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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
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)
..
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
Table 1
Physical properties of the base asphalt.
Table 2
Descriptive properties of the aggregate.
Test
Value
9.2
0.16
14.5
1.5
2.11
2.643
2.709
2.732
2.778
2.823
200
80
40
10
100
Type-1 Gradation limits
Aggregate gradation
303
80
60
40
20
Test
Value
Standard
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
304
Fig. 2. Additives derived from PET bottle waste by glycolysis reactions; (a) Thin Liquid Polyol PET (TLPP); (b) Viscous Polyol PET (VPP).
(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
5.20
5.00
4.80
4.60
4.40
2.40
90oC
0.20
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
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
(a)
10
10
(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.
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.
306
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.
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.
980
960
0% (w/w) TLPP
1% (w/w) TLPP
2% (w/w) TLPP
3% (w/w) TLPP
5% (w/w) TLPP
940
920
900
880
860
840
820
800
4
4.5
5.5
1040
0% (w/w) VPP
3% (w/w) VPP
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
5.5
308
Fig. 9. SEM images and EDS analyses of asphalt samples; (a) base asphalt; (b) TLPP modied asphalt; (c) VPP modied asphalt.
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.
TLPP
VPP
309
10
60
60
70
95
75
90
100
90
95
95
90
90
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
[1] H.S. Carson, S.L. Colbert, M.J. Kaylor, K.J. McDermid, Small plastic debris changes
water movement and heat transfer through beach sediments, Mar. Pollut. Bull.
62 (2011) 17081713.
[2] M.R. Gregory, Environmental implications of plastic debris in marine
settingsentanglement, ingestion, smothering, hangers-on, hitch-hiking and
alien invasions, Philos. T. Roy. Soc. B 364 (2009) 20132025.
[3] S. Katsanevakis, G. Verriopoulos, A. Nicolaidou, M. Thessalou-Legaki, Effect of
marine litter on the benthic megafauna of coastal soft bottoms: a manipulative
eld experiment, Mar. Pollut. Bull. 54 (2007) 771778.
310
[15] D. Arslan, M. Gr, M.K. Cubuk, Improvement of bitumen and bituminious mixtures performance properties with organic based zincphosphate compound, J.
Fac. Eng. Archit. Gazi. Univ. 27 (2012) 459466.
[16] J. Liu, S. Saboundjian, P. Li, B. Connor, B. Brunette, Laboratory evaluation of
sasobit-modied warm-mix asphalt for Alaskan conditions, J. Mater. Civil Eng.
23 (2011) 14981505.
[17] J.R.M. Oliveira, H.M.R.D. Silva, L.P.F. Abreu, S.R.M. Fernandes, Use of a warm
mix asphalt additive to reduce the production temperatures and to improve
the performance of asphalt rubber mixtures, J. Clean. Prod. 41 (2013) 1522.
[18] J. Read, D. Whiteoak, The Shell Bitumen Handbook, fth ed., Thomas Telford
Publishing, London, 2003.
[19] P. Cong, P. Xun, M. Xing, S. Chen, Investigation of asphalt binder containing
various crumb rubbers and asphalts, Constr. Build. Mater. 40 (2013) 632641.
[20] J. Yu, X. Zeng, S. Wu, L. Wang, G. Liu, Preparation and properties of montmorillonite modied asphalts, Mat. Sci. Eng. A-Struct. 447 (2007) 233238.
[21] C. Gorkem, B. Sengoz, Predicting stripping and moisture induced damage of
asphalt concrete prepared with polymer modied bitumen and hydrated lime,
Constr. Build. Mater. 23 (2009) 22272236.
[22] M. Cubuk, M. Gr, M.K. Cubuk, Improvement of bitumen performance with
epoxy resin, Fuel 88 (2009) 13241328.
[23] B. Sengoz, G. Isikyakar, Analysis of styrene-butadiene-styrene polymer modied bitumen using uorescent microscopy and conventional test methods, J.
Hazard. Mater. 150 (2008) 424432.
[24] S. Haddadi, E. Ghorbel, N. Laradi, Effects of the manufacturing process on the
performances of the bituminous binders modied with EVA, Constr. Build.
Mater. 22 (2008) 12121219.
[25] M. Attaelmanan, C.P. Feng, A. Al, Laboratory evaluation of HMA with high density polyethylene as a modier, Constr. Build. Mater. 25 (2011) 27642770.
[26] D. Arslan, M. Gr, M.K. Cubuk, Preventing of rutting and crackings in the
bituminous mixtures by monoethylene and diethylene glycol based synthetic
polyboron compounds, Constr. Build. Mater. 50 (2014) 102107.
[27] D. Arslan, M. Gr, M.K. Cubuk, M. Cubuk, Improvement of bitumen and bituminous mixtures performances by triethylene glycol based synthetic polyboron,
Constr. Build. Mater. 25 (2011) 38633868.