Journal of Hazardous Materials 279 (2014) 302310

Contents lists available at ScienceDirect

Journal of Hazardous Materials

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

An approach to the usage of polyethylene terephthalate (PET) waste

as roadway pavement material
Metin Gr a, , M. Krsat Cubuk b , Deniz Arslan b , S. Ali Farzanian b , I brahim Bilici c
a

Gazi University, Eng. Fac., Chem. Eng. Depart., 06570 Maltepe-Ankara, Turkey
Gazi University, Eng. Fac., Civil Eng. Depart., 06570 Maltepe-Ankara, Turkey
c
Hitit University, Eng. Fac., Chem. Eng. Depart., 19100 Corum, Turkey
b

h i g h l i g h t s

g r a p h i c a l

We derived two novel additive mate-

a r t i c l e

i n f o

Article history:
Received 4 April 2014
Received in revised form 13 June 2014
Accepted 10 July 2014
Available online 18 July 2014
Keywords:
Modied asphalt
Polyethylene terephthalate
Thin Liquid Polyol PET
Viscous Polyol PET
Fatigue
Stripping resistance

1040
0% (w/w) VPP
3% (w/w) VPP

1000
Marshall Stability (kg)
..

rials from PET bottle waste: TLPP and

VPP.
We used them to modify the base
asphalt separately.
The additives improved both the
asphalt and the asphalt mixture performance.
TLPP, VPP offer a benecial way about
disposal of ecologically hazardous
PET waste.

1% (w/w) VPP
5% (w/w) VPP

2% (w/w) VPP
10% (w/w) VPP

960
920
880
840
800
4

4.5

5.5
Asphalt Content (%)

a b s t r a c t
This study investigates an application area for Polyethylene Terephthalate (PET) bottle waste which has
become an environmental problem in recent decades as being a considerable part of the total plastic
waste bulk. Two novel additive materials, namely Thin Liquid Polyol PET (TLPP) and Viscous Polyol PET
(VPP), were chemically derived from waste PET bottles and used to modify the base asphalt separately for
this aim. The effects of TLPP and VPP on the asphalt and hot mix asphalt (HMA) mixture properties were
detected through conventional tests (Penetration, Softening Point, Ductility, Marshall Stability, Nicholson
Stripping) and Superpave methods (Rotational Viscosity, Dynamic Shear Rheometer (DSR), Bending Beam
Rheometer (BBR)). Also, chemical structures were described by Scanning Electron Microscope (SEM)
equipped with Energy Dispersive Spectrometer (EDS) and Fourier Transform Infrared (FTIR) techniques.
Since TLPP and VPP were determined to improve the low temperature performance and fatigue resistance
of the asphalt as well as the Marshall Stability and stripping resistance of the HMA mixtures based on
the results of the applied tests, the usage of PET waste as an asphalt roadway pavement material offers
an alternative and a benecial way of disposal of this ecologically hazardous material.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Plastics create considerable amount of solid waste in the world
due to their usage in many areas of our lives like packaging, building
and construction, automotive, electric and electronic applications.

Corresponding author. Tel.: +90 312 5823555; fax: +90 312 2308434.
E-mail address: mguru@gazi.edu.tr (M. Gr).
http://dx.doi.org/10.1016/j.jhazmat.2014.07.018
0304-3894/ 2014 Elsevier B.V. All rights reserved.

a b s t r a c t

They are synthetic materials derived mainly from petroleum or

natural gas and composed substantially of carbon, hydrogen and
oxygen combinations. Since they have high decomposition temperature, high resistance to ultraviolet radiation and are mostly
not biodegradable, they can remain on both land and sea for
years causing environmental pollution. Plastics tend to break into
smaller fragments called macro/meso/micro-plastics which have
specic and signicant set of impacts on ecosystem and can affect
human and animal health negatively associated with their chemical

M. Gr et al. / Journal of Hazardous Materials 279 (2014) 302310

Table 1
Physical properties of the base asphalt.

Table 2
Descriptive properties of the aggregate.
Test

Value

Los Angeles abrasion, %

MgSO4 freezing loss, %
Flakiness index, %
Methylene blue
Water absorption, %
Coarse aggregate specic gravity (g/cm3 ), bulk
Apparent
Fine aggregate specic gravity (g/cm3 ), bulk
Apparent
Filler specic gravity (g/cm3 ), bulk
Apparent

9.2
0.16
14.5
1.5
2.11
2.643
2.709
2.732
2.778

2.823

process and investigates the effects of PET waste both on

asphalt and on HMA mixture performances through conventional
tests (Penetration, Softening Point, Ductility, Marshall Stability,
Nicholson Stripping) and Superpave methods (Rotational Viscosity, Dynamic Shear Rheometer (DSR), Bending Beam Rheometer
(BBR)). Also, chemical structures were described by results of SEM
equipped with EDS and FTIR instruments.
2. Materials and methodology
2.1. Asphalt and aggregate
The base asphalt was sourced from Krkkale/Turkey Petroleum
Renery and used throughout the study. Table 1 displays the physical properties of the base asphalt.
100 percent crushed basalt aggregate was used to manufacture
the asphalt mixtures. The descriptive properties of the aggregate
were given in Table 2. Gradation characteristics of the aggregate
used in Marshall Test samples were shown in Fig. 1 which are the
average values of the Type-1 wearing course gradation limits of
Turkeys Highway Technical Specication.
2.2. Preparation of synthetic PET additives
PET waste consisting post-consumer soft-drink bottles was
collected from environment. Collected PETs were purged from contaminants such as PVC, labels and cut by shredder into small pieces
as ake under 10 mm sieve. The akes were washed with soup and
dried 8 h at 105 C. The glycolysis reactions of PET were carried
out in a 1 L ve-necked ask equipped with stirrer, thermocouple and reuxing condenser unit under nitrogen atmosphere to
avoid oxidation. The established glycols, PET and catalyst (0.02% of
ASTM Sieves

200

80

40

10

3/8" 1/2" 3/4"

100
Type-1 Gradation limits
Aggregate gradation

Percent Passing (%)

structure. Toxic chemicals within the plastic can bioaccumulate up

the food chain through ingestion by wildlife meaning that human
can also be subjected to those chemicals.
Plastics are used by almost all end-use segment of the economy
and their usage is quite likely to increase with the developments in
the plastic industry, which in turn causes increase of plastic wastes.
Since they are found to alter the working of ecosystem [13], prevention/minimization of plastic becoming waste and recovery of
this ecologically hazardous waste should be taken into account
instead of being left freely in nature or landlled. Available waste
management systems include recycling and/or energy recovery
operations, but they need to be improved more. New policies
should thus be developed before plastic waste becomes an unsolvable problem.
Being lighter, more durable and less bulky than many alternative materials, one of the main application and so the main
post-consumer waste for plastics is packaging and polyethylene
terephthalate (PET) bottles generate considerable part of this sector. PET has exceptional gas and moisture barrier properties with
high shatter resistance and can contain carbon dioxide which
makes it ideal for use in water and beverage bottles. Single-use
PET bottles have a short service life and therefore turn into residential (post-consumer) plastic waste in a short period of time.
Since PET recycling has not been carried out in the same amount
as its production [4,5], it would be worthwhile to nd out new
application areas for PET bottle wastes to maximize their end-ofservice life management effectiveness. The usage of PET waste as
a reinforcement component for asphalt concrete pavement material, Hot Mix Asphalt (HMA), can be a research area for such an
aim which is still in its infancy. In the previous studies, PET waste
was generally added to the asphalt mixture with dry process (mixture modication) or used as aggregate in the asphalt mixture
(aggregate replacement) in order to improve HMA performance.
Researches have shown that permanent deformation resistance,
Marshall Stability, stiffness and fatigue life of the asphalt mixtures
were increased while moisture damage resistance was decreased
when PET was used as additive in the mixture (mixture modication) [69]. The replacement of aggregate with PET was also
found to increase permanent deformation resistance but decrease
Marshall Stability and stiffness of the mixtures [10,11]. However,
specic gravity of the asphalt mixtures was found to be decreased
by either method [7,11]. Different from the mentioned studies
above, asphalt was modied with additive derived from PET by
aminolysis and found to improve the Marshall Stability depending
on the asphalt and additive contents [12].
The selected additive can be incorporated to the asphalt mixture
by dry process or wet process. The dry process covers mixing the
additive with aggregates prior to adding the binder to the mixture while wet process refers to the modication of the binder
with the additive at an elevated temperature prior to adding the
binder to the mixture. In this study, two novel additive materials,
Thin Liquid Polyol PET (TLPP) and Viscous Polyol PET (VPP), were
derived chemically from PET bottle wastes. This paper presents a
novel approach about the incorporation of PET waste in the form
of TLPP and VPP to HMA mixtures by means of a feasible wet

303

80
60
40
20

Test

Value

Standard

Specic gravity, 25 C (g/cm3 )

Penetration 25 C, 100 g, 5 s (0.1 mm)
Softening point ( C)
Viscosity, 130 C (Pa s)
140 C (Pa s)
Ductility, 15 C (cm)

1.02
45
51.5
0.186
0.126
+105

ASTM D-70
ASTM D-5
ASTM D-36
ASTM D-4402
ASTM D-4402
ASTM D-113

0
0.01

0.1

10

100

Sieve Size (mm), Log

Fig. 1. Gradation characteristics of the Marshall Test samples and specication limits.

304

M. Gr et al. / Journal of Hazardous Materials 279 (2014) 302310

Fig. 2. Additives derived from PET bottle waste by glycolysis reactions; (a) Thin Liquid Polyol PET (TLPP); (b) Viscous Polyol PET (VPP).

PET) were placed in the reactor. Propylene glycol (PG), supplied by

Aklar Kimya, and titanium IV butoxide (TBT), supplied by Aldrich,
were used as glycol and catalyst. Experiments were carried out at
220 C and the reaction was ended when the last piece of PET was
disappeared. Glycolized products, shown in Fig. 2, were labeled
according to the moiety of PET which is 1:2 for Thin Liquid Polyol
PET (TLPP) and 1:1 for Viscous Polyol PET (VPP).
The acid number is dened as the amount of potassium hydroxide required to neutralize 1.00 g of polyol and determined by
titration of the sample solution with 0.1 N KOH solutions (ASTM
D3644). During the glycolysis reactions, acid number was measured
at 1 h intervals. The hydroxyl number (OH number) is dened as the
amount of potassium hydroxide equivalent to the amount of acetic
acid involved in the esterication reaction with 1.00 g of polyol and
determined by the conventional acetic anhydride/pyridine method
(ASTM D4662-03). Acid numbers and OH number of glycolyzed
products (TLPP and VPP) were recorded as 16.4 and 430 for TLPP,
6.7 and 340 for VPP, respectively which were found to be proper
for the glycolysis reaction of PET with PG.
2.3. Modication of asphalt with PET additives
Each additive was added to the base asphalt at ve different proportions: 1%, 2%, 3%, 5% and 10% by asphalt mass. The base asphalt
was put into a metal container and heated to 120 C in an oven
and then the selected additive (TLPP or VPP) was added as abovementioned proportions. Modication process was performed in an
oil bath at 120 C by blending the base asphalt and the additive for
10 min with a mechanical four-armed mixer rotating at 1300 rpm.
2.4. Methodology
This study includes the results of a group of conventional and
Superpave test methods in order to evaluate the effects of PET
modication on the asphalt and HMA mixture performances. Rotational viscosity tests were applied on the base and PET modied
asphalt samples according to ASTM D-4402 using Brookeld DV III
Rheometer with spindle no. 29. Penetration, softening point and
ductility of the asphalt samples with and without PET were measured in accordance with ASTM D-5, ASTM D-36 and ASTM D-113,
respectively. Softening point tests were performed with EL46-4502
model ring and ball apparatus. Ductility tests were carried out at
15 C. Complex shear modulus (G*) and phase angle () values of the
base and modied asphalt samples were measured through DSR
tests at 64 C, 70 C for rutting characteristics and 28 C, 25 C for
fatigue characteristics with respect to AASHTO T315 using Gemini
Rheometer (Bohlin Instrument) with 10 rad/s (1.59 Hz) frequency.
G* and were used as G*/sin and G* sin to compare rutting
resistance and fatigue resistance of the asphalt samples. BBR tests

(AASHTO T313) were carried out with Thermoelectric BBR Instrument (Cannon) at 6 C, 12 C and 18 C through which the creep
stiffness (S) and creep ratio (m) values of the base and modied
asphalt samples were determined in order to evaluate low temperature performance of the asphalt samples. The effect of PET
on the mechanical properties of the HMA mixtures were detected
through Marshall Test (ASTM D1559) and Nicholson Stripping test
(ASTM D1664). Marshall Test samples were produced with 1150 g
basalt aggregate and compacted by 75 blows on each side with
Marshall Compactor device (EL45-6600). The stripping resistances
of the mixtures with and without PET were examined with Nicholson stripping test. The coarse basalt aggregate (6.39.5 mm) was
coated with base and PET modied asphalts separately at 110 C
and then immersed in distilled water at 60 C for 24 h without any
compaction. The stripping resistance of each mixture was visually
determined and the effect of PET on the adhesive bond strength
at the asphalt-aggregate interface was evaluated. The chemical
changes on the base asphalt arisen from the PET modication were
examined by FTIR between 400 and 4000 cm1 using Jasco 480 plus
model test device. FTIR test samples were produced with KBr under
7 tons pressure. SEM images of the asphalt samples were recorded
with JEOL 6360 model SEM (equipped with EDS) apparatus through
which the chemical differences between the test samples were discussed.
3. Results and discussion
3.1. Evaluation of viscosity test results
Viscosity is a fundamental characteristic of any asphalt and
denes the ow resistance of the material at a certain temperature. Related with the fabrication and construction temperatures
of HMA, viscosity tests were applied between 90 C and 160 C
and the results were presented in Fig. 3 as a function of additive
concentration.
The viscosity of the base asphalt was found to be decreased at
all test temperatures by the increase of TLPP concentration. The
decrement has reached to 32.5% at 160 C for 10% (w/w) showing that TLPP can keep its effectiveness at high temperatures and
allows to lower asphalt plant working temperature like organicbased synthetic asphalt modier compounds [1315] and Warm
Mix Asphalt (WMA) additives [16,17]. When the optimum asphalt
viscosity of 0.2 Pa s is considered during HMA mixture fabrication
[18], it is clear from Fig. 3b that TLPP can reduce plant temperature
up to 3.5 C (from 130 C to 126.5 C) through which the heat energy
required for the fabrication of HMA mixtures, the short-term aging
of asphalt and the emissions produced from the asphalt plant will
also be reduced but not much as WMA additives do. Similar viscosity results, except for the concentration rate of 1% (w/w), were

M. Gr et al. / Journal of Hazardous Materials 279 (2014) 302310

5.20
5.00
4.80
4.60
4.40
2.40

90oC

0.20

VPP Modified Asphalt

TLPP Modified Asphalt

0.18

,
Viscosity (Pa.s)

Viscosity (Pa.s)

1.80
1.20
1.10
1.00
0.90
0.80
0.48
0.44
0.40
0.36
0.32

VPP Modified Asphalt

TLPP Modified Asphalt
130 oC

0.16

2.20
100oC

2.00

305

,
110oC

0.14
0.12

140oC

0.10
0.08

150 o C

0.06
120oC

160 oC

0.04
0

Additive Concentration (% w/w)

(a)

10

10

Additive Concentration (% w/w)

(b)

Fig. 3. Viscosity test results of the base and modied asphalts; (a) between 90 C and 120 C; (b) between 130 C and 160 C.

obtained by VPP modication. 1% (w/w) VPP has resulted small

amounts of increases on viscosity varying between 0.4% and 5.4%
due to increased cohesion of asphalt at low VPP amounts whereas
higher VPP concentrations decreased viscosity up to 21.1%. VPP
also keeps its effectiveness at high temperatures and as the temperature increases, in general, the viscosity-reducing effect of VPP
was observed to increase (Fig. 3) leading to reduce the fabrication
temperature of HMA mixtures like TLPP.
3.2. Evaluation of penetration, softening point and ductility tests
results
Table 3 exhibits the penetration, softening point and ductility
tests results of the base and modied asphalt samples. As expected
from the previous test, penetration was increased and softening
point was decreased by TLPP and VPP modications except 1%
(w/w) of VPP. These parameters were found to stay at the same level
for 1% (w/w) VPP. The ductility property was not changed by TLPP
but decreased with the increasing content of VPP which can be seen
in literature studies carried out with different asphalt additives
[19,20]. Softer asphalts may be less susceptible to low temperature
cracking and thus preferred to use in cold regions in terms of better low temperature cracking property as they become less harden
at low temperatures. So, TLPP and VPP modied asphalts were
Table 3
Penetration, softening point and ductility tests results.
Asphalt

Penetration
(0.1 mm)

Softening
point ( C)

Base asphalt
TLPP modied asphalt, 1% (w/w)
2% (w/w)
3% (w/w)
5% (w/w)
10% (w/w)
VPP modied asphalt, 1% (w/w)
2% (w/w)
3% (w/w)
5% (w/w)
10% (w/w)

45
51
54
55
56
61
45
50
54
57
60

51.5
48.7
48.3
48.1
47.9
47.5
51.6
50.3
50.1
50.0
49.8

Ductility @
15 C (cm)
+105a
+105a
+105a
+105a
+105a
+105a
+105a
84
77
68
55

a
The measuring capacity of the ductility test device was 105 cm and the sample
was not broken in the test.

expected to show improved performance at cold climate regions

due to the decreased viscosity and softening point and increased
penetration.
3.3. Evaluation of BBR and DSR test results
The effects of TLPP and VPP modications on the low, medium
and high temperature performance of the base asphalt were
detected through BBR and DSR tests. Laboratory facility limitations
made us reduce the number of test samples. The most effective
and remarkable amounts of each additive performing signicant
changes on asphalt rheology were determined from Fig. 3 as 3%
(w/w) TLPP, 5% (w/w) TLPP, 1% (w/w) VPP and 2% (w/w) VPP and
have been selected to compare with the base asphalt.
Creep stiffness (S) and creep rate (m) values of the PAV-aged
asphalt samples were determined from BBR tests and the results
were graphically summarized in Figs. 4 and 5. According to the
Superpave binder specication, S should not exceed 300 MPa and
m should be at least 0.3. All the test samples provided these limitations at 6 C and 12 C but none of them was successful at
18 C. Asphalt with lower S and higher m performs better at low
temperatures in terms of low temperature cracking resistance. As
seen from Figs. 4 and 5, S was decreased by both of the additives at
all test temperatures while m was increased by 3% (w/w) TLPP and
1% (w/w) VPP, reduced slightly with 2% (w/w) VPP and stayed about
at the same level with 5% (w/w) TLPP modications. As lower S and
higher m is desired, asphalt with lower S/m value can be said to have
more low temperature cracking resistance [13,14]. S/m values of the
base asphalt at different temperatures were found to be decreased
ranging from 0.9% to 29.8% (Table 4) showing the improved performance of the TLPP and VPP modied asphalts at low temperatures.
Besides, 3% (w/w) TLPP modied asphalt gave better S/m values at
all test temperatures among the compared asphalt samples.
DSR tests were conducted on the original (unaged), RTFOT-aged
and PAV-aged asphalt samples in order to determine the complex
shear modulus (G*) values and phase angles () (Table 5) to use
in rutting and fatigue evaluation. G* is the total resistance of the
asphalt sample against deformation and can be considered as the
measure of the asphalt stiffness. denes the elastic/viscous behavior of the asphalt at the testing temperature. ranges between 0
and 90 and the lower the , the more elastic the asphalt is. Lower

306

M. Gr et al. / Journal of Hazardous Materials 279 (2014) 302310

Fig. 4. BBR test results (creep stiffness).

Fig. 5. BBR test results (m-value).

is desirable for better rutting and fatigue resistances. TLPP and VPP
modications, in general, were found to reduce insignicantly for
unaged and RTFOT-aged samples. Asphalt should be stiff/elastic to
resist deformation (rutting) whereas should be elastic and not too
stiff to resist fatigue cracking. As can be seen in Table 5, modications decreased G*, except for 1% (w/w) VPP, resulting to reduce
rutting resistance parameter (G*/sin ) which can also be obtained
with the other viscosity-reducing asphalt modiers [1315]. Conrming the previous tests results, a small increment in G*/sin
was obtained with 1% (w/w) VPP. Minimum of G*/sin should be
1.00 kPa and 2.20 kPa for unaged and RTFOT-aged samples, respectively. All the tested samples fullled these limitations at 64 C.
None of them was found to be sufcient at 70 C. G*x sin is the
fatigue resistance parameter derived by Superpave binder specication to a maximum value of 5000 kPa for PAV-aged samples. All of
the tested samples met the fatigue criteria of G*x sin 5000 kPa at
28 C. TLPP and VPP modications were found to decrease G*x sin
value of the base asphalt signicantly (Table 5). Since too stiff and
viscous asphalts are sensitive to fatigue cracking, TLPP and VPP
offer improved fatigue cracking resistance by decreasing G*x sin
of the base asphalt in the range of 8.8% to 12.2% at 28 C. At 25 C,
base asphalt was not able to satisfy the specication limit with
6177.3 kPa but TLPP brought it within the limitation by reducing

Table 4
S/m values of the asphalt samples with and without additive.
S/m

Base asphalt
3% (w/w) TLPP modied asphalt
5% (w/w) TLPP modied asphalt
1% (w/w) VPP modied asphalt
2% (w/w) VPP modied asphalt

6 C

12 C

18 C

314.8
240.2
261.4
268.9
303.5

695.0
567.6
678.2
622.0
688.9

1902.0
1335.8
1812.7
1553.4
1828.7

G*x sin at 30.034.3% level. VPP was also found to improve the
fatigue resistance parameter of the base asphalt by 12.713.5% at
25 C. In literature, PET modied mixture (with dry process) has
been determined to have better fatigue life [9].
3.4. Evaluation of Nicholson stripping test results
Incompatible polarity properties of HMA mixture constituents
make stripping more serious pavement problem. Polar aggregate
particles tend to bond with polar water rather than to bond with
non-polar asphalt. Even if the aggregate and asphalt bond each
other strongly, stripping can occur when they exposed to moisture.

M. Gr et al. / Journal of Hazardous Materials 279 (2014) 302310

307

Table 5
DSR test results.
Asphalt status

Test temp.

Variables

Base asphalt

3% (w/w) TLPP
modied asphalt

5% (w/w) TLPP
modied asphalt

1% (w/w) VPP
modied asphalt

2% (w/w) VPP
modied asphalt

Original (Unaged)

64 C

G* (kPa)
( )
G*/sin (kPa)
G* (kPa)
( )
G*/sin (kPa)
G* (kPa)
( )
G*/sin (kPa)
G* (kPa)
( )
G*/sin (kPa)
G* (kPa)
( )
G*x sin (kPa)
G* (kPa)
( )
G*x sin (kPa)

1.4195
88.07
1.4203
0.63931
88.85
0.6394
3.0898
86.24
3.0965
1.5679
87.69
1.5692
5206.2
53.47
4183.4
8031
50.28
6177.3

1.3564
86.94
1.3583
0.62465
88.01
0.6250
3.0213
85.79
3.0295
1.3596
87.23
1.3612
n.d.a
n.d.a
n.d.a
5357.3
53.80
4323.1

1.1969
86.18
1.1996
0.57001
87.46
0.5706
3.0292
85.36
3.0392
1.3538
86.90
1.3558
4699.9
53.23
3764.8
5297.2
50.05
4060.9

1.4337
87.93
1.4346
0.64879
87.33
0.6495
3.1275
85.12
3.1389
1.6017
87.02
1.6039
4501.2
54.72
3674.5
6870.7
51.69
5391.2

1.3097
87.76
1.3107
0.61173
88.62
0.6119
3.0793
85.81
3.0876
1.3729
87.25
1.3745
4732.1
53.75
3816.2
6768.4
52.14
5343.7

70 C

RTFOT residue

64 C

70 C

PAV residue

28 C

25 C

Not determined.

Several anti-stripping additives were used to improve the stripping

resistance of the asphalt mixtures and successfully outcomes were
obtained [1315,21,22]. In this part of the study, the effects of TLPP
and VPP modications on the stripping resistance of the asphaltaggregate mixtures were examined through Nicholson stripping
test and the results were presented in Table 6.

Basalt aggregate was used in the tests and stripping resistance of

60% was observed with the base asphalt. The asphalt mixture was
highly affected by the water as 40% of the total aggregate surface
was found to be stripped although the aggregate is known to have
good stripping resistance. Stripping resistance was improved signicantly by TLPP and VPP and reached to 95100%. No stripping

980

Marshall Stability (kg)

..

960

0% (w/w) TLPP

1% (w/w) TLPP

2% (w/w) TLPP

3% (w/w) TLPP

5% (w/w) TLPP

10% (w/w) TLPP

940
920
900
880
860
840
820
800
4

4.5

5.5

Asphalt Content (%)

Fig. 6. Marshall Stability of the TLPP modied samples.

1040

0% (w/w) VPP
3% (w/w) VPP

Marshall Stability (kg..)

1000

1% (w/w) VPP
5% (w/w) VPP

2% (w/w) VPP
10% (w/w) VPP

960

920

880
840

800
4

4.5

Asphalt Content (%)

Fig. 7. Marshall Stability of the VPP modied samples.

5.5

308

M. Gr et al. / Journal of Hazardous Materials 279 (2014) 302310

Fig. 8. FTIR patterns of the base and modied asphalt samples.

Fig. 9. SEM images and EDS analyses of asphalt samples; (a) base asphalt; (b) TLPP modied asphalt; (c) VPP modied asphalt.

M. Gr et al. / Journal of Hazardous Materials 279 (2014) 302310

Table 6
Stripping resistances (%).

and 2.765% for the VPP modied asphalt. The signicant increase
in the amount of sulphur in the modied asphalts was supported
by FTIR results.

Additive concentration (%, w/w)

TLPP
VPP

309

10

60
60

70
95

75
90

100
90

95
95

90
90

was observed with 3% (w/w) TLPP. Similar results were obtained

with PET additive in literature [12]. The increasing of stripping
resistance with TLPP and VPP implies that the adhesion force at
the asphalt-aggregate interface was improved through these modications.
3.5. Evaluation of Marshall Test results
Marshall Tests were applied in order to detect the effects of TLPP
and VPP on the stability of asphalt mixtures. Tests were performed
at four different asphalt contents from 4% to 5.5%. The test results
for TLPP and VPP modied asphalts were graphically shown in
Figs. 6 and 7, respectively as a function of asphalt content used. Each
result seen in gures was obtained from the average of 3 samples.
PET was seen to lead different variations on the stability of
asphalt mixtures. The replacement of aggregate with PET granules
decreased Marshall Stability [11] while PET modication of mixture with dry process resulted to increase the stability depending
on the PET content [7]. In our study, TLPP was found to increase the
Marshall Stability of the mixtures at low asphalt contents (44.5%)
for all concentrations of TLPP, this trend was however reversed
when higher amounts of asphalt were used within the mixtures
(55.5%) such as the study carried on with PET modied asphalt
[12]. Although not as effective as TLPP, stability was also increased
by VPP at 4% and 4.5% asphalt contents and the increment, unlike
TLPP, was kept on for low VPP concentrations (1% (w/w), 2% (w/w)
and 3% (w/w)) at higher asphalt contents (5% and 5.5%) resulting to
improve the mixture resistance against permanent deformations
for a wide range of asphalt content like the polymers SBS, EVA,
polyethylene [2325] and the polyboron additives [26,27].
3.6. Evaluation of FTIR test results
The FTIR patterns of the base and modied asphalt samples were
given in Fig. 8. As seen in the patterns, the modied samples were
observed to contain different bond structures of the PET additives
(TLPP, VPP). The C O bonds which were formed by the additives
were recorded at 1700 cm1 evidently. This result is consistent with
the fact that esterication takes place with glycolysis reaction existing C O bonds as explained in the preparation of PET additives
subsection. The C C double bond was seen in the FTIR pattern of
the base asphalt at 1600 cm1 . After the modication process, bond
cleavage proceeded at 1600 cm1 for the base asphalt and alkenes
converted to alkanes. So, the C C double bond (at 1600 cm1 ) was
found to be rather poor for the modied asphalt samples. The SO2
bond at 1300 cm1 , which was not available in the base asphalt FTIR
pattern, reected the additive properties to the modied asphalts.
The other bond structures were found to be similar with respect to
the FTIR patterns given in Fig. 8.

4. Conclusion
Two novel additive materials, TLPP and VPP, were derived chemically from PET bottle wastes and used as additive within the asphalt
in this study. The effects of each additive on the asphalt and HMA
mixture properties were examined through conventional tests and
Superpave methods. The outcomes were summarized below:
TLPP and VPP, except for 1% (w/w) VPP, were found to decrease
the viscosity and softening point and increase the penetration of
the base bitumen. The ductility property was not affected by TLPP
while decreased by the increase of VPP concentration.
The low temperature cracking resistance of the base asphalt was
improved by TLPP and VPP according to the BBR test results showing the improved performance of the modied asphalts at low
temperatures.
TLPP and VPP modications, except for 1% (w/w) VPP, reduced
the rutting resistance but both of them were found to offer signicantly improved fatigue cracking resistance based on the DSR
tests.
According to the Nicholson stripping test, TLPP and VPP increased
the stripping resistance of the asphalt mixture signicantly which
implies that the adhesion force at the aggregate-asphalt interface
was strengthened through these modications.
At low asphalt contents, the mixture stability was found to be
improved by TLPP modication while similar phenomenon was
obtained by low VPP concentrations for a wider range of asphalt
content resulting to improve the mixture performance against
permanent deformations.
TLPP and VPP modied asphalts were produced at 120 C and
10 min which allow to reducing the required heat energy and
aging of asphalt during modication process with respect to the
other polymer based asphalt additives.
Consequently, TLPP and VPP modied asphalts were recommended to use in cold and humid regions, in roadway sections with
high trafc volume and heavy vehicle, in expressways, at bus stations, at curved roadway sections and at roadway junctions in order
to improve the roadway performance. Moreover, the usage of PET
waste as an asphalt modier in the form of TLPP and VPP can be
accepted as a new practice about the maximization of its end-ofservice life management effectiveness beside the recycling and/or
energy recovery processes and will offer not only an alternative
but also a benecial way of disposal of this ecologically hazardous
material.
Acknowledgements
The authors are grateful to Gazi University and Turkish General
Directorate of Highways for the laboratory facilities.
References

3.7. Evaluation of SEM results

SEM images and EDS results were shown in Fig. 9. When the SEM
images have been examined, it is clear that the removing of volatile
components lead to porosity in the samples. The uniformity has
been observed in all the SEM images of the asphalt samples given
in Fig. 9. According to the EDS results, sulphur was determined as
0.513% for the base asphalt, 3.706% for the TLPP modied asphalt

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