Properties of Bituminous Binder Modified With Waste Polyethylene

Terephthalate(PET)
Zahra KALANTAR, Abdelaziz MAHREZ, Mohamed Rehan KARIM
Civil Engineering Department, Faculty of Engineering, University of Malaya
50603 Kuala Lumpur - Malaysia
Email: niloofar.kl@gmail.com, mahrez@um.edu.my, rehan@um.edu.my

ABSTRACT

The purpose of this research is to investigate the possibility of using Polyethylene Terephthalate
as polymer additives in Bituminous Mix. The characteristics of PET-modified binder obtained by
fix mixing temperature. was investigated. The binders were prepared by mixing the PET in 2%,
4%, 6%, 8% and 10% (by the weight of optimum bitumen) with 80/100 penetration grade
bitumen at temperature of 150 ºC. It may be inferred that PET-modified bituminous binders
provide better resistance against permanent deformations due to their higher complex shear
modulus and lower phase angle as compared to conventional binder. It also contributes to
recirculation of plastic wastes as well as to the protection of the environment.

Keywords: Polyethylene Terephthalate, modified bitumen, binder test.

1. INTRODUTION

The performance of the road pavement is determined by the properties of the bitumen, as
bitumen is the continuous phase and the only deformable component (Yuonne et al., 2001). And
also is a viscoelastic material with suitable mechanical/rheological properties for traditional
paving and roofing applications because of their good adhesion properties to aggregates
(González Uranga, 2008).
The most important property of the bitumen mixture in the wearing course design is its ability to
resist shoving and rutting under traffic. Therefore, stability should be high enough to handle
traffic adequately, but not higher than the traffic conditions required. The lack of stability in an
asphalt mixture causes unraveling and flow of the road surface. Flow is the ability of an HMA
(Hot Mixture Asphalt) pavement to adjust to gradual settlements and movements in the sub
grade without cracking. The flow may be regarded as an opposite property to the stability,
determining the reversible behavior of the wearing course under traffic loads and affecting
plastic and elastic properties of the asphalt (Kulog¢lu, 1999).
The chemical composition of the bitumen has a significant effect on its viscoelastic properties
and hence on its performance as road paving material in asphalts. Rutting at high temperatures,
crack initiation, and propagation in the low temperature region and other forms of pavement
defects are due not only to traffic loads but also to the capability of the asphalt concrete to
sustain temperature changes. Increased traffic factors such as heavier loads, higher traffic
volume, and higher tire pressure demand higher performance pavements. A higher performance
pavement requires bitumen that is less susceptible to high temperature rutting or low
temperature cracking, and has excellent bonding to stone aggregates
Some improvements in asphalt properties have been achieved by selecting the proper starting
crude, or tailoring the refinery processes used to make asphalt. Unfortunately, there are only a
few crudes that can produce very good asphalts, and only a limited number of actions that can
be taken to control the refining process to make improved asphalts (Yuonne et al., 2001). The
next step taken by the industry was to modify the asphalt. Air blowing makes asphalt harder.
Fluxing agents or diluent oils are sometimes used to soften the asphalt. Another method that
can significantly improve asphalt quality is the addition of polymers (Yuonne et al., 2001).
It’s well known that the addition of both, some waste material and certain polymers to asphalt
binders can improve the performance of road pavement. To achieve this improvement, it is
necessary the addition of natural or synthetic polymers to the bitumen and a common method
of modifying the rheological properties of bitumen is by blending with polymers (González
Uranga, 2008).
For the past two decades significant research has been conducted on polymer modified asphalt
(PMA) mixtures. Polymers can successfully improve the performance of asphalt pavements at
low, intermediate and high temperatures by increasing mixture resistance to fatigue cracking,
thermal cracking and permanent deformation (Aflaki & Tabatabaee, 2008). The addition of
polymers to enhance service properties over a wide range temperature in road paving
applications was considered a long time ago and nowadays has become a real alternative.
Addition of natural or synthetic polymers to bitumen is known to impart enhanced service
properties. By adding small amounts of polymers to bitumen, the life span of the road pavement
may be considerably increased. The purpose of bitumen modification using polymers is to
achieve desired engineering properties such as increased shear modulus and reduced plastic
flow at high temperatures and/or increased resistance to thermal fracture at low temperatures
and decreased permanent deformation under load (rutting). Other benefits include greater
adhesion to the aggregate and increased tire traction (González Uranga, 2008).
Improvement in rutting resistance, thermal cracking, fatigue damage, stripping, and temperature
susceptibility have led polymer modified binders to be a substitute for asphalt in many paving
and maintenance applications, including hot mix, cold mix, chip seals, hot and cold crack filling,
patching, recycling, and slurry seal. They are used wherever extra performance and durability
are desired. In many cases, they are selected to reduce life cycle costs (Yuonne et al., 2001).
Polymer modified binders also show improved adhesion and cohesion properties (Awwad &
SHbeeb 2007).
Polymer modification of asphalt binders has increasingly become the norm in designing
optimally performing pavements. Mixing polymers into bitumen has important consequences on
the engineering properties of bituminous binders. Thus, structural and chemical changes may
be observed during processing of polymer-modified bitumen (Pe´rez-Lepe,A et al., 2003).
The uses of virgin polymers in bitumen to improve the characteristics of resulting polymer
modified bitumen have been accomplished for many years (González Uranga, 2008).
Nevertheless, recently there is interest in the substitution of commercial virgin material by
recycled polymers. Reclaimed rubber obtained from used tires has been used with beneficial
effects in paving (González Uranga, 2008).
The high cost of the polymers compared to bitumen means that the amount of polymer needed
to improved pavement performance should be as small as possible. From an environmental and
economic standpoint, it is possible to envisage the possibility of disposing of troublesome waste
plastics within road bitumens because recycled polymers can show similar performance to
those which contain virgin polymers. Thus, the use of crumb tire rubber or polymers used in
greenhouses, like polyethylene or ethylene-vynil acetate (EVA), as a bitumen-modifying agent
may contribute to solve a waste disposal problem and to improve the quality of road pavements
(González Uranga, 2008).Many polymers have been used as binder modifiers, and they can be
classified into five groups. Table 1 presents a summary of these polymers and their advantages
and disadvantages as asphalt modifiers (Yuonne et al., 2001).
The polymers used in modifying bitumen are also classified as plastomers and elastomers.
Plastomers include ethylene vinyl acetate, Polyethylene and various compounds based on
polyethylene. These products may require high shear mixing which depends on the modification
process. They increase the viscosity and stiffness of bitumen at normal service temperatures.
 However, they do not increase the elasticity of bitumen significantly and on heating, they do not
perform satisfactory (Awwad & SHbeeb 2007).
Table 1 Characteristics of polymers used to modify bitumen (Yuonne et al., 2001).
Polymer Advantages Disadvantages Uses
Polyethylene High temperature resistance Hard to disperse in the bitumen Industrial uses
(PE) Aging resistance Instability problems
High modulus High polymer contents are Few road
Low cost required to achieve better applications
properties.
No elastic recovery
Polypropylene No important viscosity increase Separation problems Isotactic PP is
(PP) not commercially
even though high amounts of No improvement in elasticity or applied
polymer are necessary (ease of mechanical properties
handling and layout) Atactic PP is
High R&B Low thermal fatigue cracking used for roofing
Low penetration resistance.
Widens the plasticity range and
improves the binder's load
resistance
PVC Lower cracking PVC disposal Acts mostly as filler Not commercially
applied
Styrene- Higher flexibility at low High cost Paving and
butadiene temperatures roofing
block copolymer Better flow and deformation Reduced penetration resistance
(SBS) resistance at high temperatures
Strength and very good Higher viscosity at layout
Styrene-isoprene elasticity temperatures
block Increase in rutting resistance Resistance to heat and to
copolymer (SIS) oxidation is lower than that of
polyolefins (due to the presence
of double bonds in the main
chain)

The main reasons to modify asphalts with polymers could be summarized as follows
(Lewandowski,1994).
• To obtain softer blends at low service temperatures and reduce cracking
• To reach stiffer blends at high temperatures and reduce rutting
• To reduce viscosity at layout temperatures
• To increase the stability and the strength of mixtures
• To improve the abrasion resistance of blends
• To improve fatigue resistance of blends
• To improve oxidation and aging resistance
• To reduce structural thickness of pavements
• To reduce life costs of pavements.

Polyethylene has been found to be one of the most effective polymer additives (Hinisliglu &
Agar 2004). Polyethylene is the most popular plastic in the world. Polyethylene is semi-
crystalline materials with excellent chemical resistance, good fatigue and wear resistance and a
wide range of properties. It has a very simple structure. A molecule of polyethylene is a long
chain of carbon atoms, with two hydrogen atoms attached to each carbon atom They are light in
weight; provide good resistance to organic solvents with low moisture absorption rates (Awwad
& Shbeeb 2007).
Polyethylene terephthalate (PET) is a linear, aromatic polyester (Bing Sh et al., 2006). PET is
commonly recycled, and has the number "1" as its recycling symbol. (Figure1) The chemical
structure of PET is shown in Figure 2.

Figure 2 PET recycling symbol

Figure 1 Chemical structure of polyethylene terephthalate (http://scifun.chem.wisc.edu)
(Bing Sh et al., 2006)

2. MATERIALS AND METHODS

2.1. Bituminous material

Asphalt binder 80/100 penetration grade bitumen was used in this research. The laboratory
tests performed to evaluate the bitumen properties were: Specific Gravity, Ductility, Penetration
and Softening point. The properties of asphalt binder, which are presented in Table 2, are within
the specification of penetrated bitumen grade 80/100.

2.2. Polyethylene

In this investigation, waste PET in the powdered form in 2%, 4%, 6%, 8% and 10% (by the
weight of bitumen) was used as a modifier. About 50 waste mineral water bottles were crushed
in the crusher machine and then were sieved. The properties of PET are as follows: density
1370 kg/m3 and melting point 260 °C. The gradation of PET is presented in Table 3.

Table 2 The results of tests performed on bitumen

Test Test result
Ductility (cm) < 100
Penetration (0.1 mm) 84-100
Softening point (C°) 46
Specific Gravity 1.03
(g/cm3)

Table 3 Gradation of PET

Sieve size Percent passing
701 µm 100
450 µm 0

2.3. Sample preparation

The method used in this study is dry mix. Bitumen was heated for about 1 hour in temperature
of 130 ºC then PET was added and blended for about 2 min. Immediately after mixing DSR test
samples were prepared then mixture were placed in viscosity sample chambers after that,
softening point rings and then penetration cups. After having cool in room temperature for 1 day
samples were tested.

3. RESULTS AND DISCUSSION

This chapter discusses the results of laboratory tests. Binders are characterised by using a
number of standard physical tests such as penetration test (temperature, load and time are
25ºC, 100g and 5sec respectively), softening point test, viscosity test using Brookfield
viscometer (temperature range from 90 to 170 ºC, spindle No.27, and a rotating speed of
20rpm), and also rheological measurements by using a Dynamic Shear Rheometer (tests
conducted by using a fix temperature 76 ºC, and the frequency is 1.159Hz).

3.1 Penetration test

The Penetration test equipment first published in 1959, describes the following basic procedure:

• Melt and cool the asphalt binder sample under controlled conditions.
• Measure the penetration of a standard needle into the asphalt binder sample under
the following conditions:

o Load = 100 grams

o Temperature = 25º C (77º F)
o Time = 5 seconds

The depth of penetration is measured in units of 0.1 mm and reported in penetration units (e.g.,
if the needle penetrates 8 mm, the asphalt penetration number is 80). Penetration Grading is
based on the penetration test (Pavement Interactive).
Figure 3 shows the variation of penetration value with the various percentages of bitumen
modified PET and it shows that consistency decreases with the addition of PET. The
penetration values for the modified binders decrease as the PET content in the mix increase.
The decrease is 2.4%, 4.9%, 8.5%, 11% and 14.6% with the addition of 2%, 4 %, 6%, 8% and
10% of PET, respectively, as compared to the original bitumen. This means that the addition of
PET makes the modified bitumen harder and more consistent. This is good in one sense since it
might improve the rutting resistance of the mix, but on the other hand this may affect flexibility of
the bitumen by making the asphalt much stiffer, thus the resistance to fatigue cracking can be
affected.

3.2 Softening point

The softening point is defined as the temperature at which a bitumen sample can no longer
support the weight of a 3.5-g steel ball. Basically, two horizontal disks of bitumen, cast in
shouldered brass rings are heated at a controlled rate in a liquid bath while each supports a
steel ball. The softening point is reported as the mean of the temperatures at which the two
disks soften enough to allow each ball, enveloped in bitumen, to fall a distance of 25 mm (1.0
inch) (AASHTO, 2000).
Figure 4 shows that softening point increases with increasing PET content. It appears clearly
from the results that the addition of PET to bitumen increases the softening point value, and as
the PET content increase the softening point also increases. This phenomenon indicates that
the resistance of the binder to the effect of heat is increased and it will reduce its tendency to
soften in hot weather. Thus, with the addition of PET the modified binder will be less susceptible
to temperature changes.
The effect of softening point of a binder on resistance to permanent deformation of bituminous
pavement mixes has been studied by various researchers. An example is hot rolled asphalt
where it was found that the rate of rutting in the wheel tracking test at 45°C, was halved by
increasing softening point by approximately 5ºC (Fernando & Guirguis, 1984). Therefore it is
expected that by using the PET in the bituminous mix the rate of rutting will decrease due to the
increase in softening point.

85

80 R2 = 0.9977
pentration (0.1 mm)

75

70

65
0% 2% 4% 6% 8% 10% 12%
PET percentages

Figure 3 Penetration grade vs. different percentage of PET

51

50
Softening point (°C)

R2 = 0.9918
49

48

47

46

45
0% 2% 4% 6% 8% 10% 12%
PET Percentage

Figure 4 Softening point vs. different percentage of PET

3.3 Rotational Viscosity

The Rotational Viscometer (RV) is used to determine the viscosity of asphalt binders in the high
temperature range of manufacturing and construction. This measurement is used in the
Superpave PG asphalt binder specification. The RV test can be conducted at various
temperatures, but since manufacturing and construction temperatures are fairly similar
regardless of the environment, the test for Superpave PG asphalt binder specification is always
conducted at 135°C. The RV test helps ensure that the asphalt binder is sufficiently fluid for
pumping and mixing (Roberts et al., 1996).
The basic RV test measures the torque required to maintain a constant rotational speed (20
RPM) of a cylindrical spindle while submerged in an asphalt binder at a constant temperature.
This torque is then converted to a viscosity and displayed automatically by the RV.
The viscosity of asphalt binder at high manufacturing and construction temperatures (generally
above 135°C is important because it can control the following:

• Pumpability. The ability of the asphalt binder to be pumped between storage facilities
and into the HMA manufacturing plant.
• Mixability. The ability of the asphalt binder to be properly mixed with and to coat
aggregate and other HMA constituents in the HMA manufacturing plant.
• Workability. The ability of the resultant HMA to be placed and compacted with
reasonable effort (Pavement Interactive).

Modified asphalt binders are usually more viscous than unmodified ones (Aflaki & Tabatabaee,
2008). Figure 5 shows the viscosity curves of Modified bitumen and Table 4 shows the ratio of
viscosity of the modified asphalt binders to viscosity of the base binder at 135 °C. This ratio
varies between 1 and 2 for the modifiers used in this study. In the extreme case of adding 10 %
PET to the base binder, the viscosity increased from 275 mPas to 538 mPas. This value is less
than 3000 mPas and therefore satisfies the ASTM D6373 criterion for asphalt binder workability
(Aflaki & Tabatabaee, 2008).

Table 4 Viscosity ratio of modified asphalt binders

Viscosity
Sample Viscosity Ratio
(mPas)

Original Binder 275.0 --

Modified with 2% PET 290 1

Modified with 4% PET 305 1.1

Modified with 6% PET 325 1.2

Modified with 8% PET 394 1.4

Modified with 10% PET 538 2

 10000

9000

8000

Viscosity (mPas) 7000

6000
0%
5000
2%
4000
4%
3000
6%
2000 8%
1000 10%

0
80 90 100 110 120 130 140 150 160 170 180

Temprature (°C)

Figure 5 Viscosity vs. Temperature

3.4 Dynamic Shear Rheometer (DSR)

The dynamic shear rheometer (DSR) is used to characterize the viscous and elastic behavior of
asphalt binders at medium to high temperatures.
The basic DSR test uses a thin asphalt binder sample sandwiched between two circular plates.
The lower plate is fixed while the upper plate oscillates back and forth across the sample at 10
rad/sec (1.59 Hz) to create a shearing action. DSR tests are conducted on unaged, RTFO aged
and PAV aged asphalt binder samples. The test is largely software controlled.
Asphalt binders are viscoelastic. This means they behave partly like an elastic solid
(deformation due to loading is recoverable – it is able to return to its original shape after a load
is removed) and partly like a viscous liquid (deformation due to loading is non-recoverable – it
cannot return to its original shape after a load is removed). Having been used in the plastics
industry for years, the DSR is capable of quantifying both elastic and viscous properties. This
makes it well suited for characterizing asphalt binders in the in-service pavement temperature
range (Pavement Interactive).
The DSR measures a specimen's complex shear modulus (G*) and phase angle (δ). The
complex shear modulus (G*) can be considered the sample's total resistance to deformation
when repeatedly sheared, while the phase angle (δ), is the lag between the applied shear stress
and the resulting shear strain. The larger the phase angle (δ), the more viscous the material.
Phase angle (δ) limiting values are: (FHWA, 1995)

• Purely elastic material: δ = 0 degrees

• Purely viscous material: δ = 90 degrees (Zaniewski, 2004)

The specified DSR oscillation rate of 10 radians/second (1.59 Hz) is meant to simulate the
shearing action corresponding to a traffic speed of about 55 mph (90 km/hr).
G* and δ are used as predictors of HMA rutting and fatigue cracking. Early in pavement life
rutting is the main concern, while later in pavement life fatigue cracking becomes the major
concern.
The phase angle, δ, represents the relative distribution between the elastic response and the
viscous response to loading of the asphalt binder (Basu et al., 2003). Figure 6 presents with
increasing the PET content δ doesn’t change. The δ of contents is 88 °_ 90 °. For all contents
sin δ = 1.
The complex shear modulus (G*) is a ratio of the applied shear stress (τ) to the resulting shear
strain (γ). A lower value of complex shear modulus G* means that the asphalt is softer, and it
can deform without developing large stresses (Samsuri & Karim, 1997). In addition binders with
high complex shear modulus G* may reduce rutting problems (deformations) in the asphalt. In
order to resist rutting, an asphalt binder should be stiff (it should not deform too much) and it
should be elastic (it should be able to return to its original shape after load deformation) (Kose
et al., 2000). Therefore, the complex shear modulus elastic portion, G*/sin δ, should be large.
Since sin δ = 1 complex shear modulus elastic portion is depends on G*. Figure 7 shows G*
increases with increasing the PET content then adding polymer can reduce rutting problems.

90
phase angle, δ (°)

60

30

0
0% 2% 4% 6% 8% 10% 12%
PET Percentage

Figure 6 Phase angles vs. different percentage of PET

450
complex modulus G* (Pa)

400 R2 = 0.96

350

300

250

200
0% 2% 4% 6% 8% 10% 12%
PET Percentage

Figure 7 Complex shear modulus vs. different percentage of PET

4. CONCLUSIONS
Based on the laboratory test results the mixture containing PET resulted in higher resistance to
permanent deformation and higher resistance to rutting. It appears that polyethylene
Terephthalate (PET) decreases the consistency and increases the resistance of the material to
temperature changes while the resistance to flow also increases. It may be inferred that PET-
modified bituminous binders provide better resistance against permanent deformations due to
their higher complex shear modulus and lower phase angle as compared to conventional
binder. It also contributes to recirculation of plastic wastes as well as to the protection of the
environment.

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