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

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DOI: 10.1016/j.jhazmat.2014.07.018 · Source: PubMed

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 Journal of Hazardous Materials 279 (2014) 302–310

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 Gürü a,∗ , M. Kürşat Çubuk b , Deniz Arslan b , S. Ali Farzanian b , İbrahim Bilici c
a
Gazi University, Eng. Fac., Chem. Eng. Depart., 06570 Maltepe-Ankara, Turkey
b
Gazi University, Eng. Fac., Civil Eng. Depart., 06570 Maltepe-Ankara, Turkey
c
Hitit University, Eng. Fac., Chem. Eng. Depart., 19100 Çorum, Turkey

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• We derived two novel additive mate-

1040
rials from PET bottle waste: TLPP and 0% (w/w) VPP 1% (w/w) VPP 2% (w/w) VPP
1000 3% (w/w) VPP 5% (w/w) VPP 10% (w/w) VPP
VPP.
Marshall Stability (kg)
..

• We used them to modify the base 960

asphalt separately. 920

• The additives improved both the
880
asphalt and the asphalt mixture per-
formance. 840
• TLPP, VPP offer a beneficial way about 800
disposal of ecologically hazardous 4 4.5 5 5.5

PET waste. Asphalt Content (%)

a r t i c l e i n f o a b s t r a c t

Article history: This study investigates an application area for Polyethylene Terephthalate (PET) bottle waste which has
Received 4 April 2014 become an environmental problem in recent decades as being a considerable part of the total plastic
Received in revised form 13 June 2014 waste bulk. Two novel additive materials, namely Thin Liquid Polyol PET (TLPP) and Viscous Polyol PET
Accepted 10 July 2014
(VPP), were chemically derived from waste PET bottles and used to modify the base asphalt separately for
Available online 18 July 2014
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
Keywords:
Stripping) and Superpave methods (Rotational Viscosity, Dynamic Shear Rheometer (DSR), Bending Beam
Modified asphalt
Polyethylene terephthalate
Rheometer (BBR)). Also, chemical structures were described by Scanning Electron Microscope (SEM)
Thin Liquid Polyol PET equipped with Energy Dispersive Spectrometer (EDS) and Fourier Transform Infrared (FTIR) techniques.
Viscous Polyol PET Since TLPP and VPP were determined to improve the low temperature performance and fatigue resistance
Fatigue of the asphalt as well as the Marshall Stability and stripping resistance of the HMA mixtures based on
Stripping resistance the results of the applied tests, the usage of PET waste as an asphalt roadway pavement material offers
an alternative and a beneficial way of disposal of this ecologically hazardous material.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction They are synthetic materials derived mainly from petroleum or

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. Gürü).
natural gas and composed substantially of carbon, hydrogen and
oxygen combinations. Since they have high decomposition tem-
perature, 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
specific and significant set of impacts on ecosystem and can affect
human and animal health negatively associated with their chemical

http://dx.doi.org/10.1016/j.jhazmat.2014.07.018
0304-3894/© 2014 Elsevier B.V. All rights reserved.
 M. Gürü et al. / Journal of Hazardous Materials 279 (2014) 302–310 303

structure. Toxic chemicals within the plastic can bioaccumulate up Table 2

Descriptive properties of the aggregate.
the food chain through ingestion by wildlife meaning that human
can also be subjected to those chemicals. Test Value
Plastics are used by almost all end-use segment of the economy Los Angeles abrasion, % 9.2
and their usage is quite likely to increase with the developments in MgSO4 freezing loss, % 0.16
the plastic industry, which in turn causes increase of plastic wastes. Flakiness index, % 14.5
Since they are found to alter the working of ecosystem [1–3], pre- Methylene blue 1.5
Water absorption, % 2.11
vention/minimization of plastic becoming waste and recovery of
Coarse aggregate specific gravity (g/cm3 ), bulk 2.643
this ecologically hazardous waste should be taken into account Apparent 2.709
instead of being left freely in nature or landfilled. Available waste Fine aggregate specific gravity (g/cm3 ), bulk 2.732
management systems include recycling and/or energy recovery Apparent 2.778
Filler specific gravity (g/cm3 ), bulk –
operations, but they need to be improved more. New policies
Apparent 2.823
should thus be developed before plastic waste becomes an unsolv-
able problem.
Being lighter, more durable and less bulky than many alter- process and investigates the effects of PET waste both on
native materials, one of the main application and so the main asphalt and on HMA mixture performances through conventional
post-consumer waste for plastics is packaging and polyethylene tests (Penetration, Softening Point, Ductility, Marshall Stability,
terephthalate (PET) bottles generate considerable part of this sec- Nicholson Stripping) and Superpave methods (Rotational Viscos-
tor. PET has exceptional gas and moisture barrier properties with ity, Dynamic Shear Rheometer (DSR), Bending Beam Rheometer
high shatter resistance and can contain carbon dioxide which (BBR)). Also, chemical structures were described by results of SEM
makes it ideal for use in water and beverage bottles. Single-use equipped with EDS and FTIR instruments.
PET bottles have a short service life and therefore turn into res-
idential (post-consumer) plastic waste in a short period of time.
2. Materials and methodology
Since PET recycling has not been carried out in the same amount
as its production [4,5], it would be worthwhile to find out new
2.1. Asphalt and aggregate
application areas for PET bottle wastes to maximize their end-of-
service life management effectiveness. The usage of PET waste as
The base asphalt was sourced from Kırıkkale/Turkey Petroleum
a reinforcement component for asphalt concrete pavement mate-
Refinery and used throughout the study. Table 1 displays the phys-
rial, Hot Mix Asphalt (HMA), can be a research area for such an
ical properties of the base asphalt.
aim which is still in its infancy. In the previous studies, PET waste
100 percent crushed basalt aggregate was used to manufacture
was generally added to the asphalt mixture with dry process (mix-
the asphalt mixtures. The descriptive properties of the aggregate
ture modification) or used as aggregate in the asphalt mixture
were given in Table 2. Gradation characteristics of the aggregate
(aggregate replacement) in order to improve HMA performance.
used in Marshall Test samples were shown in Fig. 1 which are the
Researches have shown that permanent deformation resistance,
average values of the Type-1 wearing course gradation limits of
Marshall Stability, stiffness and fatigue life of the asphalt mixtures
Turkey’s Highway Technical Specification.
were increased while moisture damage resistance was decreased
when PET was used as additive in the mixture (mixture modi-
2.2. Preparation of synthetic PET additives
fication) [6–9]. The replacement of aggregate with PET was also
found to increase permanent deformation resistance but decrease
PET waste consisting post-consumer soft-drink bottles was
Marshall Stability and stiffness of the mixtures [10,11]. However,
collected from environment. Collected PETs were purged from con-
specific gravity of the asphalt mixtures was found to be decreased
taminants such as PVC, labels and cut by shredder into small pieces
by either method [7,11]. Different from the mentioned studies
as flake under 10 mm sieve. The flakes were washed with soup and
above, asphalt was modified with additive derived from PET by
dried 8 h at 105 ◦ C. The glycolysis reactions of PET were carried
aminolysis and found to improve the Marshall Stability depending
out in a 1 L five-necked flask equipped with stirrer, thermocou-
on the asphalt and additive contents [12].
ple and refluxing condenser unit under nitrogen atmosphere to
The selected additive can be incorporated to the asphalt mixture
avoid oxidation. The established glycols, PET and catalyst (0.02% of
by dry process or wet process. The dry process covers mixing the
additive with aggregates prior to adding the binder to the mix-
ture while wet process refers to the modification of the binder ASTM Sieves 200 80 40 10 4 3/8" 1/2" 3/4"

with the additive at an elevated temperature prior to adding the 100

Type-1 Gradation limits
binder to the mixture. In this study, two novel additive materials, Aggregate gradation
Thin Liquid Polyol PET (TLPP) and Viscous Polyol PET (VPP), were 80
Percent Passing (%)

derived chemically from PET bottle wastes. This paper presents a

novel approach about the incorporation of PET waste in the form
60
of TLPP and VPP to HMA mixtures by means of a feasible wet

40
Table 1
Physical properties of the base asphalt.
20
Test Value Standard

Specific gravity, 25 ◦ C (g/cm3 ) 1.02 ASTM D-70 0

Penetration 25 ◦ C, 100 g, 5 s (0.1 mm) 45 ASTM D-5
Softening point (◦ C) 51.5 ASTM D-36
0.01 0.1 1 10 100
Viscosity, 130 ◦ C (Pa s) 0.186 ASTM D-4402
Sieve Size (mm), Log
140 ◦ C (Pa s) 0.126 ASTM D-4402
Ductility, 15 ◦ C (cm) +105 ASTM D-113 Fig. 1. Gradation characteristics of the Marshall Test samples and specification lim-
its.
304 M. Gürü et al. / Journal of Hazardous Materials 279 (2014) 302–310
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 defined as the amount of potassium hydrox-
ide 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 defined as the
amount of potassium hydroxide equivalent to the amount of acetic
acid involved in the esterification 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. Modification of asphalt with PET additives
Each additive was added to the base asphalt at five different pro-
portions: 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 above-
mentioned proportions. Modification 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
modification on the asphalt and HMA mixture performances. Rota-
tional viscosity tests were applied on the base and PET modified
asphalt samples according to ASTM D-4402 using Brookfield DV III
Rheometer with spindle no. 29. Penetration, softening point and
ductility of the asphalt samples with and without PET were mea-
sured 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 (ı) values of the
base and modified 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 ı were used as G*/sin ı and G* sin ı to compare rutting
resistance and fatigue resistance of the asphalt samples. BBR tests
(AASHTO T313) were carried out with Thermoelectric BBR Instru-
ment (Cannon) at −6 ◦ C, −12 ◦ C and −18 ◦ C through which the creep
stiffness (S) and creep ratio (m) values of the base and modified
asphalt samples were determined in order to evaluate low tem-
perature 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 Nichol-
son stripping test. The coarse basalt aggregate (6.3–9.5 mm) was
coated with base and PET modified 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 modification were
examined by FTIR between 400 and 4000 cm−1 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 dis-
cussed.
3. Results and discussion
3.1. Evaluation of viscosity test results
Viscosity is a fundamental characteristic of any asphalt and
defines the flow resistance of the material at a certain tempera-
ture. 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) show-
ing that TLPP can keep its effectiveness at high temperatures and
allows to lower asphalt plant working temperature like organic-
based synthetic asphalt modifier compounds [13–15] 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 vis-
cosity results, except for the concentration rate of 1% (w/w), were
 M. Gürü et al. / Journal of Hazardous Materials 279 (2014) 302–310 305

5.20 90oC 0.20

VPP Modified Asphalt VPP Modified Asphalt
5.00
4.80 TLPP Modified Asphalt TLPP Modified Asphalt
0.18
4.60 130 oC
4.40
2.40
, 0.16

2.20
0.14

Viscosity (Pa.s)
Viscosity (Pa.s)
2.00 100oC

1.80
1.20 , 0.12
140oC
1.10
0.10
1.00 110oC
0.90
0.08
0.80
0.48
, 150 o C
0.44 0.06
0.40
120oC 160 oC
0.36 0.04
0.32

0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
Additive Concentration (% w/w) Additive Concentration (% w/w)
(a) (b)
Fig. 3. Viscosity test results of the base and modified asphalts; (a) between 90 ◦ C and 120 ◦ C; (b) between 130 ◦ C and 160 ◦ C.

obtained by VPP modification. 1% (w/w) VPP has resulted small expected to show improved performance at cold climate regions
amounts of increases on viscosity varying between 0.4% and 5.4% due to the decreased viscosity and softening point and increased
due to increased cohesion of asphalt at low VPP amounts whereas penetration.
higher VPP concentrations decreased viscosity up to 21.1%. VPP
also keeps its effectiveness at high temperatures and as the tem- 3.3. Evaluation of BBR and DSR test results
perature increases, in general, the viscosity-reducing effect of VPP
was observed to increase (Fig. 3) leading to reduce the fabrication The effects of TLPP and VPP modifications on the low, medium
temperature of HMA mixtures like TLPP. and high temperature performance of the base asphalt were
detected through BBR and DSR tests. Laboratory facility limitations
3.2. Evaluation of penetration, softening point and ductility tests made us reduce the number of test samples. The most effective
results and remarkable amounts of each additive performing significant
changes on asphalt rheology were determined from Fig. 3 as 3%
Table 3 exhibits the penetration, softening point and ductility (w/w) TLPP, 5% (w/w) TLPP, 1% (w/w) VPP and 2% (w/w) VPP and
tests results of the base and modified asphalt samples. As expected have been selected to compare with the base asphalt.
from the previous test, penetration was increased and softening Creep stiffness (S) and creep rate (m) values of the PAV-aged
point was decreased by TLPP and VPP modifications except 1% asphalt samples were determined from BBR tests and the results
(w/w) of VPP. These parameters were found to stay at the same level were graphically summarized in Figs. 4 and 5. According to the
for 1% (w/w) VPP. The ductility property was not changed by TLPP Superpave binder specification, S should not exceed 300 MPa and
but decreased with the increasing content of VPP which can be seen m should be at least 0.3. All the test samples provided these lim-
in literature studies carried out with different asphalt additives itations at −6 ◦ C and −12 ◦ C but none of them was successful at
[19,20]. Softer asphalts may be less susceptible to low temperature −18 ◦ C. Asphalt with lower S and higher m performs better at low
cracking and thus preferred to use in cold regions in terms of bet- temperatures in terms of low temperature cracking resistance. As
ter low temperature cracking property as they become less harden seen from Figs. 4 and 5, S was decreased by both of the additives at
at low temperatures. So, TLPP and VPP modified asphalts were 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 modifications. As lower S and
Table 3
Penetration, softening point and ductility tests results.
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
Asphalt Penetration Softening Ductility @ base asphalt at different temperatures were found to be decreased
(0.1 mm) point (◦ C) 15 ◦ C (cm)
ranging from 0.9% to 29.8% (Table 4) showing the improved perfor-
Base asphalt 45 51.5 +105a mance of the TLPP and VPP modified asphalts at low temperatures.
TLPP modified asphalt, 1% (w/w) 51 48.7 +105a
Besides, 3% (w/w) TLPP modified asphalt gave better S/m values at
2% (w/w) 54 48.3 +105a
3% (w/w) 55 48.1 +105a all test temperatures among the compared asphalt samples.
5% (w/w) 56 47.9 +105a DSR tests were conducted on the original (unaged), RTFOT-aged
10% (w/w) 61 47.5 +105a and PAV-aged asphalt samples in order to determine the complex
VPP modified asphalt, 1% (w/w) 45 51.6 +105a
shear modulus (G*) values and phase angles (ı) (Table 5) to use
2% (w/w) 50 50.3 84
3% (w/w) 54 50.1 77
in rutting and fatigue evaluation. G* is the total resistance of the
5% (w/w) 57 50.0 68 asphalt sample against deformation and can be considered as the
10% (w/w) 60 49.8 55 measure of the asphalt stiffness. ı defines the elastic/viscous behav-
a
The measuring capacity of the ductility test device was 105 cm and the sample ior of the asphalt at the testing temperature. ı ranges between 0◦
was not broken in the test. and 90◦ and the lower the ı, the more elastic the asphalt is. Lower ı
306 M. Gürü et al. / Journal of Hazardous Materials 279 (2014) 302–310

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 Table 4
S/m values of the asphalt samples with and without additive.
modifications, in general, were found to reduce ı insignificantly for
unaged and RTFOT-aged samples. Asphalt should be stiff/elastic to S/m
resist deformation (rutting) whereas should be elastic and not too
−6 ◦ C −12 ◦ C −18 ◦ C
stiff to resist fatigue cracking. As can be seen in Table 5, modifica-
Base asphalt 314.8 695.0 1902.0
tions decreased G*, except for 1% (w/w) VPP, resulting to reduce
3% (w/w) TLPP modified asphalt 240.2 567.6 1335.8
rutting resistance parameter (G*/sin ı) which can also be obtained 5% (w/w) TLPP modified asphalt 261.4 678.2 1812.7
with the other viscosity-reducing asphalt modifiers [13–15]. Con- 1% (w/w) VPP modified asphalt 268.9 622.0 1553.4
firming the previous tests results, a small increment in G*/sin ı 2% (w/w) VPP modified asphalt 303.5 688.9 1828.7
was obtained with 1% (w/w) VPP. Minimum of G*/sin ı should be
1.00 kPa and 2.20 kPa for unaged and RTFOT-aged samples, respec-
tively. All the tested samples fulfilled these limitations at 64 ◦ C. G*x sin ı at 30.0–34.3% level. VPP was also found to improve the
None of them was found to be sufficient at 70 ◦ C. G*x sin ı is the fatigue resistance parameter of the base asphalt by 12.7–13.5% at
fatigue resistance parameter derived by Superpave binder specifi- 25 ◦ C. In literature, PET modified mixture (with dry process) has
cation to a maximum value of 5000 kPa for PAV-aged samples. All of been determined to have better fatigue life [9].
the tested samples met the fatigue criteria of G*x sin ı ≤ 5000 kPa at
28 ◦ C. TLPP and VPP modifications were found to decrease G*x sin ı 3.4. Evaluation of Nicholson stripping test results
value of the base asphalt significantly (Table 5). Since too stiff and
viscous asphalts are sensitive to fatigue cracking, TLPP and VPP Incompatible polarity properties of HMA mixture constituents
offer improved fatigue cracking resistance by decreasing G*x sin ı make stripping more serious pavement problem. Polar aggregate
of the base asphalt in the range of 8.8% to 12.2% at 28 ◦ C. At 25 ◦ C, particles tend to bond with polar water rather than to bond with
base asphalt was not able to satisfy the specification limit with non-polar asphalt. Even if the aggregate and asphalt bond each
6177.3 kPa but TLPP brought it within the limitation by reducing other strongly, stripping can occur when they exposed to moisture.
 M. Gürü et al. / Journal of Hazardous Materials 279 (2014) 302–310 307

Table 5
DSR test results.

Asphalt status Test temp. Variables Base asphalt 3% (w/w) TLPP 5% (w/w) TLPP 1% (w/w) VPP 2% (w/w) VPP
modified asphalt modified asphalt modified asphalt modified asphalt

Original (Unaged) 64 ◦ C G* (kPa) 1.4195 1.3564 1.1969 1.4337 1.3097

ı (◦ ) 88.07 86.94 86.18 87.93 87.76
G*/sin ı (kPa) 1.4203 1.3583 1.1996 1.4346 1.3107
70 ◦ C G* (kPa) 0.63931 0.62465 0.57001 0.64879 0.61173
ı (◦ ) 88.85 88.01 87.46 87.33 88.62
G*/sin ı (kPa) 0.6394 0.6250 0.5706 0.6495 0.6119
RTFOT residue 64 ◦ C G* (kPa) 3.0898 3.0213 3.0292 3.1275 3.0793
ı (◦ ) 86.24 85.79 85.36 85.12 85.81
G*/sin ı (kPa) 3.0965 3.0295 3.0392 3.1389 3.0876
70 ◦ C G* (kPa) 1.5679 1.3596 1.3538 1.6017 1.3729
ı (◦ ) 87.69 87.23 86.90 87.02 87.25
G*/sin ı (kPa) 1.5692 1.3612 1.3558 1.6039 1.3745
PAV residue 28 ◦ C G* (kPa) 5206.2 n.d.a 4699.9 4501.2 4732.1
ı (◦ ) 53.47 n.d.a 53.23 54.72 53.75
G*x sin ı (kPa) 4183.4 n.d.a 3764.8 3674.5 3816.2
25 ◦ C G* (kPa) 8031 5357.3 5297.2 6870.7 6768.4
ı (◦ ) 50.28 53.80 50.05 51.69 52.14
G*x sin ı (kPa) 6177.3 4323.1 4060.9 5391.2 5343.7
a
Not determined.

Several anti-stripping additives were used to improve the stripping
resistance of the asphalt mixtures and successfully outcomes were
obtained [13–15,21,22]. In this part of the study, the effects of TLPP
and VPP modifications on the stripping resistance of the asphalt-
aggregate 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 sig-
nificantly by TLPP and VPP and reached to 95–100%. No stripping

980
0% (w/w) TLPP 1% (w/w) TLPP 2% (w/w) TLPP
960
3% (w/w) TLPP 5% (w/w) TLPP 10% (w/w) TLPP
Marshall Stability (kg)

940
..

920

900

880

860

840

820

800
4 4.5 5 5.5
Asphalt Content (%)

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

1040
0% (w/w) VPP 1% (w/w) VPP 2% (w/w) VPP
1000 3% (w/w) VPP 5% (w/w) VPP 10% (w/w) VPP
Marshall Stability (kg..)

960

920

880

840

800
4 4.5 5 5.5

Asphalt Content (%)

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

308 M. Gürü et al. / Journal of Hazardous Materials 279 (2014) 302–310

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

Fig. 9. SEM images and EDS analyses of asphalt samples; (a) base asphalt; (b) TLPP modified asphalt; (c) VPP modified asphalt.
 M. Gürü et al. / Journal of Hazardous Materials 279 (2014) 302–310
Table 6
Stripping resistances (%).
Additive concentration (%, w/w)
0 1 2 3 5 10
TLPP 60 70 75 100 95
VPP 60 95 90 90 95
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 mod-
ifications.
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 modified asphalts were graphically shown in
Figs. 6 and 7, respectively as a function of asphalt content used. Each
result seen in figures 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 modification of mix-
ture 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 (4–4.5%)
for all concentrations of TLPP, this trend was however reversed
when higher amounts of asphalt were used within the mixtures
(5–5.5%) such as the study carried on with PET modified 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 [23–25] and the polyboron additives [26,27].
3.6. Evaluation of FTIR test results
The FTIR patterns of the base and modified asphalt samples were
given in Fig. 8. As seen in the patterns, the modified 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 cm−1 evidently. This result is consistent with
the fact that esterification takes place with glycolysis reaction exist-
ing 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 cm−1 . After the modification process, bond
cleavage proceeded at 1600 cm−1 for the base asphalt and alkenes
converted to alkanes. So, the C C double bond (at 1600 cm−1 ) was
found to be rather poor for the modified asphalt samples. The SO2
bond at 1300 cm−1 , which was not available in the base asphalt FTIR
pattern, reflected the additive properties to the modified asphalts.
The other bond structures were found to be similar with respect to
the FTIR patterns given in Fig. 8.
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 modified asphalt
309
and 2.765% for the VPP modified asphalt. The significant increase
in the amount of sulphur in the modified asphalts was supported
by FTIR results.
90 4. Conclusion
90
Two novel additive materials, TLPP and VPP, were derived chem-
ically 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 show-
ing the improved performance of the modified asphalts at low
temperatures.
• TLPP and VPP modifications, except for 1% (w/w) VPP, reduced
the rutting resistance but both of them were found to offer sig-
nificantly 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 significantly which
implies that the adhesion force at the aggregate-asphalt interface
was strengthened through these modifications.
• At low asphalt contents, the mixture stability was found to be
improved by TLPP modification 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 modified asphalts were produced at 120 ◦ C and
10 min which allow to reducing the required heat energy and
aging of asphalt during modification process with respect to the
other polymer based asphalt additives.
Consequently, TLPP and VPP modified asphalts were recom-
mended to use in cold and humid regions, in roadway sections with
high traffic volume and heavy vehicle, in expressways, at bus sta-
tions, at curved roadway sections and at roadway junctions in order
to improve the roadway performance. Moreover, the usage of PET
waste as an asphalt modifier in the form of TLPP and VPP can be
accepted as a new practice about the maximization of its end-of-
service life management effectiveness beside the recycling and/or
energy recovery processes and will offer not only an alternative
but also a beneficial 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.
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