPa
NB 0.1628 0.1722 1.1230 1.2119 0.1647 0.1739 1.1266 1.2125
MB 0.0115 0.0185 0.0509 0.0787 0.0170 0.0219 0.0639 0.0903
B1 0.0309 0.0493 0.1746 0.2981 0.0342 0.0515 0.1880 0.3030
B2 0.0360 0.0462 0.2403 0.3575 0.0389 0.0484 0.2538 0.3621
B3 0.0051 0.0205 0.0499 0.1204 0.0152 0.0224 0.0614 0.1258

Figure 12 shows two 3D scatter plots where the x-axis shows Jtot, the y-axis shows
G′, and the z-axis shows Jnr at the test temperatures of 40 (see Figure 12a) and 50 °C (see
Figure 12b). These graphs have been plotted to represent in a synthetic way the degree of
Sustainability 2021, 13, 13887 17 of 22

elasticity of the blends and the binders, better conveyed through a link between the three
characteristic parameters (Jnr, Jtot, and G′). As can be observed from the figure, all the
asphalt blends exhibit behavior completely different from NB and near MB, both at 40 and
50 °C. B1 and B2 appear to be closer to modified bitumen, otherwise, the deviation of B3
compared to MB seems more marked compared to other mastics, due to the higher G′
value for B3. Therefore, among all mixtures, B3 is the most elastic, even more so than MB.

50 °C
40 °C

(a) (b)
Figure 12. Scatter plot by comparing Jtot, G′, and Jnr: (a) 40 °C and (b) 50 °C.

The data in Table 7 provide an exhaustive characterization of the blends since the Jtot
reported were evaluated immediately before load removal. It is evident from the results
that no substantial difference returned the three blends between Jnr and Jtot at the same
temperature and stress level, confirming their ability to recover deformation already after
one second of the end of the creep phase after load removal.
As can be seen from the results above described, B3 returned the most suitable solu-
tion to be compared to a modified bitumen as those objects of the present research.
From the investigation carried out on the asphalt mastics, B3 resulted as the most
suitable blends to be reemployed into asphalt mixtures. Therefore, an internal laboratory
protocol was pursued for mixing the asphalt mixture with the 20% PW by the weight of
NB (HMAB3) as follows:
• The aggregates were preheated for 4 h at 180 °C.
• The PW stored at room temperature was added directly to the aggregates, before the
bitumen. The first blending with coarse aggregates, sand, and PW was performed for
2 min to obtain a homogenous dispersion of all PW particles into the aggregates.
• The next steps involved the addition of the NB, preheated for 1 h at 150 °C, and fur-
ther mixing, for approximately 5 min until the aggregates were fully coated with bi-
tumen.
• The filler was then added, and further mixing was performed for 5 min.
• After the mixing phase, the mixture was put in the oven for 2 h until it reached a
uniform compaction temperature.
Using a Ndes equal to 100 the alternative asphalt mixture, HMAB3, did not exhibit the
same volumetric properties as HMANB, since they differed in the Va values, in particular,
HMAB3 did not satisfy the Superpave requirement for a Va of 4% at Ndes. Hence, the
number of gyrations used for HMAB3 was changed and 120 was found to be the appropri-
ate Ndes. The results of the Superpave optimization for HMAB3 are reported in Table 8a.
Sustainability 2021, 13, 13887 18 of 22

Table 8. (a) Superpave optimization: HMANB vs. HMAB3 volumetric properties and (b) ITS and
ITSM results.

(a)
Asphalt Mix- Va VMA VFA %Gmm atNdes Dust Portion
ture (%) (%) (%) (%) (-)
HMANB 4 14.2 70.6 85.57% 1.1
HMAB3 4 14 71.8 97.64% 1.1
(b)
Asphalt Mix- ITS (MPa) ITSM (MPa)
ture at 10 °C at 10 °C at 20 °C at 40 °C
HMANB 3.37 14853 8120 773
HMAMB 2.97 15391 8613 1051
HMAB3 4.38 16498 9582 1440

The first mechanical characterization of the asphalt mixtures was carried out through
the ITS test, whose results are shown in Table 8b. HMAB3 showed the highest ITS at 10 °C
than the other two mixtures, in particular, it was 47.4 and 30% higher than that of the
HMAMB and HMANB, respectively. The asphalt mixture made up of MB revealed the low-
est ITS at 10 °C (2.97 MPa). This is related to the MB used for making the asphalt mixture
since no differences existed in terms of the grading curves, volumetric properties, or bitu-
men concentrations among all the optimized mixtures.
Table 8b illustrates the mean ITSM for each of the three asphalt mixtures at 10, 20,
and 40 °C. The HMAB3 exhibited a higher ITSM at all test temperatures, in particular +11%
at 10 °C, +18% at 20 °C, and +34% at 40 °C compared to HMANB. Comparing HMAB3 with
HMAMB, a slight increase of 9% at both 10 and 20 °C was observed, while at 30 °C HMAB3
turned a higher ITSM value of 37%. Therefore, it emerges that, as the temperature in-
creases, the beneficial effect produced by the plastic increases in terms of the final stiffness
of the mixture.
In order to better analyze the effect of the introduction of PW in both asphalt binder
and asphalt mixtures, all the parameters analyzed either by the mechanical characteriza-
tion of the mixtures or by the rheological analysis of the asphalt mastics are summarized
in Table 9, as a function of temperature. As it can be seen, for all the parameters analyzed
it appears that the best performance is attributable to both asphalt mixtures and the binder
containing PW (see the red values in Table 9). The highest stiffness shown by both the
binder and the mixture containing PW (via ITSM and |G*|) is fully due to the plastic con-
tent because through the FTIR analysis it has been demonstrated that the mixing phase
does not produce aging phenomena of bitumen that can stiffen it. In addition, this result
was also validated by the analysis of the descriptive parameters of the elasticity of the
asphalt mixtures and binders through G′, δ, Jnr, and Jtot which returned a higher elasticity
in the case of B3 and HMAB3; this is obviously due to the solid presence of PW as it has
emerged from the TGA and DSC analysis that at the mixing temperatures of 150 °C, used
in this case study, do not produce degrading phenomena of PW and above all that, not all
types of PW reach their melting point.
Sustainability 2021, 13, 13887 19 of 22

Table 9. Summary of the asphalt blends and mixtures results.

10 °C 20 °C 40 °C
Asphalt Mixture HMANB HMAMB HMAB3 HMANB HMAMB HMAB3 HMANB HMAMB HMAB3
ITS (MPa) 3.370 2.970 4.380 n.d. n.d. n.d. n.d. n.d. n.d.
ITSM (MPa) 14,853 15,391 16,498 8120 8613 9582 773 1051 1440
Asphalt Binder NB MB B3 NB MB B3 NB MB B3
|G*| (MPa) 20.080 13.284 25.807 3.601 3.181 5.901 0.853 0.995 0.274
G′ (MPa) 14.410 10.448 20.164 1.837 2.150 3.609 0.151 0.593 0.102
G″ (MPa) 13.8541 8.170 15.931 3.084 2.339 4.647 0.839 0.799 0.254
δ (°) 47.935 41.675 40.003 63.776 49.514 55.954 82.031 53.398 66.808
Jnr (kPa−1) n.d. n.d. n.d. n.d. n.d. n.d. 0.167 0.015 0.013
Jtot (kPa−1) n.d. n.d. n.d. n.d. n.d. n.d. 0.169 0.019 0.019

4. Conclusions
In this study, the effect of the different sizes and contents of plastic waste were as-
sessed through the chemical, thermal, and rheological investigation of asphalt blends
mixed with PW in comparison with a neat bitumen 50/70 and modified bitumen. The plas-
tic waste was a mixture of different plastic waste types with a prevalence of PET and PE.
The results obtained lead to the following conclusions:
• FTIR results highlight that the presence of PW does not affect the oxidation process
of SBS-based bitumen, but significantly improves the aging resistance if compared to
results obtained using other fillers such as crumb rubber.
• From the rheological and mechanical investigation, it can be seen that as the temper-
ature increases, there is an increase of the beneficial effect produced by the addition
of PW in both asphalt blends and mixtures.
• A total of 20% PW by weight of NB with a size range between 4 and 0.063 mm was
found to be the blend that performs better than the modified bitumen since in terms
of stiffness and elasticity; particularly, PW is beneficial to the high temperature
achieving lower phase angle and Jnr values (averagely 30% than the other asphalt
solutions investigated).
• The adoption of PW as a modifier of the mixture through the dry method, shown by
preliminary study on the mechanical characterization of the optimized asphalt mix-
ture by means of Superpave method, was found to produce an increase of the ITS
and ITSM at all test temperature in comparison to the asphalt mixtures made up of
NB and MB, despite all mixtures having the same volumetric properties.
It was discovered that during the mixing phase of 150 °C, no melting temperatures
and degradation process have been achieved by PW that increases the overall strength
and elasticity of the innovative asphalt blends and mixtures.

Author Contributions: Conceptualization, R.V. and G.G.B.; methodology, R.V., C.O. and F.R.; val-
idation, H.M., S.A.B. and F.R.; investigation, R.V., N.V. and L.V.; data curation, N.V., C.O., G.G.B.
and L.V.; writing—original draft preparation, R.V. and L.V.; writing—review and editing, G.G.B.
and F.R..; visualization, G.G.B. and F.R.; supervision, H.M., S.A.B. and F.R. All authors have read
and agreed to the published version of the manuscript.
Funding: This research was developed within the Projects of National Interest-PRIN 2017 “Stone
pavements. History, conservation, valorisation and design” (20174JW7ZL) financed by the Ministry
of Education, University and Research (MIUR) of the Italian Government.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Sustainability 2021, 13, 13887 20 of 22

Acknowledgments: The Italy/Mozambique Cooperation project Preparation And Characterization

Of Polyolefin Waste Blends/Bitumen Composites For Flexible Road Pavement funded by FIAM
(Fundo para a Investigacao Applicada e Multissectiorial) is kindly acknowledged. The authors are
grateful to Mario De Angioletti (CNR-IPCB), Fabio Docimo (CNR-IPCB), Mariarosaria Marcedula,
and Alessandra Aldi (CNR-IPCB) for technical support.
Conflicts of Interest: The authors declare no conflict of interest.

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